Feedstock Recycling and Pyrolysis of Waste Plastics

Feedstock Recycling
and Pyrolysis of Waste

Plastics:
Converting Waste Plastics into Diesel

and Other Fuels
Feedstock Recycling and Pyrolysis of Waste Plastics: Converting Waste Plastics into Diesel and Other Fuels Edited by
J. Scheirs and W. Kaminsky  2006 John Wiley & Sons, Ltd ISBN: 0-470-02152-7
Wiley Series in Polymer Science
Series Editor
John Scheirs
ExcelPlas
PO Box 2080
Edithvale, VIC 3196
Australia
scheirs.john@pacific.net.au
Modern Fluoropolymers
High Performance Polymers for Diverse Applications
Polymer Recycling
Science, Technology and Applications
Metallocene-based polyolefins
Preparations, Properties and Technology
Polymer–Clay Nanocomposites
Dendrimers and Other Dendritic Polymers
Modern Styrenic Polymers

Polystyrenes and Styrenic Copolymers
Modern Polyesters
Chemistry and Technology of Polyesters and Copolymers
Forthcoming Titles
Light Emitting Polymers
Environmentally Degradable Polymers

Feedstock Recycling
and Pyrolysis of Waste
Plastics:
Converting Waste Plastics into Diesel
and Other Fuels
Edited by
JOHN SCHEIRS
ExcelPlas Australia
and
WALTER KAMINSKY
University of Hamburg, Germany
WILEY SERIES IN POLYMER SCIENCE

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Library of Congress Cataloging-in-Publication Data:
Feedstock recycling and pyrolysis of waste plastics / editors, John

Scheirs, Walter Kaminsky.
p. cm. – (Wiley series in polymer science)
Includes bibliographical references and index.
ISBN-13: 978-0-470-02152-1 (cloth : alk. paper)
ISBN-10: 0-470-02152-7 (cloth : alk. paper)
1. Plastics–Recycling. 2. Pyrolysis. 3. Plastic scrap–Recycling. I.
Scheirs, John. II. Kaminsky, W. (Walter), 1941– III. Series.
TD798. F45 2006
668.4 192 – dc22
2005029094
British Library Cataloguing in Publication Data

A catalogue record for this book is available from the British Library
ISBN-13: 978-0-470-02152-1
ISBN-10: 0-470-02152-7
Typeset in 10/12pt Times by Laserwords Private Limited, Chennai, India

Printed and bound in Great Britain by Antony Rowe Ltd, Chippenham, Wiltshire
This book is printed on acid-free paper responsibly manufactured from sustainable forestry
in which at least two trees are planted for each one used for paper production.
Contents
Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xix
Series Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxiii
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxv
About the Editors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxix
I INTRODUCTION 1
1 Introduction to Feedstock Recycling of Plastics . . . . . . . . . . . . . 3

A. Buekens
Abbreviations 3
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3 Pyrolysis of Plastics and Rubber . . . . . . . . . . . . . . . . . . . . 6
3.1 Survey of Previous Work . . . . . . . . . . . . . . . . . . . . . 7
3.2 Products from Polymers . . . . . . . . . . . . . . . . . . . . . . 8
3.3 Hetero-atoms and Side Products . . . . . . . . . . . . . . . . 15
3.4 Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.5 Value of the Resulting Products . . . . . . . . . . . . . . . . . 20
4 Feedstock Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.1 Survey . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.2 Problems with Hetero-atoms . . . . . . . . . . . . . . . . . . . 23
4.3 Collection Systems . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.4 Logistics of Supply . . . . . . . . . . . . . . . . . . . . . . . . . 25
5 Some Feasible Processes . . . . . . . . . . . . . . . . . . . . . . . . . 27
5.1 Pilot and Industrial Plant Operation . . . . . . . . . . . . . . 27
5.2 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
6 Waste management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
6.1 Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
6.2 Plastics Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
6.3 Rubber Waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
6.4 Plastics Pyrolysis as a Waste Management Option . . . . 35
7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
vi CONTENTS
II CATALYTIC CRACKING 43
2 Acid-Catalyzed Cracking of Polyolefins: Primary Reaction

Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Robert L. White
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2 Polyethylene Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3 Polystyrene Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4 Hydrocracking Processes . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.1 PE-PtHZSM-5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.2 PE-PtHY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.3 PE-PtHMCM-41 . . . . . . . . . . . . . . . . . . . . . . . . . . 63
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3 Catalytic Upgrading of Plastic Wastes . . . . . . . . . . . . . . . . . . . 73

J. Aguado, D. P. Serrano and J. M. Escola
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
1.1 Catalytic versus Thermal Cracking . . . . . . . . . . . . . . . 74
1.2 Plastics Susceptible to Upgrading by Catalytic Cracking 77
1.3 Products Derived from the Catalytic Cracking . . . . . . . 78
2 Catalytic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2.1 Homogeneous Catalysts . . . . . . . . . . . . . . . . . . . . . . 79
2.2 Heterogeneous Catalysts . . . . . . . . . . . . . . . . . . . . . 79
3 Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.1 Batch/Semi-batch Reactors . . . . . . . . . . . . . . . . . . . . 86
3.2 Fixed-bed Reactors . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.3 Fluidized-bed Reactors . . . . . . . . . . . . . . . . . . . . . . 88
3.4 Spouted-bed Reactors . . . . . . . . . . . . . . . . . . . . . . . 90
3.5 Screw Kiln Reactors . . . . . . . . . . . . . . . . . . . . . . . . 91
4 Influence of the Main Operation Variables . . . . . . . . . . . . . . 92
4.1 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.2 Catalyst Amount . . . . . . . . . . . . . . . . . . . . . . . . . . 94
4.3 Time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.4 Plastics Waste Composition . . . . . . . . . . . . . . . . . . . 95
5 Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
5.1 Direct Catalytic Cracking . . . . . . . . . . . . . . . . . . . . . 97
5.2 Thermal Degradation and Subsequent Catalytic Upgrading 99
6 Related Technologies: Coprocessing . . . . . . . . . . . . . . . . . . 101
6.1 Coal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
6.2 Petroleum Cuts . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
6.3 Solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
7 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
CONTENTS vii
4 Thermal and Catalytic Conversion of Polyolefins . . . . . . . . . . . 111
Jerzy Walendziewski
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
2 General Scheme of Waste Polyolefin Processing . . . . . . . . . . 112
3 Waste Plastics Suitable for Cracking and Pyrolysis . . . . . . . . 113
4 Mechanism of Cracking Processes . . . . . . . . . . . . . . . . . . . 113
5 Waste Plastics Processing . . . . . . . . . . . . . . . . . . . . . . . . . 115
5.1 Catalytic and Thermal Cracking Processes: Typical
Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
5.2 Coprocessing of Waste Plastics with Other Raw Materials 119
6 Reactor Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
7 Pilot Plants and Commercial Plants . . . . . . . . . . . . . . . . . . 122
8 Economic Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
5 Thermal and Catalytic Degradation of Waste HDPE . . . . . . . . . 129

Kyong-Hwan Lee
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
2 Theory of Plastics Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . 130
3 Process Flow Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
4 Total Mass Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
5 Effect of Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
6 Effect of Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
7 Various Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
8 Effect of Addition of Other Thermoplastics . . . . . . . . . . . . . 149
9 Fractional Distillation of Products . . . . . . . . . . . . . . . . . . . 153
10 Properties of Liquid Product . . . . . . . . . . . . . . . . . . . . . . . 155
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
6 Development of a Process for the Continuous Conversion of

Waste Plastics Mixtures to Fuel . . . . . . . . . . . . . . . . . . . . . . . 161
Takao Masuda and Teruoki Tago
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
2 Recovery of Heavy Oil from Waste Plastic . . . . . . . . . . . . . 162
2.1 Degradation of Various Plastics . . . . . . . . . . . . . . . . . 162
2.2 Catalytic Cracking of Waste Plastics Without Residue . . 165
2.3 Continuous Degradation of Waste Plastics Mixtures for
the Recovery of Heavy Oil . . . . . . . . . . . . . . . . . . . . 168
3 Upgrading of Waste-plastics-derived Heavy Oil Over Catalysts 172
3.1 Catalytic Cracking of Heavy Oil over Solid-acid Catalysts 172
3.2 Production of High-quality Gasoline over REY Zeolites . 175
3.3 Kinetics of the Catalytic Cracking of Heavy Oil over
REY Zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
3.4 Usage of Steam as a Carrier Gas . . . . . . . . . . . . . . . . 183
viii CONTENTS
4 Continuous Production of Fuels from Waste Plastics . . . . . . . 188

4.1 Continuous Production of Fuels . . . . . . . . . . . . . . . . . 188
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
7 Catalytic Degradation of Plastic Waste to Fuel over Microporous

Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
George Manos
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
2 Operation Modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
3 Zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
4 Polymer-to-catalyst Ratio . . . . . . . . . . . . . . . . . . . . . . . . . 196
5 Initial Degradation Mechanism . . . . . . . . . . . . . . . . . . . . . 199
6 Product Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
6.1 Conversion, Liquid Yield, Coke Content . . . . . . . . . . . 202
6.2 Characterization of Gaseous/Liquid Products . . . . . . . . 203
6.3 Boiling Point Distribution of Liquid Fraction . . . . . . . . 203
7 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
8 Liquefaction of Municipal Waste Plastics over Acidic and

Nonacidic Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
Jale Yanik and Tamer Karayildirim
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
2 Catalytic Liquefaction of MWP . . . . . . . . . . . . . . . . . . . . . 210
2.1 Liquid Phase Contact . . . . . . . . . . . . . . . . . . . . . . . 210
2.2 Thermal Cracking plus Catalytic Upgrading . . . . . . . . . 211
2.3 Co-processing of MWP . . . . . . . . . . . . . . . . . . . . . . 216
3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
9 Kinetic Model of the Chemical and Catalytic Recycling of Waste

Polyethylene into Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
Norbert Miskolczi
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
2 Reaction Kinetics of Degradation . . . . . . . . . . . . . . . . . . . 226
2.1 Reaction Mechanism . . . . . . . . . . . . . . . . . . . . . . . . 228
3 Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.1 Monofunctional Catalysts . . . . . . . . . . . . . . . . . . . . . 239
3.2 Bifunctional Catalysts . . . . . . . . . . . . . . . . . . . . . . . 241
3.3 Solid Alkalis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
CONTENTS ix
III QUALITY OF FUELS 249
10 Production of Gaseous and Liquid Fuels by Pyrolysis and

Gasification of Plastics: Technological Approach . . . . . . . . . . . . 251
C. Gisèle Jung and André Fontana
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
2 Literature Review on Plastics Carbonization . . . . . . . . . . . . 254
2.1 Polyethylene (PE) . . . . . . . . . . . . . . . . . . . . . . . . . . 255
2.2 Polypropylene (PP) . . . . . . . . . . . . . . . . . . . . . . . . . 258
2.3 Polystyrene (PS) . . . . . . . . . . . . . . . . . . . . . . . . . . 262
2.4 Polyvinyl Chloride (PVC) . . . . . . . . . . . . . . . . . . . . 264
2.5 Polyethylene Terephthalate (PET) . . . . . . . . . . . . . . . 266
2.6 Plastic Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
3 Technological Approach . . . . . . . . . . . . . . . . . . . . . . . . . 271
3.1 Predictive Carbonization Model . . . . . . . . . . . . . . . . . 271
3.2 Scale-up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 272
3.3 Pyrolysis Technologies . . . . . . . . . . . . . . . . . . . . . . 272
3.4 Gasification Technologies . . . . . . . . . . . . . . . . . . . . . 275
3.5 Fuel Valorization . . . . . . . . . . . . . . . . . . . . . . . . . . 278
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
11 Yield and Composition of Gases and Oils/Waxes from the

Feedstock Recycling of Waste Plastic . . . . . . . . . . . . . . . . . . . . 285
Paul T. Williams
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
2 Feedstock Recycling of Plastics . . . . . . . . . . . . . . . . . . . . . 288
2.1 Product Yield . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
2.2 Gas Composition . . . . . . . . . . . . . . . . . . . . . . . . . . 292
2.3 Oil/Wax Composition from the Feedstock Recycling of
Single Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
12 Composition of Liquid Fuels Derived from the Pyrolysis of

Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
Marianne Blazsó
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
2 Experimental Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
3 Chemical Composition of Pyrolysis Liquids . . . . . . . . . . . . . 317
3.1 Relation of Major Oil Characteristics and Chemical
Features of Component Compounds . . . . . . . . . . . . . . 317
3.2 Thermal Decomposition Reactions of Polymers . . . . . . 318
4 Pyrolysis Products of Packaging Waste Plastics . . . . . . . . . . 321
4.1 Polyolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322
x CONTENTS
4.2 Vinyl Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . 326

4.3 Polyesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
5 Pyrolysis Products of Automotive Waste Plastics . . . . . . . . . 329
5.1 Styrene Copolymers . . . . . . . . . . . . . . . . . . . . . . . . 329
5.2 Rubber Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
5.3 Polyamides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
5.4 Polyurethanes (PU) . . . . . . . . . . . . . . . . . . . . . . . . . 335
6 Pyrolysis Products of Electronic Waste Plastics . . . . . . . . . . 337
6.1 Polycarbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
6.2 Epoxy Resin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
6.3 Phenol–Formaldehyde Resin . . . . . . . . . . . . . . . . . . 340
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 341
13 Production of Premium Oil Products from Waste Plastic by

Pyrolysis and Hydroprocessing . . . . . . . . . . . . . . . . . . . . . . . . 345
S.J. Miller, N. Shah and G.P. Huffman
1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 345
2 Conversion of Waste Plastics to Transportation Fuels . . . . . . 346
3 Direct Liquefaction and Co-processing of Waste Plastic . . . . . 346
4 Pyrolysis and Hydroprocessing . . . . . . . . . . . . . . . . . . . . . 347
5 Feasibility Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
6 Conversion of Waste Plastic to Lubricating Base Oil . . . . . . . 351
7 Lubricating Base Oils from Fischer–Tropsch Wax and Waste
Plastic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
8 One-gallon-per-day Pilot Plant . . . . . . . . . . . . . . . . . . . . . 354
8.1 Hydroprocessing . . . . . . . . . . . . . . . . . . . . . . . . . . 355
8.2 Pyrolysis Pilot Plant Results for Various Feedstocks . . . 355
9 Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . . . . 358
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
14 The Conversion of Waste Plastics/Petroleum Residue Mixtures to

Transportation Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
Mohammad Farhat Ali and Mohammad Nahid Siddiqui
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363
2 The Characteristics and Chemical Structure of Plastics . . . . . 364
3 The Characteristics and Chemical Properties of Petroleum
Residue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
4 Technologies for Petroleum Residue Upgrading . . . . . . . . . . 365
5 Technologies for Tertiary Recycling of Mixed Plastic Waste
(MPW) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 366
5.1 Feedstock Recycling of MPW with Low PVC Content . 367
6 Coprocessing for Fuel from Mixed Plastic Waste . . . . . . . . . 369
7 Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
7.1 Reactor Types Used for Pyrolysis . . . . . . . . . . . . . . . 375
7.2 Chemical Products of Pyrolysis . . . . . . . . . . . . . . . . . 375
CONTENTS xi
8 Environmental Impacts of Recycling of Waste Plastics . . . . . 376
9 Economic Evaluation . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
10 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 378
IV REACTOR TYPES 381
15 Overview of Commercial Pyrolysis Processes for Waste

Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
John Scheirs
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
1.1 Advantages of Pyrolysis . . . . . . . . . . . . . . . . . . . . . 385
1.2 Thermal Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . 385
1.3 Catalytic Cracking . . . . . . . . . . . . . . . . . . . . . . . . . 386
2 Feedstock Options . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 386
2.1 Polyethylene (PE) . . . . . . . . . . . . . . . . . . . . . . . . . . 387
2.2 Polypropylene (PP) . . . . . . . . . . . . . . . . . . . . . . . . . 387
2.3 Polystyrene (PS) Pyrolysis . . . . . . . . . . . . . . . . . . . . 388
2.4 PET . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
2.5 PVC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
2.6 Halogenated Polymers . . . . . . . . . . . . . . . . . . . . . . . 391
2.7 Plastic Feedstock Specification . . . . . . . . . . . . . . . . . 391
3 Operational Considerations . . . . . . . . . . . . . . . . . . . . . . . . 392
3.1 Preventing Coking . . . . . . . . . . . . . . . . . . . . . . . . . 392
3.2 Preventing Corrosion . . . . . . . . . . . . . . . . . . . . . . . . 393
3.3 Tank/Kettle Reactors . . . . . . . . . . . . . . . . . . . . . . . . 393
3.4 Reflux . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
3.5 Problems with Batch Pyrolysis . . . . . . . . . . . . . . . . . 393
3.6 Continuous Systems . . . . . . . . . . . . . . . . . . . . . . . . 394
3.7 Fluidized-bed Processes . . . . . . . . . . . . . . . . . . . . . . 394
3.8 Fluid-bed Coking . . . . . . . . . . . . . . . . . . . . . . . . . . 394
3.9 Fluid Catalytic Cracking (FCC) . . . . . . . . . . . . . . . . . 394
3.10 Catalytic Cracking . . . . . . . . . . . . . . . . . . . . . . . . . 394
4 Engineering Design Aspects . . . . . . . . . . . . . . . . . . . . . . . 395
4.1 Pyrolysis Chamber Design . . . . . . . . . . . . . . . . . . . . 395
4.2 Pyrolysis Vessel Construction . . . . . . . . . . . . . . . . . . 396
4.3 Agitator Speed . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
4.4 Burner Characteristics . . . . . . . . . . . . . . . . . . . . . . . 396
4.5 Inert Purge Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
4.6 Distillation Columns . . . . . . . . . . . . . . . . . . . . . . . . 397
4.7 Centrifuge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
4.8 Scrubber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
4.9 Dechlorination . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
4.10 Hydrotreating . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
4.11 Catalytic Dewaxing and Isomerization Dewaxing . . . . . 398
xii CONTENTS
5 Quality of the Output Fuels . . . . . . . . . . . . . . . . . . . . . . . 399

5.1 Unsaturation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
5.2 Carbon Residue in the Fuel . . . . . . . . . . . . . . . . . . . 399
5.3 Low-temperature Properties . . . . . . . . . . . . . . . . . . . 399
5.4 Fuel Instability . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400
5.5 Diesel Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
5.6 Storage Stability of Plastic-derived Diesel Fuel . . . . . . 401
5.7 Characteristics of the Solid Residue . . . . . . . . . . . . . . 403
5.8 Gaseous Emissions . . . . . . . . . . . . . . . . . . . . . . . . . 403
6 Catalytic Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
6.1 Catalyst Activity and Selectivity . . . . . . . . . . . . . . . . 404
6.2 Layered Clay Catalysts . . . . . . . . . . . . . . . . . . . . . . 405
6.3 External Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . 406
6.4 PS Catalytic Cracking . . . . . . . . . . . . . . . . . . . . . . . 406
6.5 Catalytic Dechlorination . . . . . . . . . . . . . . . . . . . . . 407
7 Commercial Plastic Pyrolysis Processes . . . . . . . . . . . . . . . 407
7.1 Thermofuel Process . . . . . . . . . . . . . . . . . . . . . . . 407
7.2 Smuda Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 414
7.3 Polymer-Engineering Process (Catalytic
Depolymerization) . . . . . . . . . . . . . . . . . . . . . . . . . 418
7.4 Royco Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
7.5 Reentech Process . . . . . . . . . . . . . . . . . . . . . . . . . . 423
7.6 Hitachi Process . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
7.7 Chiyoda Process . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
7.8 Blowdec Process . . . . . . . . . . . . . . . . . . . . . . . . . . 429
7.9 Conrad Process . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
7.10 Other Processes with Separate Catalyst Beds . . . . . . . . 431
8 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
16 Fluidized Bed Pyrolysis of Plastic Wastes . . . . . . . . . . . . . . . . . 435

Umberto Arena and Maria Laura Mastellone
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
1.1 Fluidized-bed Technology for Waste Thermal Treatments:
The Key Role of Hydrodynamics . . . . . . . . . . . . . . . 435
1.2 From Plastic Waste to Feedstocks and Energy by Means
of Fluidized-bed Pyrolysis . . . . . . . . . . . . . . . . . . . . 437
2 Different Stages in the Fluidized-bed Pyrolysis of a Plastic Waste 444
2.1 An Overview of Physical and Chemical Phenomena . . . 444
2.2 The Polymer Degradation Process . . . . . . . . . . . . . . . 452
3 Operability Range of Fluidized-bed Pyrolysers . . . . . . . . . . . 453
3.1 The Phenomenology of Bed Defluidization . . . . . . . . . 453
3.2 Predictive Defluidization Models and Operability Maps . 454
4 The Effect of the Main Process Variables on the Yield and
Composition of Pyrolysis Products . . . . . . . . . . . . . . . . . . . 456
CONTENTS xiii
4.1 Fluidized-bed Pyrolysis of Monopolymeric Waste . . . . . 462
4.2 Fluidized-bed Pyrolysis of Multipolymeric Waste . . . . . 464
4.3 Fluidized-bed Pyrolysis of Other Polymeric Wastes . . . . 466
5 Operating Experience with Industrial Fluidized-bed Pyrolysers 467
5.1 The BP Chemicals Polymer Cracking Process . . . . . . . 467
5.2 The Akzo Process . . . . . . . . . . . . . . . . . . . . . . . . . 468
5.3 The Ebara TwinRec Process . . . . . . . . . . . . . . . . . . . 469
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471
17 The Hamburg Fluidized-bed Pyrolysis Process to Recycle

Polymer Wastes and Tires . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
Walter Kaminsky
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 475
2 Pilot Plant Description . . . . . . . . . . . . . . . . . . . . . . . . . . . 476
2.1 Pyrolysis of Whole Tires . . . . . . . . . . . . . . . . . . . . . 480
3 Pyrolysis Product Composition . . . . . . . . . . . . . . . . . . . . . 482
3.1 Industrial Pilot Plants . . . . . . . . . . . . . . . . . . . . . . . 488
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 490
18 Liquefaction of PVC Mixed Plastics . . . . . . . . . . . . . . . . . . . . 493

Thallada Bhaskar and Yusaku Sakata
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 493
2 Experimental and Analytical Methods . . . . . . . . . . . . . . . . 496
2.1 Preparation of Iron and Calcium Composites . . . . . . . . 496
2.2 Experimental Procedure . . . . . . . . . . . . . . . . . . . . . . 496
2.3 Analysis procedure . . . . . . . . . . . . . . . . . . . . . . . . . 497
2.4 HCl Adsorption Capacity . . . . . . . . . . . . . . . . . . . . . 498
3 Fundamental Studies on the Decomposition of PVC . . . . . . . 498
3.1 Product Distribution and Mechanism of PVC
Decomposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
3.2 Degradation of PVC – Polymer Mixtures . . . . . . . . . . 501
4 Liquefaction with Commingled Plastics and Dechlorination . . 502
4.1 Pyrolysis of PE, PP or PS with PVC . . . . . . . . . . . . . 502
4.2 Thermal Degradation of PP/PVC by Solid Acid Catalysts
and Dechlorination with Iron Oxides . . . . . . . . . . . . . 505
4.3 Thermal Degradation of PE Mixed with PET . . . . . . . . 508
4.4 Laboratory Evaluation of Various Carbon Composites as
HCl Sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
4.5 Liquefaction of PVC Mixed Plastics and Dechlorination
with Ca-C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
4.6 Liquefaction of PP/PE/PS/PVC with HIPS-Br and
Dehalogenation with Ca-C . . . . . . . . . . . . . . . . . . . . 518
4.7 Liquefaction of Real Municipal Waste Plastics . . . . . . . 521
5 Pilot Plant Scale Studies for the Liquefaction of PVC Mixed
Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 523
xiv CONTENTS
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
19 Liquid Fuel from Plastic Wastes Using Extrusion–Rotary Kiln

Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 531
Sam Behzadi and Mohammed Farid
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 531
2 Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 532
2.1 Industrial-scale Pyrolysis Processes . . . . . . . . . . . . . . 533
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547
20 Rotary Kiln Pyrolysis of Polymers Containing Heteroatoms . . . . 549

Andreas Hornung and Helmut Seifert
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
2 Technical Variations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
2.1 Conrad Process . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
2.2 Double Rotary Kiln Pyrolysis . . . . . . . . . . . . . . . . . . 550
2.3 Pyrolysis of Tires: Faulkner System . . . . . . . . . . . . . . 550
2.4 VTA Pyrolysis: A Rotary Kiln for the Treatment of
Petrochemical Residues and Hydrocarbon Residues . . . . 551
3 State of the Art of Rotary Kiln Technology . . . . . . . . . . . . . 551
3.1 Haloclean Gas-tight Rotary Kiln . . . . . . . . . . . . . . . . 552
4 Rotary Kiln Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . 553
5 Treatment of Thermoplastics: PVC . . . . . . . . . . . . . . . . . . 553
6 Pyrolysis of Mono Fractions: Polymethylmethacrylate
PMMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 556
7 Treatment of Shredder Light Fractions/Shredder Residues . . . 557
8 Treatment of Electronic Scrap . . . . . . . . . . . . . . . . . . . . . . 557
8.1 The European Dimension . . . . . . . . . . . . . . . . . . . . . 558
8.2 The Pyrocom Rotary Kiln . . . . . . . . . . . . . . . . . . . . 558
8.3 The Haloclean Rotary Kiln Process . . . . . . . . . . . . . . 559
9 Dehalogenation of Pyrolysis Oils . . . . . . . . . . . . . . . . . . . . 562
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
21 Microwave Pyrolysis of Plastic Wastes . . . . . . . . . . . . . . . . . . . 569

C. Ludlow-Palafox and H.A. Chase
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 569
2 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 570
2.1 Microwave Heating . . . . . . . . . . . . . . . . . . . . . . . . 570
2.2 Microwave Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . 572
3 Microwave Pyrolysis of Plastics in the Scientific Literature . . 575
3.1 Microwave Pyrolysis Equipment . . . . . . . . . . . . . . . . 575
3.2 Results from the Microwave Pyrolysis of Plastics . . . . . 577
3.3 Microwave Effect in Microwave Pyrolysis . . . . . . . . . 581
CONTENTS xv
4 Microwave Pyrolysis in the Commercial Literature . . . . . . . . 582
4.1 Patents History and Comparison with Scientific Literature 582
4.2 Companies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
22 Continuous Thermal Process for Cracking Polyolefin Wastes to

Produce Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595
Jean Dispons
1 Background . . . . . . . . . . . . . . . . . . . . . . . ....... . . . . 595
2 Introduction . . . . . . . . . . . . . . . . . . . . . . . ....... . . . . 596
3 The Two Principal Phases of Polyolefin Waste Cracking . . . . 597
4 Thermal Valorization of Polyolefin Wastes . . ....... . . . . 598
5 Continuous Feeding of the Cracking Reactors ....... . . . . 598
6 Heating Methods . . . . . . . . . . . . . . . . . . . ....... . . . . 599
23 Waste Plastic Pyrolysis in Free-Fall Reactors . . . . . . . . . . . . . . 605

Ali Y. Bilgesü, M. Çetin Koçak, and Ali Karaduman
1 Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
2 Previous Pyrolysis Work . . . . . . . . . . . . . . . . . . . . . . . . . 605
3 Design Aspects of FFR to be Used in Pyrolysis . . . . . . . . . . 609
4 A Free-Fall Reactor System for Flash Pyrolysis . . . . . . . . . . 610
4.1 Set-up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
4.2 Experimental Procedure . . . . . . . . . . . . . . . . . . . . . . 611
5 Plastic Waste Recycling . . . . . . . . . . . . . . . . . . . . . . . . . . 612
6 Results from Ateklab Free-Fall Reactor . . . . . . . . . . . . . . . 613
6.1 LDPE Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613
6.1 Polystyrene Results . . . . . . . . . . . . . . . . . . . . . . . . . 617
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621
V MONOMER RECOVERY 625
24 Monomer Recovery of Plastic Waste in a Fluidized Bed Process . 627

Walter Kaminsky
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 627
2 Fluidized-bed Process . . . . . . . . . . . . . . . . . . . . . . . . . . . 628
3 Pyrolysis of PMMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
3.1 Pure PMMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 629
3.2 Filled PMMA . . . . . . . . . . . . . . . . . . . . . . . . . . . . 631
4 Pyrolysis of Polystyrene . . . . . . . . . . . . . . . . . . . . . . . . . 635
5 Pyrolysis of PTFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
xvi CONTENTS
25 Feedstock Recycling of PET . . . . . . . . . . . . . . . . . . . . . . . . . . 641

Toshiaki Yoshioka and Guido Grause
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641
2 Physical Recycling (Mechanical Recycling) . . . . . . . . . . . . . 643
3 Solvolysis (Chemolysis) . . . . . . . . . . . . . . . . . . . . . . . . . . 643
3.1 Glycolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
3.2 Methanolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
3.3 Hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647
3.4 Other Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . 649
4 Pyrolysis and Other Hot Processes . . . . . . . . . . . . . . . . . . . 649
4.1 Decomposition Mechanism of PET . . . . . . . . . . . . . . 650
4.2 Pyrolysis Processes . . . . . . . . . . . . . . . . . . . . . . . . . 653
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 659
VI ASIAN DEVELOPMENTS 663
26 The Liquefaction of Plastic Containers and Packaging

in Japan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
A. Okuwaki, T. Yoshioka, M. Asai, H. Tachibana, K. Wakai, K. Tada
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 665
1.1 Brief History of Plastics Liquefaction in Japan . . . . . . . 665
1.2 The Law for Promotion of Sorted Collection and
Recycling of Containers and Packaging . . . . . . . . . . . 666
1.3 Feedstock Recycling of Plastic Containers and
Packaging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 667
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
2 Niigata Waste Plastic Liquefaction Process . . . . . . . . . . . . . 670
2.1 Plant Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
2.2 Process Description . . . . . . . . . . . . . . . . . . . . . . . . 671
2.3 Quality of Waste Plastics . . . . . . . . . . . . . . . . . . . . . 673
2.4 Properties of Outputs . . . . . . . . . . . . . . . . . . . . . . . 673
2.5 Material Balance and Consumption Figures . . . . . . . . . 675
2.6 Heat Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
2.7 Application of the Outputs . . . . . . . . . . . . . . . . . . . . 676
2.8 Environmental Measurement . . . . . . . . . . . . . . . . . . . 678
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
3 Sapporo Waste Plastics Liquefaction Process . . . . . . . . . . . . 678
3.1 Plant Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
3.3 Quality of Waste Plastics . . . . . . . . . . . . . . . . . . . . . 682
3.4 Properties of Outputs . . . . . . . . . . . . . . . . . . . . . . . 684
3.5 Material Balance and Consumption Figures . . . . . . . . . 687
3.6 Heat Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 688
3.7 Application of the Outputs . . . . . . . . . . . . . . . . . . . . 691
CONTENTS xvii
3.8 Environmental Aspects . . . . . . . . . . . . . . . . . . . . . . 692
3.9 Characteristics of the Plant . . . . . . . . . . . . . . . . . . . . 693
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 695
4 Mikasa Waste Plastic Liquefaction Plant . . . . . . . . . . . . . . . 695
4.1 Plant Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 695
4.3 Quality and Application of Reclaimed Oil . . . . . . . . . . 698
4.4 Material Balance . . . . . . . . . . . . . . . . . . . . . . . . . . 698
4.5 High Energy Collection . . . . . . . . . . . . . . . . . . . . . . 700
4.6 Characteristics of the Plant . . . . . . . . . . . . . . . . . . . . 700
4.7 Application of the System . . . . . . . . . . . . . . . . . . . . 702
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 702
5 The Scope of Liquefaction in Japan . . . . . . . . . . . . . . . . . . 702
5.1 Present Status of Feedstock Recycling . . . . . . . . . . . . 702
5.2 Scope for Liquefaction . . . . . . . . . . . . . . . . . . . . . . 706
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 708
27 Process and Equipment for Conversions of Waste Plastics into

Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 709
Alka Zadgaonkar
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 709
2 Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 709
2.1 Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 709
2.2 Plastics Suitable for Pyrolysis . . . . . . . . . . . . . . . . . . 710
3 Pyrolysis: Mode of Operation and Apparatus . . . . . . . . . . . . 710
3.1 Batch Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 710
3.2 Types of Pyrolyzers . . . . . . . . . . . . . . . . . . . . . . . . 711
4 Pyrolysis: Thermal Cracking/Noncatalytic Cracking . . . . . . . 712
4.1 Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 712
4.2 Process Mechanism . . . . . . . . . . . . . . . . . . . . . . . . 713
4.3 Degradation of Polymers . . . . . . . . . . . . . . . . . . . . . 713
5 Pyrolysis Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
5.1 Role and Effect of Catalyst . . . . . . . . . . . . . . . . . . . 715
5.2 Properties of Catalyst . . . . . . . . . . . . . . . . . . . . . . . 716
6 Pyrolysis: Output Characteristics . . . . . . . . . . . . . . . . . . . . 719
6.1 Effect of Temperature on Pyrolysis Products . . . . . . . . 719
6.2 By-products of Pyrolysis . . . . . . . . . . . . . . . . . . . . . 719
7 Pyrolysis of Heteroatom Polymers . . . . . . . . . . . . . . . . . . . 720
7.1 Pyrolysis of PVC . . . . . . . . . . . . . . . . . . . . . . . . . . 720
7.2 Pyrolysis of ABS . . . . . . . . . . . . . . . . . . . . . . . . . . 721
8 Refinement of Pyrolysis Output Products . . . . . . . . . . . . . . 721
8.1 Removal of Unsaturation and Olefinic Products . . . . . . 721
8.2 Various Examples of Pyrolysis . . . . . . . . . . . . . . . . . 722
8.3 Comparison of Pyrolysis of PE and PP . . . . . . . . . . . . 724
9 Recently Developed Innovative Technologies . . . . . . . . . . . . 724
xviii CONTENTS
9.1 Thermofuel of Waste Plastic by Ozmotech . . . . . . . . . 724

9.2 Conversion of Waste Plastics to Fuels: Zadgaonkar’s
Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 724
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 728
28 Converting Waste Plastics into Liquid Fuel by Pyrolysis:

Developments in China . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 729
Yuan Xingzhong
1 Progress in Converting Waste Plastics into Liquid Fuel by
Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 729
2 Theory of Plastics Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . 730
2.1 Mass Balance for the Pyrolysis Process . . . . . . . . . . . 730
2.2 Energy Balance for the Pyrolysis Process . . . . . . . . . . 732
2.3 Mechanism of Plastics Pyrolysis . . . . . . . . . . . . . . . . 734
2.4 Methods for Plastics Pyrolysis . . . . . . . . . . . . . . . . . 735
3 Process of Plastics Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . 738
3.1 Veba Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
3.2 BP Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 738
3.3 Fuji Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
3.4 BASF Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
3.5 Hamburg University Process . . . . . . . . . . . . . . . . . . . 741
3.6 Hunan University Process . . . . . . . . . . . . . . . . . . . . 742
3.7 United Carbon Process . . . . . . . . . . . . . . . . . . . . . . 743
3.8 Likun Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . 743
3.9 Other Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . 744
4 Main Factors in Plastics Pyrolysis . . . . . . . . . . . . . . . . . . . 744
4.1 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 744
4.2 Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 746
5 Pyrolysis of PVC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 747
6 Catalytic Reforming of Cracked Gas . . . . . . . . . . . . . . . . . 748
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 750
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757
Contributors
José Aguado, Thallada Bhaskar,

Rey Juan Carlos University, Yusaku Sakata Laboratory,
ESCET, Department of Applied Chemistry,
c/Tulipán s/n, Faculty of Engineering,
28933 Móstoles, Spain Okayama University,
3-1-1 Tsushima Naka,
700–8530 Okayama, Japan
Mohammad Farhat Ali,
Department of Chemistry,
King Fahd University of Petroleum and Ali Y. Bilgesü,
Minerals, Chemical Engineering Department,
Dhahran 31261, Engineering Faculty,
Saudi Arabia Ankara University,
Tando an 06100 Ankara, LK, Turkey
Umberto Arena,
M. Blazsó,
Department of Environmental Sciences,
Institute of Materials and Environmental
University of Naples II,
Chemistry,
Via Vivaldi 43,
Chemical Research Center Hungarian
81100 Caserta, Italy
Academy of Sciences,
Pf. 17, H-1525 Budapest,
Masao Asai, Pusztaszeri ut́ 58–67,
Rekisei Kouyu Co. Ltd, H-1025 Budapest, Hungary
Niigata Plastic Liquefaction Center,
3-1 Heiwa, Alfons Buekens,
Niigata, Japan Vrije Universiteit Brussel (V.U.B.),
Domstraat 7,
Sam Behzadi, 1602 Vlezenbeek, Belgium
Department of Chemical and Materials
Engineering, H.A. Chase,
The University of Auckland, Department of Chemical Engineering,
Private Bag 92019, University of Cambridge,
Auckland, New Zealand New Museums Site,
xx CONTRIBUTORS
Pembroke Street, P.O. Box 3640,
Cambridge CB2 3RA, UK 76021 Karlsruhe, Germany
Jean Dispons, G.P. Huffman,

Chemical Engineering Adviser University of Kentucky,
France Consortium for Fossil Fuel Science,
107 Whalen Building,
533 S. Limestone St,
J.M. Escola,
Lexington,
Rey Juan Carlos University,
KY 40506-0043, USA
ESCET,
c/Tulipán s/n,
28933 Móstoles, Spain C. Gisèle Jung,
Chercheur de l’Université,
Université Libre de Bruxelles,
Mohammed Farid, Solvay Business School – Centre Emile
Department of Chemical and Materials Bernheim,
Engineering The University of Auckland, Service de Chimie Industrielle,
Private Bag 92019, 50, Av.F.D.Roosevelt,
Auckland, New Zealand CP165/63, 1050 Bruxelles, Belgium
André Fontana, Walter Kaminsky,

Université Libre de Bruxelles, Institute for Technical and
Solvay Business School – Centre Emile Macromolecular Chemistry,
Bernheim, University of Hamburg,
50, Av. F.D. Roosevelt, Bundesstr. 45,
CP 145/1, 1050 Brussel, Belgium 20146 Hamburg, Germany
Guido Grause, Ali Karaduman,

Laboratory for Chemical Process Ankara University,
Engineering, Engineering Faculty,
Materials Process Engineering, Chemical Engineering Department,
Division of Materials Science and Tando an 06100 Ankara, LK, Turkey
Engineering,
Graduate School of Engineering, Çetin Koçak
Hokkaido University, Ankara University, Engineering Faculty,
N13 W8 Kita-ku, Chemical Engineering Department,
Sapporo 060–8628, Japan Tando an 06100 Ankara, Turkey
Andreas Hornung, Kyong-Hwan Lee,

Forschungszentrum Karlsruhe GmbH, Clean Energy Research Department,
Institut für Technische Chemie, Korea Institute of Energy Research
Thermische (KIER),
Abfallbehandlung – ITC-TAB, 71-2 Jang dong,
Hermann-von-Helmholtz-Platz 1, Yusong ku,
76344 Eggenstein-Leopoldshafen, Daejeon 305–343, Korea
CONTRIBUTORS xxi
Carlos Ludlow-Palafox, 31-9 Hagurodai,
Department of Chemical Engineering, Taihaku-ku,
University of Cambridge, Sendai 982-0817, Japan
New Museums Site,
Pembroke Street,
Cambridge CB2 3RA, UK Yusaku Sakata,
Department of Applied Chemistry,
Faculty of Engineering,
George Manos,
Okayama University,
Department of Chemical Engineering,
700–8530 Okayama, Japan
University College London,
Torrington Place,
London WC1E 7JE, UK John Scheirs,
ExcelPlas Polymer Technology,
Maria Laura Mastellone, PO Box 2080,
Department of Environmental Sciences, Edithvale,
University of Naples II, VIC 3196, Australia
Via Vivaldi 43,
81100 Caserta, Italy
Helmut Seifert,
ITC-TAB,
Takao Masuda,
Forschungszentrum Karlsruhe
Laboratory for Chemical Process
Hermann-von-Helmholtz-Platz 1,
Engineering,
76344 Eggenstein-Leopoldshafen,
Materials Process Engineering,
Germany
Division of Materials Science and
Engineering,
Graduate School of Engineering, D.P. Serrano,
Hokkaido University, Rey Juan Carlos University,
N13 W8 Kita-ku, ESCET,
Sapporo 060–8628, Japan c/Tulipán s/n,
Móstoles, Spain
S.J. Miller,
Chevron Texaco,
N. Shah,
100 Chevron Way,
University of Kentucky,
Richmond,
Consortium for Fossil Fuel Liquefaction,
CA 94802, USA
107 Whalen Building,
533 S. Limestone st,
Norbert Miskolczi,
Lexington,
University of Veszprém,
KY 40506–0043, USA
Department of Hydrocarbon and Coal
Processing,
Egyetem u. 10, Mohammad Nahid Siddiqui,
Veszprem, Department of Chemistry,
H-8200, Hungary King Fahd University of Petroleum and
Minerals,
Akitsugu Okuwaki, KFUPM,
Tohoku University, Dhahran 31261, Saudi Arabia
xxii CONTRIBUTORS
Hideaki Tachibana, Paul T. Williams,
2879-52 Kikuma, Energy and Resources Research Institute,
Ichihara, Houldsworth Building,
Chiba 290-0007, Japan The University of Leeds,
Leeds LS2 9JT, UK
Kazuhiko Tada,
Kubota Corporation, Yuan Xingzhong,
3-1-3 Muromachi, Department of Environmental Science
Nihonbashi, and Engineering,
Chuo-ku, Hunan University,
Tokyo 103–8310, Japan Changsha,
Hunan Province,
Teruoki Tago, 410082, P.R. China
Division of Materials Science and
Engineering, Jale Yanik,
Graduate School of Engineering, Ege University,
Hokkaido University, Faculty of Science,
N13 W8 Kita-Ku, Chemistry Department,
Sapporo 060–8628, Japan 35100 Bornova/Izmir, Turkey
Keiji Wakai, Toshiaki Yoshioka,

Sapporo Plastics Recycling Co. Ltd, Graduate School of Environmental
45–57 Nakanuma-chou, Studies,
Higashi-Ku, Tohoku University,
Sapporo 007–0890, Japan Aramaki Aza Aoba 6-6-07,
Aoba-ku,
Jerzy Walendziewski, Sendai 980–8579, Japan
Institute of Chemistry and Technology of
Petroleum and Coal, Alka Zadgaonkar,
Technical University of Wroclaw, Department of Applied Chemistry,
ul. Gdańska 7/9, G.H. Raisoni College of Engineering,
50–344 Wroclaw, Poland 9 Buty Layout,
RPTS Road,
Robert L. White, Laxmi Nagar,
Department of Chemistry and Nagpur 440016, India
Biochemistry,
University of Oklahoma,
Norman,
OK 73019, USA
Series Preface
The Wiley Series in Polymer Science aims to cover topics in polymer science where sig-
nificant advances have been made over the past decade. Key features of the series will be
developing areas and new frontiers in polymer science and technology. Emerging fields
with strong growth potential for the twenty-first century such as nanotechnology, pho-
topolymers, electro-optic polymers will be covered. Additionally, those polymer classes in
which important new members have appeared in recent years will be revisited to provide
a comprehensive update.
Written by foremost experts in the field from industry and academia, these books have
particular emphasis on structure–property relationships of polymers and manufacturing
technologies as well as their practical and novel applications. The aim of each book in
the series is to provide readers with an in-depth treatment of the state-of-the-art in that
field of polymer technology. Collectively, the series will provide a definitive library of
the latest advances in the major polymer families as well as significant new fields of
development in polymer science.
This approach will lead to a better understanding and improve the cross-fertilization of
ideas between scientists and engineers of many disciplines. The series will be of interest
to all polymer scientists and engineers, providing excellent up-to-date coverage of diverse
topics in polymer science, and thus will serve as an invaluable ongoing reference collection
for any technical library.
John Scheirs
June 1997
Preface
This book covers thermal and catalytic pyrolysis processes that produce liquid fuels (or
other useful chemicals) from waste plastics. The book provides a comprehensive overview
of the main commercial plastics pyrolysis processes, the types of plastics that can be
processed, the properties of the respective fuels produced and the key variables influenc-
ing the pyrolysis of plastics such as temperature, residence time, pressure and catalyst
types.
Only some 15–20% of all waste plastics can be effectively recycled by conventional
mechanical recycling technologies (i.e. sort/grind/wash/extrusion). Beyond this level the
plastics become increasingly commingled and contaminated with extraneous materials
such as soil, dirt, aluminium foils, paper labels and food remnants.
Pyrolysis is a tertiary or feedstock recycling technique capable of converting plastic
waste into fuels, monomers, or other valuable materials by thermal and catalytic cracking
processes. This method can be applied to transform both thermoplastics and thermosets in
high-quality fuels and chemicals. Moreover it allows the treatment of mixed, unwashed
plastic wastes.
In its simplest definition pyrolysis is the degradation of polymers at high temperatures
under nonoxidative conditions to yield valuable products (e.g. fuels and oils). Pyrolysis
is also referred to as polymer cracking and its main advantages are that it can deal with
plastic waste which is otherwise difficult to recycle and it creates reusable products with
unlimited market acceptance.
As feedstock recycling and pyrolysis is not incineration there are no toxic or environ-
mentally harmful emissions. Pyrolysis recycling of mixed plastics thus has great potential
for heterogenous plastic waste that cannot be economically separated.
This book provides an overview of the science and technology of pyrolysis of waste
plastics. The book will describe the types of plastics that are suitable for pyrolysis recy-
cling, the mechanism of pyrolytic degradation of various plastics, characterization of the
pyrolysis products and details of commercially mature pyrolysis technologies.
The major advantage of the pyrolysis technology is its ability to handle unsorted,
unwashed plastic. This means that heavily contaminated plastics such as mulch film
(which sometimes contains as much as 20% adherent dirt/soil) can be processed with-
out difficulty. Other normally hard to recycle plastics such as laminates of incompat-
ible polymers, multilayer films or polymer mixtures can also be processed with ease,
xxvi PREFACE
unlike in conventional plastic recycling techniques. In fact, most plastics can be pro-
cessed directly, even if contaminated with dirt, aluminium laminates, printing inks, oil
residues, etc.
The production of gasoline, kerosene and diesel from waste plastics is an emerging
technological solution to the vast amount of plastics that cannot be economically recovered
by conventional mechanical recycling.
Pyrolysis recycling of mixed waste plastics into generator and transportation fuels is
seen by many as the answer for recovering value from unwashed, commingled plastics
and achieving their desired diversion from landfill. Pyrolytic recycling of plastic wastes
has already been achieved on commercial scale albeit to a limited extent. Nevertheless, the
development and improvement of the pyrolysis plastics recycling technologies in recent
years has great commercial potential. The development of bench-scale experiments carried
out in laboratories to full-scale pyrolysis processes have now resulted in a number of
technically mature processes.
Through the use of low-temperature vacuum pyrolysis and cracking catalysts, liquid
fuels yield of up to 80% are possible with the resultant product resembling diesel fuel,
kerosene, gasoline or other useful hydrocarbon liquids. There are now emerging a number
of processes which will take post-consumer plastics and catalytically convert them into
gasoline and low-sulfur diesel fuel. The diesel fuel meets or exceeds both European and
Federal EPA standards for emissions and is designed specifically for the solid waste
disposal industry that has significant investment in diesel-powered equipment. The types
of plastic targeted as feedstock for this project have no commercial value and would
otherwise be sent to landfill.
High-temperature pyrolysis and cracking of waste thermoplastic polymers, such as
polyethylene, polypropylene and polystyrene is an environmentally acceptable method of
recycling. These type of processes embrace both thermal pyrolysis and cracking, catalytic
cracking and hydrocracking in the presence of hydrogen. Mainly polyethylene, polypropy-
lene and polystyrene are used as the feedstock for pyrolysis since they have no heteroatom
content and the liquid products are theoretically free of sulfur.
The principal output products are gaseous and liquid hydrocarbon fractions that are
remarkably similar to the refinery cracking products. Their chemical composition and
properties strongly depend on the input feed composition, (i.e. proportion of polyethylene,
polypropylene and polystyrene in the feedstock) and they can also be unstable due to their
high reactive olefins content (especially from polyethylene and polystyrene cracking).
The book also explores the application of various acidic catalysts, such as silica–
alumina, zeolites (HY, HZSM-5, mordenite) or alkaline compounds such as zinc oxide.
However, the main problem with catalytic cracking is that in the course of the crack-
ing process all catalysts deactivate very quickly. Expensive zeolite catalysts increase the
cost of waste plastics cracking process to the point where it becomes economically unac-
ceptable since the catalyst becomes contained in coke residue and therefore cannot be
recovered and regenerated.
Effective engineering design of the cracking reactor for waste plastic processing is very
important since the carbonaceous solid residue is one of the cracking products (levels up
to 10% or more) and its continuous removal from the reactor is necessary to ensure
profitable running. Stirred vessel reactors which have augers in the bases to facilitate
continuous char removal are presented.
PREFACE xxvii
This book is truely international in scope with contributing authors from Spain, Saudi
Arabia, Italy, New Zealand, Japan, Turkey, Hungary, Poland, Belgium, France, Germany,
Korea, UK, USA, India, China and Australia.
John Scheirs
Walter Kaminsky
8 August, 2005
About the Editors
Dr John Scheirs is a polymer research specialist with an emphasis on plastic recycling and
pyrolysis of waste plastics into fuels. He serves as a consultant for Ozmotech Australia and
has worked on the development of their Thermofuel process which can convert unwashed
mixed plastics into low-sulfur diesel transportation fuel. He has studied the pyrolysis of
HDPE, PP, PET and engineering plastics.
John Scheirs is the author of the leading book on plastics recycling entitled Polymer
Recycling: Science, Technology and Applications published by John Wiley & Sons Ltd,
Chichester in 1998. He is also a member of the editorial board of the international journal
Polymer Degradation and Stabilization, Elsevier Scientific, Netherlands.
John Scheirs is now the principal consultant with ExcelPlas Polymer Technology where
he specializes in polymer recycling, polymer degradation, polymer processing and testing.
Professor Walter Kaminsky was born 1941 in Hamburg and studied chemistry at
the University of Hamburg. His thesis was in the field of metallocene chemistry and his
habilitation in the field of recycling of polymers by pyrolysis. Since 1979, he has occupied
the role of Full Professor of Technical and Macromolecular Chemistry at the University
of Hamburg.
He is currently supervising a group of 15 students and scientists in the field of pyrol-
ysis of plastic waste in a fluidized bed process and a group in the field of metal-
locene/methylaluminoxane chemistry. His past experience includes the development of
pilot plants for the feedstock recycling of plastic wastes and scrap tires, and discovering
highly active metallocene catalysts for the polymerization of olefins. He has published
more than 300 papers and books and holds 20 patents. He has organized several interna-
tional symposia in the field of pyrolysis and olefin polymerization.
In 1987 he received, together with Hansjörg Sinn, the European Research Prize for
the development of the Hamburg process for pyrolysis of polymers. In 1997 he received
the Carothers Award of the American Chemical Society (Delaware Section), and in the
same year the Walter Ahlström Prize in Helsinki, Finland. Since 1998 he has been an
Honorary Member of the Royal Society of Chemistry in London, and Honorary Professor
of the Zhejiang University in China. In 1999 he received the Benjamin Franklin Medal
for Chemistry, Philadelphia and in 2003 the Hermann Staudinger Prize of the German
Chemical Society (GDCh).
PART I
Introduction
1
Introduction to Feedstock Recycling

of Plastics
A. BUEKENS
Vrije Universiteit Brussel (V.U.B.), Brussels, Belgium
ABBREVIATIONS
ABS acrylonitrile–butadiene–styrene
APP atactic polypropylene
ASR automobile shredder residue
EVA ethylene vinyl acetata
HDPE high-density polyethylene
HIPS high impact polystyrene
LDPE low-density polyethylene
Low (LD)PE low-molecular-weight polyethylene
MSW municipal solid waste
MW molecular weight
PA polyamides, Trade Name Nylons
PC polycarbonate
PE polyethylene
PET polyethylene terephthalate
PIB polyisobutylene
PP polypropylene
PS polystyrene
PTFE polytetrafluorethylene, Trade Name Teflon
PU or PUR polyurethane
PVC polyvinyl chloride
WEEE waste electric and electronic equipment
1 INTRODUCTION
This review focuses on some technical and practical aspects of the pyrolysis or thermal
cracking of waste plastics, to yield liquid fuels and monomers as a main product. It
4 A. BUEKENS
briefly enumerates some alternative products, such as synthesis gas, carbon, hydrogen
chloride, or bromine, or techniques, such as combustion, partial oxidation or gasification,
or feedstock recycling by chemical rather than thermal methods.
Some of the practical aspects to be considered are:
• the adequate availability and ensured supply of waste plastics,
• their collection, transportation, handling, storage, pre-treatment, and conditioning for
feedstock recycling;
• their general management, as well as the typical cost of such operations.
2 NOMENCLATURE
Plastics are a generic group of synthetic or natural materials, composed of high-molecular

chains whose sole or major element is carbon. In common usage the terms plastics,
polymers and resins are roughly equivalent. A plastic material is (Society of Plastics
Industry, cited in Brady and Clauser, [1]) ‘any one of a large group of materials consisting
wholly or in part of combinations of carbon with oxygen, hydrogen, nitrogen, and other
organic or inorganic elements which, while solid in the finished state, at some stage in its
manufacture is made liquid, and thus capable of being formed into various shapes, most
usually through the application, either singly or together, of heat and pressure.’
Plastics are manufactured from monomers, i.e. a repeatable molecular unit and building
block, by means of various chemical processes, such as:
• a catalytic or peroxide-initiated polymerization of monomer(s), e.g. ethylene, pro-
pylene, or butadiene + styrene (copolymers);
• a polycondensation of dissimilar monomers (e.g. bifunctional organic acids and alco-
hols or amines);
• polyaddition of reactive monomer molecules.
Especially the first group forms an attractive feedstock for pyrolysis processes.
Important monomers are polymerization grade (i.e. very high purity) ethylene, pro-
pylene, butadiene, three products obtained by thermal cracking or pyrolysis of e.g. naph-
tha, light gas-oil, or liquefied petroleum gases (LPG = propane or butane) and purified by
low-temperature, high-pressure distillation, up to polymerization grade chemicals. Adding
hetero-atoms to the monomer, such as chlorine in vinyl chloride monomer, creates addi-
tional difficulties in pyrolysis processes and methods for separating waste plastics at
the source or by mechanical means, e.g. sink/float, froth flotation, separation after iden-
tification on the basis of absorption or reflection spectra, or electrostatic sorting after
tribo-electric charging, is an important practical consideration.
Before its conversion into plastic products the resulting resin is almost always com-
pounded with various additives of different nature and constitution, meant to improve
processing, stability, or mechanical specifications as a function of a given application
(outdoors, i.e. UV-light exposed, oxidation, high-temperature processing). Such additives
are regularly used as:
• antioxidants (1%),
• heat and light stabilizers (5%),
• plasticizers (40%),
INTRODUCTION 5
• impact resistance enhancers (10%),
• pigments, colorants and dyestuffs (5%),
• flame retardants (15%),
• mould-release agents,
• foaming agents (2%),
• fillers (40%)
(maximum amount encountered, in weight percent). Other additives are used as anti-
blocker, anti-fogging and anti-static agents, bio-stabilizers, chemical blowing agents,
cross-linking agents, high polymeric impact strength additives and processing aids, lubri-
cants, metal deactivators, optical brighteners, property modifiers, reinforcements, smoke
and afterglow suppressants, wetting agents, etc. Their presence, as well as chemicals used
in initiating or terminating polymerization, is a complicating factor in feedstock recycling,
also termed chemical recycling or, in a more restricted sense, pyrolysis or thermal crack-
ing of waste plastics, since their nature, amount, and behaviour during pyrolysis (thermal
volatilization or breakdown) and eventual influence upon reaction products and mecha-
nism are somewhat unpredictable, especially for waste plastics of unknown origin and
formulation. PVC absorbs more additive volume than any other resin.
Plastics can be classified on the basis of numerous criteria, e.g.:
• chemical composition, directly connected with the nature of the monomer(s) and
the method of polymerization. Plastics are thus subdivided into classes, e.g. poly-
olefins, vinyl polymers, styrenics, polyamides, polyesters, epoxy resins, polycarbon-
ates, polyurethanes, etc.;
• chemical structure, e.g. linear (high-density polyethylene), branched (low-density poly-
ethylene), cross-linked and three-dimensionally networked (thermosets, rubbers);
• stiffness: elastic, flexible, or rigid;
• type of application: commodity vs engineering, general purpose vs specialty plastics;
• processing method used (injecting moulding, extrusion, film blowing, blow moulding,
thermoforming, casting, calendaring, and many other techniques);
Thermoplastics still soften when heated and harden again when cooled, because there
is little or no bonding between individual molecular chains. Thermosets show three-
dimensional structures and rather than softening, thermally decompose while heating. All
commodity plastics are thermoplastic.
Rubber has a structure intermediate between thermosets and thermoplastics, with molec-
ular chains linked by sulphur bridges during vulcanization. In pyrolysis, the main material
is tyre rubber, a compound of styrene- butadiene- and isoprene-based rubber (SBR), of
carbon black, sulphur, vulcanization aids, and zinc oxide.
The history, statistics, classification, barrier properties, main resins of bulk plastics,
etc. can be read from websites [2], with typical applications [3]. Plastics also show some
other characteristic properties:
• an amorphous, i.e. noncrystalline structure, related to disorder among polymer chains;
• low thermal conductivity;
• high electrical resistance;
• low softening temperatures;
• viscous–elastic behaviour.
6 A. BUEKENS
The world production of plastics keeps rising, and so does waste generation, albeit
with a time lag, dictated by lifetime. This lifetime spans from weeks (packaging), over
months (agricultural film) and years (cars, household appliances, furniture), even to the
order of a century (in some building applications). In numerous building applications
(water distribution ducts, flooring, roofing, window frames) such lifetimes are not known
with certainty. Still, take-back schemes more and more affect important markets, such
as packaging, automobile, or electrical and electronic equipment. Such schemes are still
developing, confronted with the immense variety in applications, resins, additives, and
with the difficulty in identification and light weight of plastics.
Plastics waste arises at the levels of production, conversion, and consumption. In the first
two categories source separation, identification, and recycling, is straightforward. Such
simple source separation concepts no longer hold for post-consumer recycling, where
entropy is immense: plastic products both geographically and functionally are widely
spread, more often than not compounded with unknown additives, or mixed, soiled, com-
posite, and difficult to collect at a reasonable cost.
Mechanical recycling, i.e. reusing as a plastic material in similar applications (closed-
loop recycling, e.g. film-to-film) provides the highest value to waste plastics. Loss in
mechanical properties restricts recycling to simpler applications and geomembranes, some-
times simply replacing low-grade wood, as in urban furniture, such as park benches.
Feedstock recycling converts plastics into monomer, mixes of chemicals, or into syn-
thesis gas or reducing gas. Thermal recycling (combustion) merely recovers the heat of
combustion.
3 PYROLYSIS OF PLASTICS AND RUBBER
Pyrolysis, also termed thermolysis (Greek: pur = fire; thermos = warm; luo = loosen),
is a process of chemical and thermal decomposition, generally leading to smaller mole-
cules. Semantically, the term thermolysis is more appropriate than pyrolysis, since fire
implies the presence of oxygen and hence of reactive and oxygen-bearing intermediates. In
most pyrolysis processes, however, air is excluded, for reasons of safety, product quality,
and yield.
Pyrolysis can be conducted at various temperature levels, reaction times, pressures, and
in the presence or absence of reactive gases or liquids, and of catalysts. Plastics pyrolysis
proceeds at low (<400◦ C), medium (400–600◦ C) or high temperature (>600◦ C). The
pressure is generally atmospheric. Subatmospheric operation, whether using vacuum or
diluents, e.g. steam, may be selected if the most desirable products are thermally unstable,
e.g. easily repolymerizing, as in the pyrolysis of rubber or styrenics.
The thermal decomposition of polymers yields gases, distillates and char, albeit in
widely variable relative amounts. These can be applied as fuels, petrochemicals, and
monomers. Depending on the polymers or polymer mixtures fed and the operating con-
ditions used, yields can vary widely. As a rule both gaseous and liquid products are
mixtures of numerous different compounds. The problem of fractionating these effluents
and upgrading to commercial specifications, while separating undesirable impurities, must
be investigated on a case-by-case basis. The char incorporates fillers, pigments, and ash.
Pyrolysis processes involve breaking bonds and are often endothermic, so that ensuring
a supply of heat to the reacting material is essential and generally rate-determining. Partial
INTRODUCTION 7
oxidation supplies such heat internally, but the pyrolysis products are diluted by oxidation
or combustion products.
Polyolefin resins contain only carbon and hydrogen, and additives, such as some antiox-
idants and UV stabilizers. Moreover, the presence of hetero-elements, such as chlorine
and bromine is undesirable, as these elements distribute over the three product phases-gas,
liquid, and solids, reducing the market potential and value of each of these. Studying their
elimination is a major consideration in developing processes for mixed plastics.
3.1 SURVEY OF PREVIOUS WORK

Most work on plastics pyrolysis has been academic and directed at the analysis of poly-
mers, their molecular structures and thermal stability, at the study of pyrolysis products,
e.g. fire research, or at feedstock recycling at a laboratory or pilot scale. An early survey
was given by Madorsky [4]. Given the large number of possible purposes, or different
resins, additives, and operating conditions, the field is as wide as the sky!
Since the introduction of modern instruments (ca 1962) the thermal analysis of polymers
as a research field has expanded very rapidly, encompassing specific techniques such as:
• differential scanning calorimetry (DSC), for measurements of specific heat and enthal-
pies of phase transition;
• differential thermal analysis (DTA), measuring the temperature difference between the
sample and a reference and indicating the occurrence of any heat effect and of abrupt
changes in heat capacity;
• thermogravimetric analysis (TGA), for assessing thermal stability and decomposition
temperatures;
• thermomechanical analysis (TMA), for establishing the mechanical response of poly-
mer systems to temperature changes. It includes dilatometry, penetration, torsion
modulus, and stress/strain behaviour, as well as establishing the softening temper-
ature, as determined by the Vicat penetration test, the deflection temperature or heat
distortion test, the zero strength temperature test, the polymer melt or stick temperature
test;
• flammability testing. Plastics used in furniture, mattresses, cars, electronics, etc. must
satisfy specifications regarding fire behaviour and flame retardancy.
These techniques are often coupled with evolved gas analysis. TGA is a basic technique
in studies on thermal decomposition. An excellent introduction is given in [5]. A system-
atic study of both physical and chemical aspects in plastics pyrolysis was launched in the
E.U. Cycleplast project [6], aiming at a systematic scientific evaluation of various steps.
The (German) Society for Thermal Testing listed methods relating to thermal testing [7].
Since 1965, prestigious, at present biannual meetings on Analytical and Applied Pyrolysis
have been chaired by authoritative scientists such as G. Guiochon (1965), C.E.R. Jones
(1972), J. Kistemaker (1976), T. Szekely (1979), K.J. Voorhees (1982), I. Lüderwald &
H.-R. Schulten (1984), C. Gutteridge (1986), I. Ericsson (1988), J.J. Boon (1990), W.
Kaminsky (1992), S. Tsuge (1994), G. Audisio (1996), A. Kettrup (1998), F.J. Gonzalez-
Vila (2000), J. Fink (2002), R. Font & A. Marcilla (2004), and M. Blaszo (2006). Themes
such as instrumentation and analytical methods, elucidation of chemical structure, thermo-
oxidation and photo-oxidation, mechanisms and kinetics are much more central in such
work than is feedstock recycling.
8 A. BUEKENS
On the industrial side, there has been a lively interest in plastics pyrolysis, since the
breakthrough of mass production of plastics in the 1960s. A major tribute is to be paid
to a first wave of Japanese enterprise, actively promoting plastics pyrolysis as a technical
solution. New initiatives in Japan were launched in the 1980s and 1990s, such as the dou-
ble fluid bed systems operated by Ebara Co. (Stardust Project, Yokohama), and, with less
success, Tsukishima Kikai. At present these steady efforts are culminating in nationwide
pyrolysis systems for converting waste plastics, separately collected from households, to
yield liquid fuels and monomers, or used as a reducing agent in blast furnaces or as a
coal substitute in coking plants. Plastics are converted in liquid phase, stirred tank reac-
tors in plants at Niigata and Sapporo, PVC in rotary kiln units to coke and HCl by the
former Nihon Kokan (at present JFE Holdings). Ube Industries jointly with Ebara Co.
have developed an elevated pressure gasification process; the synthesis gas is cleaned and
piped to a synthesis plant at the same site.
Japanese ventures were confronted with their counterparts in Europe and the USA
during the International Symposia on Feedstock Recycling from Plastics, or ISFR, held
at Sendai (1999), Ostend (2002) [8, 9] or at Karlsruhe (2005).
3.2 PRODUCTS FROM POLYMERS
3.2.1 Major Operating Conditions

The major factors of influence determining the product distribution resulting from plastics
pyrolysis are summarized in Table 1.1.
Chemical composition plays a dual role:
1. Mass conservation dictates that the pyrolysis products, distributed over the three phases,
gas, liquid, and solid, consist of the same elements as the raw materials and that their
relative amounts are conserved. There is a redistribution of relevant elements during
pyrolysis, with hydrogen and chlorine enriching the gas phase, carbon in the coke.
2. There is a direct link between polymer structure and its primary pyrolysis products,
the latter primarily resulting from the breakage of bonds followed by some molecular
or free radical rearrangement. Of course, secondary reactions do occur and gradually
convert the primary products into more stable, less reactive alternatives. The product
distribution hence depends on time, and relative rates of bond breakage and subsequent
processes, but can be found only by experiment. As a rule, bond breakage becomes
easier at high temperature.
Temperature is the most important operating variable, since it determines both the
rate of thermal decomposition and the stability of feedstock and reaction products. High
temperature (>600◦ C) and both vacuum and product dilution favour the production of
simple small gaseous molecules, low temperature (<400◦ C) and increased pressure lead
to more viscous liquid products, higher rates of pyrolysis, a higher coking tendency, more
secondary products and dehydrogenation.
Pyrolysis, for most plastics, begins at ∼300◦ C and for some thermosensitive resins
even earlier, e.g. for vinyl-based polymers. The onset of the pyrolysis reaction is strongly
influenced by the presence of additives, such as stabilizers, plasticizers and pigments. In
most processes a medium temperature (400–500◦ C) is selected and the plastics are in
INTRODUCTION 9
Table 1.1 Factors affecting product distribution
Factor of influence Effect

Chemical composition of The primary pyrolysis products relate directly to the chemical
the resins structure and composition of the resin, and also to the
mechanism of its decomposition (purely thermal or catalytic)
Pyrolysis temperature and Higher operating temperatures and high heating rates both
heating rate enhance bond breaking and favour the production of small
molecules
Pyrolysis time Longer residence times favour a secondary conversion of
primary products, yielding more coke, tar, as well as
thermally stable products, thus gradually obscuring the effect
of original polymer structure
Reactor type Determines mainly the quality of heat transfer, mixing, gas and
liquid phase residence times, and the escape of primary
products
Operating pressure Low pressure reduces the condensation of reactive fragments
forming coke and heavies
Presence of reactive gases, Such presence internally generates heat, dilutes the products
such as (air) oxygen or and influences upon equilibriums, kinetics, and mechanisms
hydrogen
Use of catalysts Their use influences upon kinetics and mechanisms, and hence,
the product distribution
Additives incorporated The additives generally either evaporate or decompose. Some
may influence kinetics and mechanism
Liquid or ‘gas’ phase Liquid phase pyrolysis retards the escape of evolving products,
thus enhancing interactions
a molten state. ‘Gas phase’ processes feature liquid polymer films, distributed over the
grains of fluidized bed pyrolysis reactors.
The required reaction time is determined principally by reaction temperature. The for-
mation of primary products, e.g. monomers, is favoured by short residence times, the
formation of more thermodynamically stable products (H2 , CH4 , aromatics, carbon) by
long ones. Low pressure (under vacuum, or in the presence of inert diluent) favours the
production of primary products, including monomer, high pressure that of complex, liquid
fractions.
The reactor type is selected mainly on the basis of technical considerations, mainly its
heat transfer and feed and residue handling characteristics. In many processes proposed
the polymer is first dissolved in a bath of molten polymer or wax, or dispersed in a
salt bath, to reduce the viscosity of the melt. Other processes suggest the use of the
excellent heat transfer and mixing properties of fluidized bed thermal or catalytic reactors.
Increasing temperatures has an influence upon thermodynamics, i.e. the relative stability
of various products, as well as upon kinetics and physical conditions of the reacting
mixture. High temperatures and heating rates, low pressures and residence times favour the
formation of primary products. Conversely, long residence times lead to a preponderance
of stable products. In the Hamburg pyrolysis process developed by Professor Kaminsky
and Professor Sinn, conditions were so selected that the main output was aromatics,
whatever the feedstock.
10 A. BUEKENS
In the presence of oxygen, part of the feedstock is oxidized (partial oxidation) and
carbon monoxide and dioxide are inevitable products, while oxygenated organics are
also arising as by-products. The process is termed gasification when the production of
combustible gas or synthesis gas is emphasized. Gasification is a high temperature process
that completely destroys the original chemical structures. However, the resulting gas is
tailor-made to requirements using well-known and large-scale techniques.
Pyrolysis or gasification, as processes, are both much easier to control than direct
firing of plastics. The latter is impossible on mechanical grates, equipping conventional
incinerators for municipal solid waste (MSW). On the other hand, thermal conversion is
feasible by means of fluidized bed technology. The few percent of plastics, as in traditional
MSW is unproblematic and the calorific content is converted into heat and often into
power, albeit at a disappointing level of conversion efficiency, of the order of 15–25%.
Theoretically, waste plastics have excellent fuel value, quite comparable to that of
gas oil, when only polyolefins are considered. Introducing hetero-atoms, such as oxygen,
nitrogen, or chlorine, reduces the heating value. Moreover, chlorine acts as an inhibitor and
generates strongly acid gas. In practice, however, plastics are difficult to burn, because
of an almost uncontrollable combustion rate, locally leading to oxygen deficiency and
products of incomplete combustion.
Hydrogenating conditions lead to the elimination of hetero-atoms and yield more sat-
urated products as well, an important consideration regarding the marketing of pyrolysis
products.
Catalysts are a class of compounds specially selected, designed and optimized for influ-
encing the reaction mechanism. The main purpose of catalysts is to convert vapour-phase
products into a higher-octane petrol (gasoline). Another purpose may be in accelerating
decomposition, using acids and bases for promoting the decomposition of polyamides
and polyesters. Throw-away catalysts may be used for scavenging impurities. Catalyst
activity, selectivity, and stability are major considerations. Some research directions can
be derived from the themes of 2nd ISFR papers [9]:
• catalytic cracking of polyolefins, possibly containing EVA, by J. Aguado et al.;
• the presence of polycyclic aromatic hydrocarbons in the product fractions, by P.T.
Williams and R. Bagri;
• co-catcracking with residues from light Arabian crude, by M. F. Ali;
• comparison of fresh, steam deactivated, and used FCC catalyst, by S. Ali and A.
Garforth;
• PP and PET cracking over TiO2 /SiO2 catalysts, by K. Nakano et al.;
• using red mud as a low-grade hydrocracking catalyst by J. Yanik et al.;
• hydro-cracking of MSW-plastics with vacuum gas oil by T. Karayildrim et al.;
Catalytic cracking is potentially an important route to produce high-value products
from plastic feedstock. The catalyst converts naphtha to higher-value petrol (gasoline).
Little is known on the effect of fillers or coke precursors (styrene, butadiene) on catalytic
activity and catalyst fouling, coking, or clogging. Another area of interest is the effect
of catalyst addition on the thermal decomposition in the liquid phase. It seems unlikely
that the macromolecules can contact the internal catalyst surface in a productive fashion.
Some additives may also influence the product distribution by modifying the cracking
mechanism and hence, product distribution. Generally, their effect is unknown but also
often much smaller than that expected from catalysts.
INTRODUCTION 11
3.2.2 Decomposition Modes
As a rule, the pyrolysis of plastics follows complex routes that cannot be described by
one or more chemical reactions, but only and still rather imperfectly by either empiri-
cal formulas featuring fractional stoichiometric coefficients or comprehensive systems of
elementary reactions, i.e. reactions that really proceed as written. Moreover, the composi-
tion and structure of these reaction systems may vary with details of molecular structure,
such as chain irregularities, incorporation of initiators or catalysts, etc. As a consequence,
precise mechanisms are of only scientific interest, an industrial approach being limited to
overall considerations, such as the heat effect and the product distribution resulting under
particular reaction conditions.
Decomposition modes are often subdivided according to the prevailing reaction patterns,
which are mainly dictated by molecular structure and the presence of catalysts:
1. Decomposition into monomer units (PMMA, PA 6) mainly, often termed unzipping.

This decomposition mode is of very large practical interest, since monomer is a high-
value product, typically commanding a price several times the equivalent of fuel value.
The pyrolysis of PMMA is in general use and economically warranted, with typical
scrap prices of the order of 300–400 ¤/tonne, monomer yields well in excess of 90%,
and monomer values of the order of up to 1500 ¤/tonne. Hence, PMMA waste is
highly valued! The MMA generated is not necessarily fit as polymerization grade, and
often used as a viscosity index improver of lubricating oil, in acrylic varnishes, rather
than as a monomer.
2. Random fragmentation of the principle polymer chain (PE, PP) into fragments of
variable, intermediate length. The size distribution over the resulting fragments is
largely Gaussian, with the average M.W. continuously descending with rising pyrolysis
temperature and time. Thus, polyolefins are converted into PE waxes and oils, often
high in α-olefins and a sulphur-free, premium diesel oil. Conversely, PP products yield
a much more branched product mix.
3. Decomposition according to both previous schemes combined (PS, PIB). In a polysty-
rene production plant, PS could conveniently be converted into monomer, since facili-
ties for separating the various pyrolysis products (styrene and its oligomers, ethylben-
zene, toluene, benzene, etc.) are available already on site. However, huge PS production
plants generally generate insufficient off-spec. scrap to feed a pyrolysis unit of even a
small industrial size!
4. Elimination of simple, stable molecules from adjacent atoms (PVC yields HCl, PVAc
yields acetic acid, PVOH yields water). Such thermal cleavage leaves unsaturated,
charring, residual chain residues.
5. Elimination of side-chains, followed by cross-linking and creating a porous charred
residue, including the non-volatile additives. This scheme is followed by most ther-
mosets and other cross-linked polymers.
Polymer resins and their major possible products are collected in Table 1.2. A high
purity of the feedstock is the best guarantee of clean and possibly marketable products.
Generally, the value of the products obtained is insufficient to warrant the process. How-
ever, recently the concept of feedstock recycling created a political current that is more
favourable to pyrolysis than the corresponding economic context.
12 A. BUEKENS
Table 1.2 Polymer resins and major possible products of thermal decomposition
Resin Mode of thermal decomposition Low-temperature High-temperature

products products
PE Random chain rupture Waxes, paraffin oils, Gases and light oils
α-olefins
PP Random chain rupture Vaseline, olefins Gases and light oils
PVC Elimination of HCl from the HCl (<300◦ C), Toluene (>300◦ C)
chain, chain dehydrogenation benzene
and cyclization
PS Combination of unzipping, and Styrene and its Styrene and its
chain rupture, forming oligomers oligomers
oligomers
PMMA Unzipping MMA Less MMA, more
decomposition
PTFE Unzipping Monomer TFE
PET β-Hydrogen transfer, Benzoic acid and
rearrangement and vinyl terephthalate
de-carboxylation
PA-6 Unzipping Caprolactam
3.2.3 Resins and Products

A systematic study of both physical and chemical aspects in plastics pyrolysis was
launched in the Cycleplast project [6]. Thermal degradation of commodity polymers,
including kinetic factors and mechanism, were systematically investigated by Professor
Bockhorn and collaborators, using thermogravimetry, linked with mass spectrometry, as
well as closed loop laboratory-scale pyrolysis reactors. The resulting kinetic parameters
are discussed further.
Polyolefins, mainly PE and PP, the main commodity plastics, decompose into a range
of paraffins and olefins, according to route 2. The molecular weight distribution and the
paraffin-to-olefin ratio decrease with rising reaction temperature and time.
Polystyrene PS mainly yields styrene, as well as its oligomers, mainly dimers and
trimers. Mixtures of PS + PE decompose as usual in the case of PS, with the pyrol-
ysis products somewhat more saturated, the PE providing the required hydrogen. The
decomposition of PE is somewhat accelerated by the presence of PS.
Polyvinylchloride (PVC) decomposes into two distinct steps, the first yielding hydrogen
chloride and benzene, the second a mix of aromatics. The kinetic results vary with the
amount of sample and the experimental modes (programmed heating or isothermal) are
different for hydrogen chloride evolution, with activation energy 136 vs 120 kJ/mol, and
reaction order 1.54 and 1.98.
PET decomposes via β-hydrogen transfer, rearrangement and decarboxylation, with
major products benzoic acid and vinyl terephthalate.
Polyamide 6 depolymerizes into caprolactam with high yields. The decomposition is
catalysed by both strong acids and bases.
Kinetic study may describe decomposition, generally using first-order models and a
reaction rate parameter linked to temperature by the Arrhenius law. Closer scrutiny
reveals a more complex behaviour, with kinetic parameters that continuously evolve
with experimental conditions. These studies yield values for activation energy ranging
INTRODUCTION 13
from ∼140 kJ/mol (PVC-dechlorination) to 290 kJ/mol (second step in PVC-pyrolysis,
and dynamic cracking of PS). Also the reaction orders observed vary widely, from 0.3
(dynamic cracking of PP) to 2 (dynamic cracking of PVC, second step). However, such
kinetic parameters vary with the experimental conditions, in line with the complexity of
the reaction system, composed of innumerable elementary chemical reactions.
In actual industrial practice, these figures are relatively meaningless, since actual pyrol-
ysis kinetics are normally determined by the rate of heat transfer [10]. A number of
interesting simulations of the effect of heat transfer upon apparent rates were performed by
both Hornung et al. and by Vergneaud in the framework of the E.U. Cycleplast project [6].
Other studies focused on a mix of MSW plastics, whether resulting from selective
collection or mechanical separation. Six thermoplastics, which represent more than two-
thirds of all polymer production in western Europe, were pyrolysed in a static batch reactor
in a nitrogen atmosphere. These were high-density polyethylene (HDPE), low-density
polyethylene (LDPE), polystyrene (PS), polypropylene (PP), polyethylene terephthalate
(PET) and polyvinylchloride (PVC). The heating rate used was 25◦ C min−1 to a final
temperature of 700◦ C. These six plastics were then mixed together to simulate the plastic
fraction of municipal solid waste found in Europe. The effect of mixing on the product
yield and composition was examined. The results showed that the polymers studied did
not react independently, but some interaction between samples was observed. The product
yield for the mixture of plastics at 700◦ C was 9.63% gas, 75.11% oil, 2.87% char and
2.31% HCl. The gases identified were H2 , CH4 , C2 H4 , C2 H6 , C3 H6 , C3 H8 , C4 H8 , C4 H10 ,
CO2 and CO. The composition of oils were determined using Fourier transform infrared
spectrometry and size exclusion chromatography. Analysis showed the presence mainly
of aliphatic compounds with small amounts of aromatic compounds [11].
The results of an interesting study on copyrolysis of naphtha and added polyolefins
or their kinetics and degradation products were presented at the Analytical and Applied
Pyrolysis meeting at Alicante [12] (Table 1.3). The product yields from cracking (450◦ C)
of LDPE and PP are quite different, with more liquid fraction from PP:
The relative and absolute amount of paraffin thus decreases with temperature, that of
olefins and di-olefins tends to increase; simultaneously, the ratio of light products (C<15 )
Table 1.3a Product distribution in the cracking

of polyolefins at 450◦ C
Feedstock Gas Oil/wax Residue

LDPE 20.0 75.0 5.0
PP 11.0 87.8 1.2
Table 1.3b Product distribution in the polyolefins cracking: distribution of C15 and Ratio C<15 /
C>15
Temperature n-Pentadecane, wt 1-Pentadecene, wt 1,14-Pentadecadiene, wt Ratio C<15 /C>15

450◦ C 2.80 3.58 0.64 1.27
550◦ C 0.97 2.16 0.59 2.22
650◦ C 0.46 1.23 0.42 2.67
14 A. BUEKENS
to heavies (C>15 ) rises continuously with temperature. The authors also determined the
overall kinetic parameters and product distribution for naphtha cracking proper, or after
adding LDPE or PP. The kinetics and product distribution were little affected but the rate
of coking somewhat increased in the sequence:
Naphtha < naphtha + LDPE naphtha + PP
These authors studied the possibility of blending LDPE and PP into the feedstock of
a naphtha cracker. Such units have huge yearly capacity, of the order of 400 000 tonne
ethylene or about 1 Mton of feedstock (naphtha). Most plastics pyrolysis units have only
a modest scale, ranging from an annual 2000 to 20 000 tonne. This difference in scale
obviously reflects in differences in cost, since labour is almost identical for small, medium,
or large plant, whereas investment cost I of petrochemical plant typically varies with
capacity C as (R = reference basis):
I /IR = (C/CR )2/3
This means that plant cost varies as shown in Table 1.4.
3.2.4 By-products
The major product of pyrolysis is either a monomer (PMMA, PS), or a series of fuel
fractions. By-products of plastics pyrolysis are related to the presence of:
Heteroatoms:
• oxygen in the resin or the pyrolysis atmosphere leads to the formation of water and
oxygenated products;
• chlorine leaves pyrolysis units mainly as (an irritating and corrosive) hydrogen chloride
gas. Normally, no chlorine gas is formed, due to the strongly reducing conditions.
Bromine, under similar conditions, is somewhat easier to form;
• nitrogen yields various substances of concern, such as ammonia, hydrogen cyanide,
and possibly organic compounds, such as nitriles and amines.
Additives:
• mineral additives generally report to the coke fraction;
• organic additives either volatilize, or decompose. A major additive, in relative amounts,
are PVC plasticizers. Some PVC products (flooring) may contain more additives than
PVC resin.
Table 1.4 Plant investment cost, relative values, or per unit capacity
Plant investment cost

Capacity (relative values) Relative values per unit capacity
(tonne/year)
1 0.215 2.15
3 0.448 1.49
10 1.000 1.00
30 2.080 0.69
INTRODUCTION 15
Secondary reactions: Under pyrolysis conditions, most pyrolysis products have only a
precarious stability, as well as a marked residual reactivity towards more stable products
and ultimately its elements carbon, hydrogen, as well as simple, stable molecules, such
as water, ammonia, hydrogen chloride, etc. In some cases conversion along the pyrolytic
route will be halted at some point, in order to preserve high-value primary products and
reduce the difficulty of separating more complex mixtures.
Coke formation:
• generally, coke formed by pyrolysis is a by-product only. It is a main result of
pyrolysing thermosets and PVC. Moreover, resins can be ordered on the basis of
coking tendency, but the reaction conditions as well as external surfaces, such as
reactor walls or fillers, play a major role;
• coke could be upgraded, by activating it to activated carbon, or leaching out fillers
There is no evidence, however, that this has ever been contemplated seriously;
• depending on pyrolysis conditions, polyolefins can be converted almost quantitatively
into volatiles. Polystyrene has stronger their coking tendency, and polyvinylchloride
always leaves some coke. Thermosets and rubbers leave coke as a major product;
• coking tendency, however, depends on operating conditions and polymer structure,
as analysed by Van Krevelen [13]. Moreover, some coke may derive from secondary
reactions, involving readily polymerizable products, such as dienes and olefins, or
coke precursors, such as aromatics. Metal surfaces and coke may actively catalyse
coking.
3.3 HETERO-ATOMS AND SIDE PRODUCTS
A major problem in pyrolysis is in the rather unpredictable specifications of both feed-

stock, if it is a mix of plastics, and products. Especially the presence of halogens has been
considered problematic, both because of product quality and operating problems, such as:
• corrosion by HCl, especially in the presence of water vapour;
• clogging by CaCl2 , a problem that once plagued the plant at Ebenhausen, based on
the Hamburg University pyrolysis process.
3.3.1 Reactor Types and Processes (Table 1.5)

Professor Fontana and Dr Jung classified all major gasification routes and pyrolysis pro-
cesses, studying their mass and energy balances as well as operating conditions (refer
2nd ISFR Ostend) [9], predicting the behaviour of mixed plastics during pyrolysis and
gasification, in order to assess the production of valuable substitution fuels. Their model
was validated by laboratory-scale experiments and the quality of the resulting substitution
fuels evaluated, to choose the best thermal process for industrial plants according to the
properties of available waste streams.
Extruders are available with capacity of more than 1 tonne/h, to mix and melt plastics
and provide profiles, tubes, sheet, etc. They are mostly heated electrically, or else using
circulating thermal oil, and can be used in pyrolytic systems for feeding plastics, straining
the molten feed, eliminating HCl from PVC at temperatures up to some 400◦ C. Professor
16 A. BUEKENS
Table 1.5 Reactor types and their characteristics
Reactor type Particular characteristics Applications

Extruder Operating temperature is limited. Production of waxes
Degassing of premature from PE
decomposition products is essential
Tubular reactor Simplicity Molten polyolefins
Stirred tank reactor, Conventional liquid phase reactor. Mixed plastics: BASF,
possibly with Stirring improves heat transfer. Ludwigshafen
external heating Clogging of downstream ducting has Chiyoda Engineering,
loop and/or reflux to be avoided Niigata
cooler
Vertical or shaft Gravity flow Rubber pyrolysis Foster
reactor Wheeler
Fixed bed reactor Mainly for catalytic reactions, converting
vapours from a first reactor
Salt or lead bath The bath acts as a heat transfer agent. PMMA pyrolysis
reactor Residues accumulate on top of the
layer, requiring a periodic shutdown
for cleaning
Fluidized bed reactor The fluidized bed acts as a heat transfer
agent, dispersing the melting plastic in
thin layers. Residues are carried out
with the products, requiring a delicate
filtration of fines (pigments, fillers)
Rotary kiln Simple units, featuring tumbling action NKK PVC-pyrolysis
and gravity flow. Sealing is delicate. process
Autoclave Reactor for operating under pressure, Hydrogenation
generally in a batch mode
Menges and his successor Professor Michaelis conducted pyrolysis at RWTH-Aachen in

an externally heated extruder, up to 430◦ C, a temperature maximum dictated by materi-
als selection considerations. Early extruder pyrolysis systems were developed by Union
Carbide and Japan Steel Works [14].
Tubular, or fixed-bed thermal or catalytic reactors, are a conventional technology in
chemical engineering, and provide plug flow, but lack the positive displacement, mixing
and plasticizing effect of single or double screw extruders. They were used to a limited
extent, e.g. by Japanese Gasoline and Sanyo Electric Co., the latter featuring dielectric
heating. Shaft reactors have been proposed for rubber pyrolysis, e.g. the cross-flow units
in the Warren Spring Laboratories developed process, proposed by Foster Wheeler. Rotary
kiln reactors have provided an alternative in rubber pyrolysis and were used by Sumitomo
Cement and Kobe Steel, at present by Nippon Kokan for PVC [14].
The stirred tank reactor, possibly with external heating loop and/or reflux cooler, is
widely proposed as a plastics liquid phase pyrolysis reactor. Both BASF [15] and Profes-
sor Bockhorn [6] have used a cascade of well-mixed reactors to produce a step-by-step
pyrolysis of resin mixtures.
The required heat of reaction is supplied by external heating of the reaction vessel,
or, for laboratory-scale or pilot units, by electrical heating. Full-scale plant is either
directly fired, or heated by circulating reacting liquids through an external pipe still. Some
INTRODUCTION 17
processes propose a circulating heat carrier, e.g. superheated steam, molten salts, sands or
pebbles, to heat the charge. One process (Sanyo Co.) used dielectric losses, arising from
the high-frequency oscillation of electrically polarized molecules. The problem of heat
transfer can be eliminated altogether by partial oxidation of the reactor contents. In this
case, the product stream is diluted, by combustion products that dilute and oxidize the
pyrolysis products. This makes the recovery of useful products more difficult and reduces
the calorific value of the pyrolysis gas produced.
Numerous liquid phase processes make use of a tank reactor, containing a bath of
molten plastics, or a dedicated heat transfer agent, such as molten lead, tin, or salts. The
bath is indirectly heated, generally by being mounted into a furnace. The bath contents
are stirred, to obtain homogeneous operating conditions, improve heat transfer and avoid
charred residues forming upon overheated heat transfer surfaces. A possible alternative to
stirring is to circulate the molten plastics using pumps, by transferring the reactor contents
through an external furnace or heat exchanger.
Early developments were made by Mitsui Shipbuilding and Engineering, Ruhrchemie
(molten salts), Kawasaki Heavy Industries and Mitsubishi Heavy Industries [14]. Mitsui
processed low-M.W. PE and atactic PP to form:
• 4–5% gas, mainly C1 –C4 hydrocarbons;
• 90% oil, consisting mainly of n-paraffins, 1-olefins and their isomers;
• 5–6% of residue – fillers, stabilizer residues, pigments, etc.
Mitsubishi Heavy Industries pioneered a two-step pyrolysis of mixed plastics. A pri-
mary vessel is used for decomposing PVC at 300◦ C. Then, HCl is scrubbed out from the
effluent. Molten material is fed into a second vessel operating at 400–500◦ C. The same
concept was much later applied by BASF at Ludwigshafen, and extended to achieve
a selective pyrolysis, making use of differences in thermal stability of the different
resins.
Potential operating problems may occur, due to:
• clogging of effluent lines by entrained droplets or waxy materials. At the Niigata plant
such an obstruction led to an uncontrolled pressure rise in the reactor, pushing out
part of the reactor contents through the feeder system, and eventually causing a fire;
• charring and fouling of heat transfer surfaces;
• deficient level control.
A fluidized bed is a second frequently used type of reactor. Early developments include
Japan Gasoline Co. (PS-waste), Sumitomo Shipbuilding and Machinery Co. and the Uni-
versity of Hamburg. The latter developments led to the construction of a demonstration
plant at Ebenhausen that was halted after being confronted to a number of technical
operating problems.
3.3.2 Product Specifications

Distinction should be made between monomers, specific petrochemicals, and more or less
typical oil fractions, produced by mixed plastics pyrolysis. Potential pyrolysis products
from polyolefins are naphtha, kerosene, or gas-oil. These are blends of numerous different
18 A. BUEKENS
Table 1.6 Typical naphtha specifications and testing methods [18]
Property Units Test method Value

◦ 3
Density (15.6 C) g/cm ASTM D-4052 0.735 max.
Reid vapour pressure psig ASTM D-323 12 max.
Color Saybolt ASTM D-156 18 min.
Lead content wt ppb ASTM D-3559 50 max.
Total sulfur wt ppm ASTM D-3120 100 max.
◦
Initial boiling point C ASTM D-86 50 min.
◦
Final boiling point C ASTM D-86 165 max.
Paraffins wt% G.C 80 min.
Olefins wt% G.C 1 max
Naphthenes + aromatics wt% G.C Balance
Total chlorides wt ppm IP-AK/81 10 max.
hydrocarbons, but they still need to satisfy some common commercial specifications. Off-
specification products have no market, even if they can be blended in small amounts
into other streams that are less critical with respect to the specification compliances.
The latter are measured according to established standards, e.g. those of the American
Society for Testing Materials (ASTM), the American Petroleum Institute. Most monomers
(polymerization grade) are high-purity products: 99.99% or more. The latter is difficult
to attain in plastics pyrolysis!
The terminology used in oil refining is found at numerous websites, [16, 17]. As an
example, naphtha specifications (Table 1.6) typically involve:
Specifications of other oil fractions obtained may involve (diesel oil) a cetane index,
measures of unsaturation, or handling or safety data, such as cloud point or flash point.
3.4 FUNDAMENTALS
3.4.1 Aspect of Fluids Mechanics

As their name implies, plastics are easily deformable and once molten they may be heated
not only externally, but also internally, by dissipating friction or dielectric heat. Once the
pyrolysis temperature is attained, the melt viscosity starts decreasing rapidly and rising
pyrolysis vapour bubbles agitate the mix. Many properties of plastics can be derived using
methods used and developed by Van Krevelen [13]. The pyrolyzing plastic’s rheology is
poorly-documented, however, since the evolution of molecular size and structure with
time and the effects of extraneous matter are difficult to predict.
In a number of processes the plastics prior to pyrolysis are dissolved into product oil for
example, so that the viscosity is quite controllable. Other options, though today somewhat
obsolete, are the use of a molten lead, tin or salt bath. Unfortunately, residues accumulate
on top of this bath, and periodic shut-down for cleaning is inevitable. The process has
been used commercially for PMMA.
In fluidized bed units the plastics are dispersed over the surface of innumerable sand
or catalyst particles, greatly facilitating heat and mass transfer.
INTRODUCTION 19
3.4.2 Liquid vs Gas Phase Operation
It is somewhat difficult to visualize plastics as a liquid. The viscosity of a plastic melt
markedly decreases as the temperature is raised to levels at which pyrolysis becomes
rapid for all resins, i.e. 450◦ C. Several means may be used to bridge the gap between
feed temperature, generally room temperature, and reactor temperatures, namely:
• melting, plasticizing and possibly pyrolysing the feed in an extruder–feeder;
• dissolving the cold feed into hot liquid, serving as thermal flywheel and dissolver. Part
of the bath must periodically be discharged, to prevent the accumulation of residues
and coke. Coking is often a self-catalytic process!
Some processes feature a stepwise heating and decomposition. The idea has been
applied for analytical purposes (polymer blends), but seems also attractive for industrial
purposes, since it allows initially eliminating hydrogen chloride from mixtures contain-
ing polyvinylchloride at low temperature (250–400◦ C), then passing to a second step of
pyrolysis conducted at a more conventional, higher temperature (∼450◦ C), thus ensuring
a low residual chlorine content of the products eventually produced. It is essential, how-
ever, to ensure a high-quality disengagement of HCl from the melt; otherwise, some HCl
reacts, leaving organochlorine compounds in the melt.
Liquid phase pyrolysis often yields liquid fractions of an intermediate boiling point.
When applied to polyolefins it leads to synthetic oil fractions, the boiling range of which
decreases with rising pyrolysis temperature. Since lighter fractions have higher value
than high-boiling ones, there is interest in combining pyrolysis with a simple type of
distillation, i.e. refluxing the heavier fractions into the pyrolysis vessel. Another reason
for separating heavies at an early stage is the hazard created by having downstream lines
clogged by high-molecular-weight paraffin products.
Obviously, it is unfeasible to process polymers directly in the vapour phase. Most gas
phase operations feature a fluidized bed, either constituted of inert sand particles, or of
a cracking or reforming catalyst. The plastics fed into the bed are almost immediately
melted, coating the individual bed particles and pyrolyzing as a multitude of thin layers.
3.4.3 Mass Balances – Processing Margins

It is essential to determine the yield of each major product rather precisely and at different
values of the various operating parameters, mainly temperature, residence time, and pres-
sure. Many studies are incompletely documented, considering only gas or liquid phase
products, without mention of residues or mass balances. Moreover, in practice the prod-
uct yield of pyrolysis is reduced by losses inherent to consecutive purification. Inevitable
losses occur further during storage, transfer, and separation. Moreover, each raw material
as a rule contains nonproductive constituents, such as some moisture, metal inserts, coat-
ings, reinforcement agents, or fillers. These loss factors explain why laboratory data may
lead to overly optimistic views regarding possible industrial yields!
Establishing mass balances after pyrolysis tests is also important for economic reasons.
Economic figures are related directly with the operating margins, being the difference
between the value of the products and the cost of raw materials.
[Operating margin] = [(Unit value of product)i (Yield of product)i ]
− (Unit cost of raw material)
20 A. BUEKENS
This operating margin must cover all charges, such as equipment depreciation, and the
cost of manpower, and utilities (power, steam, cooling water, compressed air, etc.). Raw
materials of good purity and quality command a reasonable price in the marketplace.
3.5 VALUE OF THE RESULTING PRODUCTS
Some pyrolysis products have high value. These are mainly monomers, such as methyl-
methacrylate, caprolactam (the monomer of PA 6), tetrafluorethylene, or styrene. Others
are comparable to standard products with specifications of naphtha, kerosene, or gas-oil.
Such fractions have a well-known market, as follows from Table 1.7.
However, it is still questionable as to how far plastics pyrolysis can yield product
fractions, according to current specifications without extensive post-pyrolysis purification.
At Sapporo University, good olefin yields were obtained in the thermal cracking of oil,
derived from the local plastics-to-oil plant. The Niigata oil is locally used in a diesel
engine and not for sale!
Today important flows of plastics originate in mandatory recycling schemes, such as
those imposed by take-back obligations on packaging, End-of life vehicles, or waste
electric and electronic equipment (WEEE). For such materials, the drive for collection
and recycling is not normally economic, but mandatory. In such cases, there is often
a dump fee, to be paid for further processing a stream of waste plastics into recycled
products. The value of such fees varies from some 50 ¤/tonne for injection into blast
furnaces in the European Community to as much as 50–100 kYen (∼370–750 ¤/tonne)
3.5.1 Heat Balances

The major terms in the heat balance of a pyrolysis reactor are:
• evaporating any moisture contained;
• supplying sensible heat and latent melting heat to the plastics;
• supplying heat of reaction to the plastics.
Process heat requirements tend to be lower if the feed is stepwise heated, as in cer-
tain multistep or selective decomposition schemes of plastics mixtures, or in case the
Table 1.7 Some commodity prices (Financial Times, 3 August 2004)
Oil-Brent Blend (Sep) 39.95 $/bbl

Unleaded gas (95R) 441–443 $/metric tonne
Gas Oil (German Htg) 376–378 $/metric tonne
Heavy Fuel Oil 163–165 $/metric tonne
Naphtha 403–405 $/metric tonne
Jet Fuel 422–424 $/metric tonne
Diesel (French) 399–401 $/metric tonne
NBP Gas (Aug) 20.65–20.70 £/MWh
Euro Gas (Zeebrugge) 22.43–22.63 £/MWh
UKPX Spot Index 22.84 £/MWh
Conti Power Index 28.9373 £/MWh
Global COAL RB Index 62.45 $/metric tonne
bbl = barrel
INTRODUCTION 21
heat of condensation of product vapours can be used to preheat the feed. On the other
hand, such provisions also complicate plant construction and operation, and add to the
investment cost.
Another important factor is the rather poor thermal conductivity of plastics. Bockhorn
et al. [6] cite values for the heat conductivity of PS and PP as low as 0.17 W m−1 K−1 ,
for PET as 0.21 W m−1 K−1 , and for HDPE 0.41 W m−1 K−1 . The viscosity at 250◦ C
attains 2–3 Pa s (20 s−1 ).
Heat transfer at a wall is related to the Reynolds number, generally to the power ∼0.7.
Thus, there is great interest in securing a low viscosity when the heat of pyrolysis is to
be supplied. Dissolving the feed in oil is a possible procedure.
3.5.2 Thermodynamics
The relative stability of molecules can be read directly from some literature data tables.
The composition corresponding to thermodynamic equilibrium and the corresponding heat
of reaction can be derived relatively easily, as long as the required thermodynamic data
is available, e.g. in the Janaf Tables [19].
3.5.3 Kinetics and Mechanism of Pyrolysis

The study of kinetics and mechanism of pyrolysis is of considerable scientific interest, with
regard to the thermal behaviour of organic molecules, the precise constitution of molecules
or copolymers, including irregularities, such as structural defects and incorporation of
initiator molecules and radical scavengers, used to control the MW.
Some important results from the team of Professor Bockhorn (Cycleplast project) [6] are
shown in Table 1.8.
The kinetic parameters given are derived from the thermogravimetric experiments. The
mechanisms of pyrolysis, as discussed by this team, are too complex and varied to be
treated here in more detail.
E. Hakejova et al. [12], studied the pyrolysis of individual hydrocarbons, and of naph-
tha, kerosene, gas oil, and hydro-cracking fractions, as well as their copyrolysis with hex-
adecane, heptane, iso-octane, cyclohexane, and also with heavier feedstocks, i.e. dewaxing
Table 1.8 Some kinetic data (By courtesy of Professor Bockhorn, University of Karlsruhe)
Type of Melting Density Temperature Maximum rate of E Apparent

resin point, range (◦ C) decomposition at (◦ C) (kJ/mol) reaction
(◦ C) order, n
PA 6 218–224 1.12 310–450 415 211 ∼1
PS 110 1.05 320–415 355 172 1.04
PVC >140 1.4 210–350 (I) 250–280 (I) 140 1.5
350–500 (II) 425 (II) 290 1.8
HDPE 134 0.954 340–500 475 262 0.83
PP 163 0.91 340–460 425 190 0.3
PET 260 1.41 360–410 400
22 A. BUEKENS
cakes, high-boiling hydro-cracking fractions, and waste polymers. Heavier feedstock could
not be separately treated, because of coke formation in steam cracking.
The purpose was to evaluate the effects on processing and the product distribution
obtained by thermal cracking at 450◦ C when adding oil and wax products as an additional
feedstock, blended with naphtha, the regular feedstock. The thermal cracking mechanism
proposed is a Rice–Herzfeld type of free radical mechanism. Using the notations β and
µ, respectively for a reactive radical, mainly engaged in H-abstraction and for a larger,
mainly decomposing radical, a simple scheme can be written as:
Initiation: µ-H → β + β
H-transfer: µ-H + β → µ + β-H
Decomposition: µ → β + Olefin
Isomerization: µ ↔ µ
µ + µ-H ↔ µ + µ-H
Addition: β + Olefin → µ
µ + Olefin → µ
H-transfer: µ-H + µ → µ + µ -H
Termination: 2µ → Products
β + µ → Products
2β → Products
for describing the kinetics and mechanism of high temperature pyrolysis. Some studies
use standard software for this purpose, e.g. Thergas, Kingas [20, 21].
Obviously, depending on the type of catalyst and the operating conditions used, different
mechanisms and modes prevail in catalytic cracking.
4 FEEDSTOCK RECYCLING
4.1 SURVEY
Feedstock recycling encompasses processes that convert polyolefins and mixed plastics
into oil products, or PVC into HCl and coke. Such plastics pyrolysis, as yet, either in
Western Europe or the USA, is not an industrially relevant process, since only the reverse
process, the polymerization of monomers to high-molecular entities, creates value. Plas-
tics pyrolysis is technically and economically feasible only for selected polymers that
yield high-value, readily marketable monomer products, e.g. PMMA or PA 6. For bulk
polymers, such as polyolefins, polystyrene, polyesters, and PVC the scale of production
is too small and the margins too low to make plastics pyrolysis an economically viable
process. The presence of additives, soil, or other resins, incorporating hetero-atoms, leads
to both operating and product specification problems, rendering pyrolysis generally eco-
nomically unviable. Another important factor is securing an adequate dump fee, to sustain
the operation financially, as well as the availability of raw materials, a problem of finding
sources, optimizing logistic factors (plastics are light and bulky), sorting, cleaning and
handling, and ensuring steady specifications.
The raison d’être of feedstock recycling, i.e. thermal or chemical conversion of plastics
that cannot be recycled by mechanical routes, is thus not to create economic value, but
INTRODUCTION 23
rather a purely political decision, with limited economic value at current cost and capacity
factors.
Polyesters, polyamides and other poly-condensation polymers can be chemically recy-
cled simply by reversing their synthesis process by raising the process temperature, using
traditional processes such as hydrolysis, ammonolysis, acidolysis, transesterification, etc.
Bayer and other interested suppliers pioneered such processes that are beyond the scope
of this book. Such processes can also be used for adjusting the MW required in one
application (e.g. PET-bottles) to that needed in a different market (e.g. polyester fibres).
Gasification is another route potentially important in feedstock recycling. Basically,
plastics are fired with a sub-stoichiometric amount of oxygen + steam or of air, generating
a synthesis gas that can eventually be converted into ammonia, methanol, OXO-alcohols,
or hydrogen. The processes required for treating and purifying such gases are well known,
as well as their fundamentals. On a pilot scale, Texaco Inc. and Shell developed propri-
etary processes, in which the more usual liquid or pulverized coal fuels are replaced by
molten plastics. A few years ago, Texaco intended testing its technology in Rotterdam,
The Netherlands at a plant capacity of 50 000 tons of waste plastics a year. The only
operating plant at present is that of Ube Industries in Japan, in which plastics arising
from households are collected and baled, then gasified in a pressurized fluid bed reactor,
developed jointly by Ube and Ebara Co. An alternative is converting mixed, but chlorine-
lean plastics into the reducing gas, required in a blast furnace to reduce iron ore and
produce pig iron. The process is used in Japan by Nihon Kokan NKK (at present merged
into JFE-Holdings). In Europe, the process was also pioneered by Bremen Stahl (Arcelor
Group).
Hydrogenation has been pursued at the industrial level at the test plant by Veba Oel in
Bottrop, Germany [15].
Some of the techniques used may also apply to other organic compounds with medium-
high or high molecular weight, such as rubber, adhesives and glues, varnishes, paints or
coatings. Pyrolysis has also been used for cleaning purposes, e.g. separating paints, plastics
or rubber from metals. Since such operations are conducted on a small scale and in view
of metal recovery, it is uneconomic to recover organics. Rather, these are destroyed by
thermal or catalytic post-combustion.
4.2 PROBLEMS WITH HETERO-ATOMS
The major hetero-atoms appearing in polymers are: oxygen, nitrogen, chlorine, bromine,
fluorine. After plastics pyrolysis, these elements either appear as intermediate organic
compounds still incorporating the hetero-element, or as stable inorganic compounds,
i.e. water, ammonia and hydrogen cyanide, hydrogen chloride, hydrogen bromide and
bromine, hydrogen fluoride. Most of these are hazardous and corrosive and require a
careful selection of construction materials, as well as methods to neutralize or inhibit
their effect.
The presence of halogenated polymers and fire retardants, of heavy metals, and the
potential formation of dioxins are some of the problems addressed in various studies
presented at the successive Symposia on Feedstock Recycling (ISFR). Dehalogenation
is a major topic. Some important commercial polymers (PVC, PVDC, chlorinated PE)
introduce the element chlorine in almost any mixed feedstock, including those that are
24 A. BUEKENS
derived from MSW plastics, WEEE, or ASR materials. Moreover, the latter two streams
also contain brominated fire retardants that may pose problems during recycling. The
following important topics were addressed at the 2nd ISFR Symposium:
• elimination of chlorine from mixed plastic fractions, to produce oil, coke and gas
fractions, free from chlorine;
• scavenging of halogens from a reaction mixture;
• scrubbing of HCl and HBr from an off-gas flow;
• closing the Br loop, to create a sustainable solution to the problem of fire retardants;
• interactions between the flame retardants based on Br and on Sb in feedstock recycling.
Dehalogenation has been studied at several levels, namely that of (Contributions pre-
sented at the 2nd ISFR Symposium [9]):
1. Dehalogenation prior to or during the pyrolysis process. Okuwaki and Yoshioka mon-
itored debromination of Printed Circuit Boards (PCBs), at rising temperatures while
heating these under helium. These researchers treated various products arising from
plastics liquefaction plant in an autoclave using a mixture of NaOH and water, and
obtaining deep dechlorination after 3 h at 250◦ C. H. Ishihara and M. Kayaba (Hitachi
Chemical Co. Ltd., Japan, Sony Co., Japan) focused on epoxy resins, used in most
PCBs, and developed a technology to depolymerize brominated epoxy resins in a
solvent, in the presence of alkali metal compound. Thus PCBs separated into resin
solvent, glass cloth, and metals, including mounted devices and solder. M. P. Luda
et al. studied the thermal degradation of brominated bisphenol A derivatives. Sakata
et al. used iron oxide and calcium carbonate compounds to produce a halogen-free
oil, or treat gaseous effluents. Kamo et al. studied liquid phase cracking in H-donor
solvents, such as tetralin and decalin.
2. Dehalogenation of liquid products, using a catalyst prepared from goethite and phenol
resins for the dechlorination of chlorocyclohexane as a test substance (Matsui et al.).
3. HCl and HBr removal from gaseous effluents. Bhaskar et al. examined Ca-, Fe-, Zn-
and Mg-based sorbents for this purpose, obtaining good results with Ca-Z. Hakata
et al. tested an iron oxide-carbon composite catalyst for the selective vapour phase
dechlorination of chloroalkanes.
4. Dehalogenation in the presence of antimony, studied by Uddin et al.
5. Closing the bromine cycle, with initiatives of the European Brominated Flame Retar-
dant Industry Panel (EBFRIP) in cooperation with the Bromine Science and Environ-
mental Forum (BSEF), including a study prepared by ECN (Petten) on a two-stage
pyrolysis/high-temperature gasification process.
4.3 COLLECTION SYSTEMS
Under pressure from legislation, in particular the Packaging and Packaging Waste Direc-
tive, 94/62/EC, recycling of packaging products has increased dramatically from 1995. In
numerous E.U. countries, collection of waste plastics is part of the mandatory recycling,
imposed by the Packaging Directive and National Laws deriving from it (Table 1.9).
Eight countries recovered over half the waste plastics from packaging in 2000: the
Netherlands, Switzerland, Denmark, Norway, Germany, Sweden, Austria and Belgium.
INTRODUCTION 25
Table 1.9 Plastics packaging waste management systems in the E.U.
Country System responsible for collecting packaging waste

Europe Pro Europe sprl
Austria ARA Altstoff Recycling Austria AG
Belgium asbl Fost Plus vzw
Bulgaria EcoPack Bulgaria
Cyprus Green Dot Cyprus Public Company Ltd.
Czech Republic EKO-KOM, a.s.
Finland PYR Ltd
France Eco-Emballages SA; Adelphe
Germany Duales System Deutschland
Greece HE.R.R.CO Hellenic Recovery and Recycling Co.
Great Britain Valpack Ltd; BIFFPACK; WASTEPACK
Hungary ÖKO-Pannon p.b.c.
Ireland Repak Ltd.
Italy CONAI (Consorzio Nationale Imballagi)
Latvia Latvijas Zalais Punkts, NPO, Ltd
Lithuania Zaliasis Taskas, UAB
Luxemburg Valorlux asbl
Malta GreenPak Malta
Norway Materialretur A/S; RESIRK
Poland RekoPol-Organizacja Odzysku S.A.
Portugal Sociedade Ponto Verde, S.A.
Slovak Republic Envi-pak, a.s.
Slovenia Slopak d.d.o.
Spain Ecoembalajes Espana, S.A.
Sweden REPA-Reparegistret AB; RETURPACK PET
The Netherlands SVM-PACT
Turkey CEVKO
Waste electrical electronic equipment (WEEE) is being selectively collected in an

increasing number of E.U. countries, so that this stream can be considered available
and harnessed. ASR is available at car shredding plants.
4.4 LOGISTICS OF SUPPLY
Plastic resins are bulk commodities. A naphtha cracker producing ethylene has a typical
yearly capacity of 500 000 tonnes of ethylene, necessitating about 1.2 Mtonnes of naphtha
feedstock! Polymerization to resins is conducted with a somewhat lower capacity, but still
at the same order of magnitude, say 150 000 tonnes. Engineering plastics are produced
at lower capacity, but this lower rank is still far superior to the capacity of the largest
feedstock recycling units conceived to date!
The problem with post-consumer plastics is their immense variety and widespread
application. One tonne of plastics can be converted into either 20 000 two-litre drinks bot-
tles or 120 000 carrier bags! Collecting, sorting, baling, and transporting such numbers of
lightweight materials is a tremendous task, with typical cost levels as shown in Table 1.10.
From a dispersed source, such as households, curbside collection, followed by sorting,
cleaning, baling, is very expensive. The only way to reduce such cost is to introduce take
back systems.
26 A. BUEKENS
Table 1.10 Cost factors in selective collection from
household refuse
Activity Cost, ¤/tonne

Curbside collection 750–1000
Sorting 200–250
Recycling 50–750
Residue elimination, ∼15% of feed 15
Total 1000–3000
In some cases plastics or rubber are easier to collect. Automobile shredder residue is
such a potential source of waste plastics, arising at car shredding plant, as can be seen
at the following web site [22]. Solving the collection problem is trivial, since the waste
accumulate only at a limited number of plants. However, it is a mix of numerous different
resins, with embedded dirt, metal, and glass, and the best way to derive value is to dis-
mantle very large items (bumpers, dashboard, tyres, battery boxes) and mechanically or
thermally treat the balance. Automotive shredding residues are at present generally sent to
landfill. Ebara developed a fluid bed gasifier with subsequent combustion of the producer
gas and melting of entrained dust in a cyclonic combustion chamber. The molten ash is
tapped and granulated in a water quench. The demonstration plant at Aomori, Japan, has
operated on two lines since March 2000.
Waste from electrical and electronic equipment arises at the sorting plant, where the
frame, the printed circuit board PCB, the cathode ray tube, etc. are separated for recycling.
The remaining plastics fraction is in part flame-retarded, hence contains brominated and
antimony compounds. The number of WEEE recycling plants is growing, so that the
logistics are no longer a major problem.
Sources of raw materials, methods of identification and sorting have been reviewed
by Buekens [14, 23, 24]. It is remarkable that the general trends have remained largely
unchanged over the years, albeit that today there is another attitude regarding waste
management priorities and conceivably a much larger choice in automated sorting systems.
Still, sorting on the workfloor has remained mainly a manual operation until very recently:
the introduction of automated scanning and take-back machines created a market for
sorters, based on spectral fingerprints of bulk plastic streams. Advances are periodically
presented at Identiplast [25].
4.4.1 Voluntary Commitment of the PVC Industry

In the frame of Vinyl 2010 [26] the PVC Industry in the European Union made a number
of voluntary commitments, regarding the control of emissions from VCM-producing plant,
the phasing out of cadmium (both already realized) and lead-based stabilizers (to be
completed by 2015) and the voluntary recycling of 200 000 tonnes per year by 2010. Some
projects allow for mechanical recycling (Solvay’s Vinyloop, at Ferrara), but feedstock
recycling is also being considered [26].
In Japan, Nihon Kokan (now merged with Kawasaki Steel into JFE Holdings) developed
a rotary kiln technology for converting PVC into HCl and coke and operates a pilot plant
at Yokohama. The organic vapours are combusted prior to the recovery of HCl by wet
scrubbing.
INTRODUCTION 27
5 SOME FEASIBLE PROCESSES
A brief survey is given of a number of processes that have been used in Europe for
plastics pyrolysis. At present, all of these projects have been mothballed. The most relevant
initiatives are according to [15] :
1. Hamburg University Pyrolysis Process, high-temperature pyrolysis of mixed plastics,
using a fluid bed reactor. Demonstration plant at Ebenhausen has not survived shake-
down, due to various operating problems.
2. BASF low-temperature pyrolysis of mixed plastics, using a battery of stirred tank
reactors for liquefaction.
3. BP low-temperature pyrolysis of mixed plastics, using a fluid bed reactor.
4. Veba Oil hydrogenation technologies.
5.1 PILOT AND INDUSTRIAL PLANT OPERATION

5.1.1 Hamburg University, Ebenhausen
A plant operating according to the Hamburg University pyrolysis process was built at
Ebenhausen, with a capacity of 5000 tonnes per year. The feasibility of converting poly-
olefins by pyrolysis was successfully demonstrated, with yields from PE/PP mixtures of
typically 51% (m/m) gas, 42% (m/m) liquids and the balance unaccounted for. However,
the gas to liquids ratio is very sensitive to pyrolysis temperature. Since gas and oil are the
major pyrolysis products, economic viability crucially depends on the price of crude oil.
Under present conditions, profitability and economic viability are unsatisfactory at this
small scale of operation.
5.1.2 BASF, Ludwigshafen

The BASF feedstock recycling process was designed to handle mixed plastic waste, as
supplied by the DSD (Duales System Deutschland) green dot packaging collection system.
A large pilot plant, with a substantial capacity of 15 000 tonne/yr, was started up in
Ludwigshafen in 1994. At that time DSD estimated the total volume of mixed packaging
plastics available for feedstock recycling at around 750 000 ton/yr. BASF offered to erect
a full-scale industrial plant with a capacity of 300 000 ton/yr, but decided in 1996 to shut
down the pilot plant, since no agreement could be reached on a guaranteed long-term
waste supply and a gate fee sufficient to cover the costs.
In the BASF process, plastic waste is converted into petrochemical products in a three-
stage process. Before feeding, the plastics are shredded, freed from other materials and
agglomerated, to improve handling and enhance the density. In the first stage, the plastics
are melted and liquefied in an agitated tank. The gaseous hydrochloric acid, evolving from
PVC at temperatures up to 300◦ C, is absorbed in a water washer, and further processed
to aqueous hydrochloric acid, to be reused in other BASF production plants.
In a second stage, the plastic oil was fed into a tubular cracker reactor, heated at over
400◦ C and thus cracked into compounds of different chain lengths, forming petrochemical
raw materials. The oils and gases thus obtained are separated in a third stage, resulting
in the production of naphtha, aromatic fractions, and high-boiling oils. About 20–30%
of gases and 60–70% of oils are produced and subsequently separated in a distillation
column.
28 A. BUEKENS
HCI
Gases
Liquefaction
Plastic Pre-treatment Separation Oils
and cracking
High boilers,
residues
Figure 1.1 Schematic representation of the BASF pyrolysis process. (Reproduced by

permission of TNO)
The naphtha produced by the feedstock process is treated in a steam cracker, and the
monomers (e.g. ethylene, propylene, butadiene) are recovered. These raw materials are
then used for the production of virgin plastic materials. High-boiling oils can be processed
into synthesis gas or conversion coke and then be transferred for further use. All these
products have outlets in the local BASF production plants.
During two years of trial operation, the pilot plant demonstrated its suitability. Although
the process can be considered proven, it is at present neither used by BASF, nor elsewhere
in Germany, because the quantities of plastic waste and dump fee needed for the plant to
be economically viable are not available in Germany (Figure 1.1).
The process products are:
• HCl, which is either neutralized, or processed in a hydrochloric acid production plant;
• naphtha to be converted into monomers in a steam cracker;
• various monomers, which can be used for the production of virgin plastic materials;
• high-boiling oils, to be processed into synthesis gas or conversion coke;
• process residues, consisting typically of 5% minerals and metals, e.g. pigments or
aluminium can lids.
Processing plastic waste by the BASF process would have required a gate fee of
160¤/tonne for a plant with a capacity of 300 000 tonne/yr and a fee of 250¤/tonne for a
plant capacity of 150 000 tonne/yr [15].
5.1.3 BP, Grangemouth

In the early 1990s BP Chemicals first tested technology for feedstock recycling, using
a fluid bed cracking process. Research on a laboratory scale was followed (1994) by
demonstration at a continuous pilot plant scale (nominal 50 kg/hr) at BP’s Grangemouth
site, using mixed waste packaging plastics. The technology was further developed with
some support from a Consortium of European companies (Elf Atochem, EniChem, DSM,
CREED) and from APME. In 1998, BP Chemicals, VALPAK and Shanks & McEwan, set
up a joint project (POLSCO), to study the feasibility of a 25 000 tonne/yr plant, including
logistics infrastructure for supplying mixed plastics from Scotland. The project was seen
as a remedy to the expected UK shortage in recycling capability, required to comply with
EU and UK Packaging and Packaging Waste Directive.
INTRODUCTION 29
Some preparation of the waste plastics feed is required before pyrolysis, including size
reduction and removal of most nonplastics. This feed is charged into the heated fluidized
bed reactor, operating at 500◦ C, in the absence of air. The plastics thermally crack to
hydrocarbons, which leave the bed together with the fluidizing gas. Solid impurities and
some coke either accumulate in the bed or are carried out as fine particles and captured
by cyclones.
The decomposition of PVC leads to HCl formation, which is eventually neutralized by
contacting the hot gas with solid lime, resulting in a CaCl2 fraction to be landfilled. The
process shows very good results concerning the removal of chlorine. With an input of
1% Cl, the products contain ∼10 ppm Cl, somewhat higher than the 5 ppm typical of
refinery use. Also, metals like Pb, Cd and Sb can be removed to very low levels in the
products. Tests have shown that all hydrocarbon products can be used for further treatment
in refineries. The purified gas is cooled, condensing to a distillate feedstock, tested against
agreed specifications before transfer to the downstream user plant. The light hydrocarbon
pyrolysis gases are compressed, reheated and returned to the reactor as fluidizing gas.
Part of this stream could be used as fuel gas for heating the cracking reactor, but as it
is olefin-rich, recovery options were also considered. The flow scheme is illustrated in
Figure 1.2.
The process flow diagram shows hydrocarbon recovery in two stages, since the heavy
fraction becomes a wax at about 60◦ C. Once recovered, the light and heavy fractions
(about 85% by weight) could be combined together for shipment to downstream refinery
processing if the plastic feed is passed on as hydrocarbon liquid to the downstream plants.
The balance is gaseous at ambient temperature and could be used to heat the process. In
this way nearly all of the plastic is used with just solids separated as a waste product.
The gas has a high content of monomers (ethylene and propylene) with only some 15%
being methane.
Conceptually, the process can run in self-sufficient heating mode. In this case, overall
gas calorific requirement may need a small net export or import as the product gas quality
Lime
Plastics absorber
waste
Filter
Reactor
Hydrocarbon
Distillate feedstock
Fuel gas
Figure 1.2 Schematic representation of the BP process. (Reproduced by permission of

TNO)
30 A. BUEKENS
varies with plastic feed specification and operating conditions. The other main utilities
needed are:
• electrical power ∼60 kWh/tonne feed plastic;
• cooling water 40 m3 /tonne feed plastic;
• steam 1.2 tonne/tonne feed.
All emissions are very low and should comply with local regulations.
The cost of treatment depends on many factors such as scale, location, scope, required
preparation stages, and economic parameters used. Hence, comparison of the processes is
difficult. The investment costs of a plant of 25 000 tpa, located in Western Europe in 1998,
were estimated as 15–20 M£. Under these conditions, a gate fee of some 250 ¤/tonne is
necessary. For a 50 000-tpa plant this gate fee could be some 150 ¤/tonne. These figures
exclude the cost of collection and of preparation.
5.1.4 Veba Oil, Bottrop, Germany

From 1981 Veba Oil AG operated a coal-to-oil hydrogenation plant at Kohleöl Anlage
Bottrop (KAB) in Germany, using the Bergius Pier coal liquefaction technology to convert
coal into naphtha and gas oil. In 1987 the plant was modified, applying Veba Combi
Cracking (VCC) technology to convert crude oil vacuum distillation residues into synthetic
crude. Since 1988 a share of the petroleum residue feedstock was substituted by chlorine-
containing waste (containing, e.g. PCBs). In 1992/1993 a depolymerization unit was added
in front, to process exclusively mixed plastics waste from packaging, as collected by DSD.
In 1998 some 87 000 tonnes were treated. DSD and Veba both agreed to terminate their
contract in 1999, instead of in 2003: hydrogenation was unable to compete economically
with treatment in blast furnaces and with the SVZ process at Schwarze Pumpe.
The plant includes first a depolymerization section and then the VCC section
(Figure 1.3). In the first section, the agglomerated plastic waste is depolymerized and
dechlorinated at 350–400◦ C. The overhead product is partly condensed. The main part
(80%) of the chlorine introduced evolves as gaseous HCl in the light gases and is
washed out, yielding technical HCl. The condensate, still containing some 18% of the
chlorine input, is fed to a hydrotreater where the chlorine is eliminated together with the
water formed. The resulting chlorine-free condensate and gas are again mixed with the
depolymerizate for further treatment in the VCC section.
There, the depolymerizate is hydrogenated under high pressure (about 10 MPa) at some
400–450◦ C, using a liquid phase reactor without internals. Separation yields a synthetic
crude oil, which may be processed in any oil refinery. Light cracking products end up in the
off-gas and are sent to a treatment section, for removal of ammonia and hydrogen sulphide.
A hydrogenated bituminous residue comprises heavy hydrocarbons, still contaminated
with ashes, metals and salts. It is blended with coal for coke production (2 wt%).
The input specifications for the plastic waste are:
• particle size <1.0 cm;
• bulk density 300 kg/m3
• water content <1.0 weight %;
• PVC <4% (2 weight % chlorine);
INTRODUCTION 31
Condensate
Wash HCI
Condensates + gas
Gas
MPW
Depolymerisation VCC-LPH VCC-GPH
Depolymerisate
Syncrude
Hydrogenation
H2
residue Cokes production
Figure 1.3 Schematic representation of the Veba Oil process. LPH = Liquid phase
hydrogenation and GPH = Gas phase hydrogenation. (Reproduced by permission of
TNO)
• inerts <4.5 weight % at 650◦ C;

• metal content <1.0 weight %;
• content of plastic resins >90.0 weight %.
The process outputs are:
• Syncrude, derived from the VCC section. It is free from chlorine and low in oxygen
and nitrogen;
• a hydrogenated solid residue, which can be blended with coal for coke production;
• HCl;
• off-gas.
In 1997, successful treatment tests were completed on electric and electronic waste
with bromine-containing flame retardants. For this test, 50 tons of WEEE plastics were
mixed with some 250 tons of DSD waste.
The liquid products of the coal oil plant in Bottrop were pumped to the Ruhrol refinery,
which also processes the plant’s let-down gas. The solid residues are coked. A comparison
of the yields obtained in pyrolysis and hydrogenation shows that, roughly speaking, 50%
of the pyrolysis product is gas and 40% is oil, whereas 10% of the hydrogenation product
is gas and 85% is oil. Hetero-atoms contained in the plastics (Cl, O, N, S) are split off and
largely absent from product oil. The presence of PVC makes the process more resource-
intensive (increased consumption of hydrogen, required neutralization of HCl, disposal of
salts) and, hence, the input of Cl should not exceed a certain limit value. Mixed waste
plastics also contain physical impurities, such as fillers, pigments and adhering dirt.
Hence, Veba Oil developed a commercial process, operating in a temperature range
of 350–450◦ C and requiring a high hydrogen partial pressure (50–100 bar). The hetero-
atoms are hydrogenated to products such as hydrochloric acid or ammonia. A synthetic oil
distillate is obtained as the main product. Solid particles are concentrated in the sump of
the distillation column. The gate fee for the VCC process was 250 ¤/tonne. The technology
was realized in the coal-to-oil plant at Bottrop, with a capacity of 40 000 tonne annually,
doubled at the end of 1995. One tonne of waste plastics yielded:
• 800 kg high-quality liquid products;
• 100 kg methane–butane gas and a further
• 100 kg hydrogenation residues, containing inert and inorganic components.
32 A. BUEKENS
Schematic representation of the Texaco process, the Shell process, the AKZO steam
gasification process, the Linde KCA process, the NCR process and the BSL incineration
process are given by TNO [15].
5.2 CONCLUSIONS
Only few polymers can be recycled by pyrolysis under economically favourable condi-
tions. Nevertheless, important amounts are collected with the aim of realizing recycling
quota that were introduced under environmental pressure. The logistical problems of plas-
tics waste collection are huge: even collecting astronomical numbers of films or bottles
generates only rather modest amounts of materials, sufficient only to feed a pilot plant.
6 WASTE MANAGEMENT
6.1 PRINCIPLES
Waste management was once a down-to-earth technical problem, to be solved under

thrifty, yet environmentally ‘acceptable’ and hygienic conditions and preferably performed
by unskilled labour. Most waste was disposed of in landfills, except in densely populated
regions, where volume reduction by incineration was a practical necessity. The recovery
of heat, distributed in district heating systems or converted into electrical power was a
means of cooling flue gases prior to their cleaning, but barely contributes to cost reduction,
especially since a deep cleaning of flue gases became mandatory.
Today, however, waste management has turned into a fashionable legislation-driven
business, a responsibility of top management, as part of the environmental profile of each
corporation, and requiring expert knowledge in Law, Ethics, Politics and Sustainable
Development. Operators belong to the world’s largest service companies.
The E.U. waste management policy focuses on waste hierarchy, giving great priority
to waste prevention or reduction (elimination of technical or economic impediments and
distortions that encourage the over-production of wastes) followed by re-use, recycling,
recovery and residual management. Such a strategy includes an integrated approach to
waste management with emphasis on material recycling that is preferred over energy
recovery.
Waste prevention (or reduction) involves both (upstream) alterations in product design
as well as in consumer habits (downstream). Such strategies assure that the two objectives
of (quantity) less waste produced and (quality) less hazardous constituents utilized in
production (so that less hazardous wastes is generated) are both met. Waste prevention
is a strategy that prevents waste and its associated risks from being produced in the first
place.
In this process also the costs have soared, starting from a logic that the more expensive
it is to engender waste, the less there will be procreated and the more one will seek to
segregate it at the source or after a selective collection, and upgrade it to a secondary raw
material.
INTRODUCTION 33
6.2 PLASTICS WASTE
Pre-consumer plastic wastes are generated during the manufacture of virgin plastics from
raw materials (oil, natural gas, salt, etc.) and from the conversion of plastics into plastic
products. The nature of waste arising in various processing methods is discussed in [14].
Such waste streams are soiled (floor sweepings, skimmings from wastewater treatment,
crusts from polymerization reactors), mixed (laboratory testing), or off-specifications. Both
production and conversion waste are easily identified and collected and handled by profes-
sional scrap dealers that discover and develop applications and market outlets that allow
the use of secondary resins with less stringent and less defined specifications.
The amount of plastic waste generated is still considerably less than that of plastics
produced: in numerous applications (building, furniture, appliances) plastics meet long-
term requirements before their disposal and therefore do not yet occur in the waste stream
in big quantities. The majority of plastic wastes are found in municipal solid waste
(MSW), as well as in waste streams arising in distribution, agriculture, construction and
demolition, furniture and household ware, automotive, electronic and electrical, or medical
applications. For a number of years the APME has ordered studies to be made that compile
inventories of on the one hand production figures, on the other waste arising, by resin,
country, and application and activity.
In their efforts to educate the public and curtail the expansion of waste arising the
authorities have devised a number of legal instruments to make inappropriate disposal
more expensive (various levies, such as landfill taxes) and recycling more attractive, if
not mandatory. More and more waste streams are forced into this route, by means of
take-back obligations and minimum recycling quota. Under pressure from legislation,
recycling of packaging products has increased dramatically from 1995. These directives
are:
• Packaging and Packaging Waste Directive 94/62/EC;
• End of Life Vehicles Directive 2000/53/EC;
• Electrical and Electronic Waste: WEEE Directive 2000/96/EC;
• ROHS Directive 2000/95/EC.
However, the effect is not identical for all materials. Table 1.11 shows the results of
such take-back obligation for different packaging materials in Belgium, the collection and
recycling of which is entrusted to Fost Plus.
It follows that in Belgium (10 M inhabitants) Fost Plus pays more than 280 ¤/ton for
ensuring the collection and recycling of used packaging, including:
• 5.77 kg PET/inhabitant per year;
• 1.65 kg HDPE/inhabitant per year.
In Denmark the amount of plastic packaging waste collected for recycling amounted
in 2001 to 3.9 kg per inhabitant or 8.6 kg per household, compared with the potential
amount, equivalent to 28.1 kg per inhabitant or 62.0 kg per household.
Waste from the automotive industry, particularly from end-of-life-vehicles (ELV), has
been identified by the E.U. as another priority waste stream. After dismantling larger parts
suitable for mechanical recycling, the vehicle is shredded, the metal fraction (about 75%)
is removed, and the remaining residue is known as automotive shredder residue (ASR),
34 A. BUEKENS
Table 1.11 Packaging materials recycled by Fost Plus, Belgium (2003)
Material recycled Tonnage (kton) Contribution (M¤) Contribution (¤/ton)

Glass 309.6 7.2 23.3
Paper and board 133.3 2.1 15.7
Steel 80.8 5.1 63.1
Aluminium 9.9 2.2 222
PET 57.7 16.3 282
HDPE 16.5 4.7 285
Beverage cartons 20.5 5 244
Other recyclables 98.2 36.8 375
Other nonrecyclables 0.8 0.3 375
Total 727.3 79.7 110
a mixture of many different materials (Wittstock, BASF, at 2nd ISFR). ASR is a major
problem, since car manufacturers in Europe and Japan are forced to respect high recycling
quotas, suggesting the following conclusions (Schaeper, Audi AG, at 2nd ISFR):
• weight-related quota for mechanical recycling impede a lightweight design;
• feedstock processes are favourable to recover lightweight cars;
• feedstock processes should count as recycling processes;
• there is a need to increase acceptance of feedstock processes.
Feedstock recovery of ASR is conceivable via conversion into reducing gases after
injecting into the blast furnace in integrated iron and steel mills. Other gasification routes
were developed by Dow, Shell, Texaco, and Lurgi (Schwarze Pumpe). Ebara Co. devel-
oped fluid bed gasifiers for MSW, ASR and plastics from selective collection. The latter
are converted into synthesis gas at an operating pressure of 2–3 MPa, a development in
collaboration with Ube Industries. Full-scale plants are operating at present on each of
these feedstocks, e.g. Sakata (MSW), Aomori (ASR) and Ube (mixed plastics).
At 2nd ISFR, T. Yamamoto presented the gasification/melting system developed by
Sumitomo Metal Industries for converting MSW into high-calorific gas using metallurgical
techniques and oxygen.
Yasuda et al. studied the hydro-gasification of HDPE. Advanced rapid coal hydro-
gasification (ARCH) in Japan is developed as a route in the conversion of coal into
synthetic natural gas.
Worldwide use of plastics in consumer electronics and electrical equipment is growing
very rapidly, as is the waste volume related to such products, albeit with a time lag.
Similar rules affect the resulting electronic and electrical scrap (E & E), consisting of a
broad mix of thermoplastics (e.g. HIPS, ABS, ABS-PC) for the casings and thermosets
(epoxy resins) as major printed circuit board (PCB) material. The material is shredded,
metal parts separated and sent to metal processing companies. Van Schijndel and Van
Kasteren consider reprocessing using reactive agents such as siloxanes. The heavy metal
content of casings, e.g. from computer monitors or TV sets, is very low and these streams
can be separately shredded. An innovative depolymerization process using supercritical
CO2 can process heavy-metal-containing thermosets. In this way monomer recovery takes
place and heavy metals are separated from the materials for reprocessing.
INTRODUCTION 35
Several case studies in electronic and electrical scrap were presented at 2nd ISFR:
• components of a telephone were pyrolysed by Day et al. (National Research Council
of America),
• Satoh et al. (Sony Co.) reclaimed the magnetic material from tapes using supercritical
water to dissolve the resin;
• Noboru Kawai et al. (Victor Company of Japan, Ltd; National Institute of Advanced
Industrial Science and Technology) tackled the Chemical Recovery of bisphenol-A
from waste CDs or other polycarbonate resins.
An interesting alternative solution was developed in Denmark by Watech. However,
industrial preference was given to another process, combining hydrolysis as a method for
converting chlorine into hydroxyl substituents.
6.3 RUBBER WASTE
Rubber tyres are by far the most visible of rubber products. Identification is trivial and
collection is well organized. Recycling and disposal, however, are less evident. A major
route for tyres is their use as a supplemental fuel in cement kilns. Major compounds in
tyres are: styrene–butadiene rubber (SBR), synthetic and natural polyisoprene rubber, steel
cord, carbon black, zinc oxide, sulphur and vulcanization-controlling chemicals. Tyres can
be retreaded, which is economic for large sizes (truck tyres), or ground to crumb or powder
(cryogenic grinding). Such materials have some limited market potential as an additive
in asphalt, and in surfaces for tennis courts or athletics.
The macromolecular structure of (vulcanized) rubber can be degraded using thermal,
mechanical, and chemical means [14]. The resulting reclaim was once incorporated in
limited amounts in new tyres. Safety and quality considerations dried up this outlet.
Pyrolysis of tyres is a feasible, yet technically difficult operation. The handling of the
remnants of the steel carcass, the carbon black, the zinc oxide, as well as the tendency to
repolymerize of the major products are serious stumbling blocks. Various rubber pyrolysis
technologies have been developed, using, e.g. fluid bed, rotary kiln (Sumitomo Cement),
molten salts, or cross-flow shaft systems (WSL/Foster Wheeler).
Microwave pyrolysis results in relatively high-molecular-weight olefins and a high
proportion of valuable products such as ethylene, propylene, butene, aromatics, etc. The
short process time contributes to a reduction in the processing cost. Whole tyres or
larger chips can be processed, which greatly reduces pre-processing cost. The rubber is
transformed from a solid to a highly viscous fluid within milliseconds. With additional
curative agents the viscous material can be moulded into new products.
Supercritical water can be used to controllably depolymerize the rubber compounds.
Tires decompose into high-molecular-weight olefins (MW 1000–10 000), or oils (max.
90%). Roy [9] discussed vacuum pyrolysis at 2nd ISFR.
6.4 PLASTICS PYROLYSIS AS A WASTE MANAGEMENT OPTION
6.4.1 Status in the E.U

Almost since its foundation (1975) the Association of Plastics Manufacturers in Europe
(APME, Brussels) has monitored plastics production, consumption and waste generation.
36 A. BUEKENS
Major sectors are packaging, building and construction, automotive, electrical and elec-
tronics (E & E), agriculture, and others (e.g. furniture, houseware, toys, engineering).
After a short (e.g. packaging), medium (e.g. toys) or long lifetime (e.g. building) the
plastic product reports to one of various waste streams, such as municipal solid waste
(MSW), separately collected packaging, other recyclables, shredding waste (cars, white
goods, etc.), construction and demolition waste, agricultural waste, E & E-waste-etc.
Such waste streams differ internally with respect to their composition, the feasible
methods or modes of collection, and their legal status: producer responsibility has been
introduced for a steadily rising number of streams, requiring separate collection, adequate
treatment, and often mandatory recycling.
Already in the early 1970s the pyrolysis of plastic wastes to liquid fuels raised con-
siderable interest, first in Japan, later also in Western Europe, with pioneering work of
Professor Hansjorg Sinn and Walter Kaminsky, who developed the fluid bed Hamburg
pyrolysis process, and of Professor Menges at the RWTH Aachen. However, despite
extensive work at laboratory, pilot, or even an industrial scale, such work was jeopar-
dized by both technical problems and disastrous economic figures. Hence, in Western
Europe and the USA it is still at best a tentative process, balancing between political
pressures and economic reality. Major corporations, such as BASF, BP, Shell, Texaco
considered various options in pyrolysis and gasification, yet concluded that their large-
scale implementation remains illusory as long as suitable dump fees fail to be guaranteed
on the basis of contracts of sufficiently long duration and consequent volumes.
In Japan, however, plastics pyrolysis can now be considered to be state-of-the-art, and
making part of the integrated waste plastics recycling system. Still, the process is operating
at huge losses at both the levels of (1) collection cost and (2) treatment cost, and very few
signs are apparent that one day this situation may reverse. Treatment cost is of the order of
100 000 Yen/tonne of household plastics supplied at the plant. At 2nd ISFR [9] Kusakawa
reviewed and explained current Japanese environmental regulations, including the status of
polymer recycling and activities in industrial segments, such as packaging, automotive,
electrical/electronic industries. He mentions the relevant technological development in
Japan and importance of polymer recycling efforts to comply with the regulations. Among
these are the Recycling Promotion Law, the Containers and Packaging Recycling Law, the
Electrical Appliances Recycling Law, the Building Recycling Law, the Foods Recycling
Law, the Automotive Recycling Law.
Thus, the average consumer and industry are paying for realizing political long-term
views based on sustainable systems and oil and gas scarcity.
6.4.2 Japanese Initiatives and Processes

Both the Ministry of International Trade and Industry (MITI) and the Plastics Waste
Management Institute (PWMI) have been very active in promoting plastics recycling from
early in the seventies. In Tokyo, plastics and metals were considered as waste, unfit for
incineration and separately collected (1973) and treated in a Nippon Steel shaft furnace.
Early Japanese systems, e.g. from Japan Steel Works, Japan Gasoline Co., Kawasaki H.
I. Co., Mitsui Shipbuilding & Engineering Co., Mitsubishi H. I. Co., Nichimen, Sanyo
Electric Co., Sumitomo Shipbuilding, Toyo Engineering Co have been reviewed [14, 26].
A large variety of pyrolysis systems, featuring extruders, tubular reactor units, as well as
INTRODUCTION 37
larger fluidized bed or stirred tank reactor units was tested, as soon as plastics became a
visible component of municipal solid waste. More recently various commercial plants for
feedstock recycling of waste plastics are operating at a full scale:
1. ‘Liquefaction’ units (not to be confused with the hydrogenation processes) using con-
tinuous stirred tank reactors, at Niigata and Sapporo.
2. Blast furnace at the NKK (now JFE Holdings) Mikasa works.
3. Coke oven pyrolysis by Nippon Steel Corp.
4. High-pressure gasification by EBARA-UBE.
5. ASR gasification at Aomori (Ebara Co.).
6. Glycolysis of PET bottles by Teijin. Separated PET bottles are now used as raw
material for polyester fibres.
These Japanese successes are related to the practical implementation of the Containers
and Packaging Recycling Law, carried out in 1997 for PET bottles and in 2000 for
the other plastics. This law affords allocating the cost for feedstock recycling of waste
plastics separated in homes. It has created attractive markets and thus the separated waste
plastics are even in short supply in Japan. Recovery of plastics increased dramatically
since 2000, when the law was carried out. On the other hand, the cost for recycling
decreased gradually. This trend suggests that active competition improves both techniques
and logistic systems.
The Home Appliances Recycling Law came into full force in 2001 and is to be revised
within a few years. In such processes, not only the plastic cases, but also printed circuit
boards are recycled. the Law for Recycling End-of-Life Vehicles passed through the
Parliament, 2002. Clearly this law should promote the recycling of automotive shredder
residue.
The environmental policy of the Japanese Government traditionally has promoted the
recycling of waste plastics in Japan [27].
6.4.3 Ethical and Political considerations

In principle, it makes no sense to collect waste streams separately, unless suitable outlets
are secured for such flows. This seems the case for soiled and mixed plastic packaging
wastes, since these cannot be reprocessed to any better materials than those that substi-
tute low-grade wood and since the option of feedstock recycling is operating at a huge
economic loss. Moreover, no serious health, toxicity, or safety problems become apparent
in case of less strict collection requirements.
However, Green parties contend that the only way to reduce waste generation is to make
it prohibitively expensive. As a counter-argument, it may be stated that the funds lost in
plastics recycling are better invested in health, education, and social needs. At present,
most recycling options have mainly been introduced on an ideological basis, with limited
attention to their economic cost and social consequences. These can be tackled using
life-cycle analysis methods, i.e. the study of all environmental elements in a product’s
life-cycle [28]. According to RDC-Environment, Belgium, and Pira International, UK, the
selective collection and recycling of plastics has a positive cost–benefit balance for some
important applications, but is negative for others. Local parameters (quality of collected
38 A. BUEKENS
material, availability of output market, efficiency of the selective collection) play an
important role.
6.4.4 Safety Aspects

Plastics are often considered quite harmless and were specifically excluded from early lists
of hazardous waste, e.g. in Belgium (1976) and the Netherlands (1977). An exception was
the plastic packaging that served for packing hazardous compounds, such as pesticides.
Still, some harmful compounds can appear in waste plastics, e.g. additives containing
antimony, cadmium, lead, zinc, or hexavalent chromium, and plasticizers. Brominated
flame retardants spreading into the environment is another reason for concern and a
rational argument for dealing with WEEE and ASR-plastics [37].
6.4.5 Environmental Aspects

Little has appeared on the environmental effects of waste plastics pyrolysis. Conceptually,
the topic can be subdivided in those environmental aspects related to:
• collection, transportation of feed materials;
• pre-processing;
• heating and pyrolysis;
• pyrolysis products.
Sorting of plastics is often manual and can cause allergic and health problems. Remark-
ably, plastic waste is not without a smell, and air extracted from storage and handling is
thermally deodorized, e.g. at the Ube Industries gasification plant. Part of the pyrolysis
products can be regarded as toxic.
6.4.6 Useful Publications

APME (Association of Plastics Manufacturers Europe, today Plastics Europe), with mem-
ber companies given in [29] has classified plastic waste in a series of categories and
monitors their origin and recycling, according to their field of application. Several early
publications are still of interest, to compare past and present. A recent book on plastics
recycling is Scheirs [38]. A few sites of interest are also:
• Community Recycling, a comprehensive guide to setting up, maintaining or expanding
a local recycling scheme [30];
• Waste at Work, a practical guide to dealing with office waste, reducing and reusing
everything from toner cartridges through to toilet rolls, as well as a step-by-step guide
to setting up an office recycling scheme [31];
• The National Recycling Directory, listing United Kingdom national and regional con-
tacts for recycling of various materials including local authority, industry and com-
munity organisations [32];
• The Recycled Products Guide, the searchable UK listing of products made from recy-
cled material [33];
INTRODUCTION 39
• Plastics in the UK Economy, a guide to polymer use and the opportunities for recycling
in different industry sectors [34, 35].
7 CONCLUSIONS
Plastics pyrolysis has long been topical in academic circles and also continues to inspire
industrial R&D and demonstration projects. Still, the pyrolysis of mixed plastics is eco-
nomically to be proven, because of the small scale of the potential pyrolysis plant and
the huge cost expenditure for collecting, cleaning and grading considerable tonnages of
plastics. It is hoped that these costs will be covered by the value of the products obtained
and, economically speaking, incineration is today a more reasonable option for the larger
part of household plastics waste. Indeed, in only very few cases plastics pyrolysis is an
economically viable process, e.g. PMMA and PA-6 pyrolysis, because of the high value
of the monomers produced. The size of pyrolysis plant there is limited by the availability
of scrap.
Still, today industry is obliged by political pressure to consider plastics pyrolysis, or
more in general, feedstock recycling attentively: under green pressure there is a legal
obligation to collect and recycle certain streams, such as those of packaging, automobile
shredder residue ASR, and waste electronic and electrical equipment. Industry has an
obligation to take back and recycle such materials, and is forced to consider all options,
optimizing or at least testing recycling processes as a function of technical possibilities,
feedstock characteristics, and, most of all, legal constraints. The boundary conditions of
directives and their translation into national laws is still open for discussion, as follows
from the different modes and levels of recycling, applied in the various member states
and from the exportation of such flows to low-labour-cost countries.
The concept of feedstock recycling is based on a thermal and sometimes catalytic
breakdown of polymer structure, yielding monomers (PMMA, PA-6, PS, PTFE), oil frac-
tions, aromatic fractions, synthetic crude, or synthesis gas. To some extent plastics can
be converted in the framework of oil refinery processes, such as viscosity breaking, fluid
catalytic cracking, hydro-cracking and delayed coking, or in coal liquefaction [36], but
these applications may require a preliminary thermal breakdown or dissolution into or
extensive dilution by more conventional feedstock. The desired product and its specifi-
cation requirements are essential in selecting operating modes and conditions and should
be considered on a case by case basis.
The ‘thermal cracking’ of this plastic waste stream is realized via pyrolysis, hydro-
genation, or gasification. Since the recovered hydrocarbon products are mostly used in
petrochemical processes, their specifications limit the amounts of halogens into the ppm
range. Subsequently, the collected mixed waste streams are pre-treated and graded accord-
ing to their chlorine content. Another possibility is thermal dehalogenation, either in a
liquid or in a fluidized bed pyrolysis, before the pre-treated product is further processed.
The hydrochloric acid produced is either neutralized or separated for industrial use, e.g.
in the pickling of steel, or in chemical industry.
Feedstock recycling is complementary to mechanical recycling since it is less sensitive
to unsorted or contaminated plastics waste and enlarges the overall recycling capacities
for large waste quantities to be supplied in the future. Examples of such mixed streams are
40 A. BUEKENS
specific composites (laminated films, artificial leather, footwear), but mainly packaging,
ASR, WEEE. These materials are connected to each other for performance reasons, but
economic separation is impossible.
Technical processes for feedstock recycling have inspired large corporations, universi-
ties, and inventors alike and are the origin of numerous patents. As many of the feedstock
recycling processes described in this chapter are still in development, their economic via-
bility also remains yet to be established. This will become clearer over the next several
years, in tandem with technical progress and the increased volumes of available plastics
wastes [38].
REFERENCES
1. G. S Brady, H. R. Clauser, Materials Handbook, 13th edn, McGraw-Hill Inc., ISBN

0-07-007074-1, 1991.
2. http://www.ftns.wau.nl/agridata/apme/plastics.htm
3. http://www.envocare.co.uk/plastics.htm
4. S. L. Madorsky, Thermal Degradation of Organic Polymers, New York: Wiley Inter-
science, 1964.
5. M. P. Duncan, D. J. Hourston, F. Dumont, Thermogravimetry of Polymers, in Ency-
clopedia of Analytical Chemistry, R. A. Meyers (ed.) pp 8094–8105 Chichester:
John Wiley & Sons, Ltd, 2000.
6. http://dbs.cordis.lu/fep-cgi/srchidadb?ACTION=D&SESSION=254642005-3-6&
DOC=4&TBL=EN PROJ&RCN=EP DUR:36&CALLER=PROJ INCO
7. http://www.gefta.uni-freiburg.de/de/normen.html
8. 1st ISFR, The 1st International Symposium on Feedstock Recycling of Plastics,
Sendai, Japan, 1999.
9. 2nd ISFR, The 2nd International Symposium on Feedstock Recycling of Plastics,
Ostend, Belgium, 2002.
10. A. G. Buekens, G. F. Froment, Fundamental aspects of the design of tubular crack-
ing units, Proceedings of the 4th European Symposium on Chemical Reaction Engi-
neering, Brussels, 9–11 September 1968.
11. E. A. Williams, P. T. Williams, The pyrolysis of individual plastics and a plastic
mixture in a fixed bed reactor. Journal of Chemical Technology and Biotechnology,
70 (1), 9–20, 1997.
12. E. Hakejova, M. Bajus, J. Daniskova, 16th Intenational Symposium on Analytical
and Applied Pyrolysis, Alicante, 24–26 May 2003.
13. D. W. Van Krevelen, Properties of Polymers, Their Estimation and Correlation with
Chemical Structure, 2nd edn, New York: Elsevier, 1976.
14. A. G. Buekens, Some observations on the recycling of plastics and rubber. Conser-
vation and Recycling 1, 247–271, 1977.
15. A. Tukker (TNO-STB), Ing H. de Groot (TNO Industrial Research), Ir.L. Simons
(TNO-STB), Ir. S. Wiegersma (TNO Industrial Research), Chemical Recycling of
Plastics Waste (PVC and Other Resins), TNO-Report STB-99-55 Final, 1999, Euro-
pean Commission, DG III
16. http://www.energy.ca.gov/oil/refinery output/definitions.html
INTRODUCTION 41
17. http://www.eia.doe.gov/glossary/glossary n.htm
18. http://www.petrochem-ir.net/expospec/sp-c5plu.htm
19. Janaf Tables: http://webbook.nist.gov/chemistry/form-ser.html
20. C. Muller, V. Michel, G. Scacchi, G. M. Côme THERGAS: a computer program
for the evaluation of thermochemical data of molecules and free radicals in the gas
phase, J. Chim. Phys. (1995) 92, 1154–1178
21. http://www.ensic.u-nancy.fr/DCPR/Anglais/GCR/softwaresdescription/kingas.htm
http://www.ensic.u-ancy.fr/DCPR/Anglais/GCR/softwaresdescription/thergas.htm
22. http://www.plastics-in-elv.org/refmatrecygenl.htm
23. A. G. Buekens, Opportunities in the Sorting of Waste Plastics, Recycling Berlin,
531–541, 1984
24. A. G. Buekens, G. Patfoort, A. Vandermeerschen, Les systèmes de collecte et de
tri des déchets des matières plastiques et les problèmes à résoudre pour optimiser
ces technologies, Colloque International sur le Recyclage des Déchets de Matières
Plastiques, Paris, 9–11 March 1988 In : Le Recyclage des Déchets de Matières
Plastiques, EUR 11717, p 96–121
25. http://www.apme.org/dashboard/business layer/template.asp?url= http://www.apme.
org/media/public documents/20030509 100340/press events identiplast overview
2003.htm
26. http://www.vinyl2010.org/
27. A. Okuwaki, in http://www.imc.cas.cz/sympo/42 micros/mainlect.htm#ML6
28. www.apme.org/LCA
29. http://www.apme.org/media/publicdocuments/20020614 112310/APME Members
Companies.pdf
30. http://www.wasteonline.org.uk/resources/WasteWatch/CommunityRecycling.htm
31. http://www.wasteonline.org.uk/resources/WasteWatch/WASTEWORK1.htm
32. http://nt.oneworld.org/wastewatch/public/index.cfm
33. http://www.recycledproducts.org.uk/
34. http://www.plasticsintheuk.org.uk/
35. http://www.bpf.co.uk/bpfindustry/process plastics recycling.cfm
36. A. G. Buekens, J. Schoeters, Technical methods in plastic pyrolysis; Macromol.
Symp., 135, 63–81, 1998.
37. UNEP/CHW.6/21, Technical guidelines for the identification and environmentally
sound management of plastic wastes and for their disposal, 23 August 2002.
38. J. Scheirs, Polymer Recycling, Science Technology and Applications, Wiley Series
in Polymer Science, 1st edn, Chichester: John Wiley & Sons, Ltd, 1998.
PART II
Catalytic Cracking
2
Acid-Catalyzed Cracking of
Polyolefins: Primary Reaction
Mechanisms
ROBERT L. WHITE
Department of Chemistry and Biochemistry, University of Oklahoma, Norman, OK
73019, USA
1 INTRODUCTION
New plastic waste recycling alternatives that are based on catalytic cracking can poten-
tially lower costs and increase yields of valuable products. Future development of effective
plastic waste recycling methods that involve catalytic cracking will require detailed knowl-
edge of the relationship between cracking conditions and product distributions. Operating
conditions that maximize the production of valuable hydrocarbon products and mini-
mize catalyst deactivation must be sought. In particular, reaction conditions under which
polymers are efficiently converted to small paraffins (C5 –C10 ) are desired because these
substances are used as feedstocks by industry and as fuels and therefore constitute high-
value products. During the past 35 years, numerous studies have been reported in which a
variety of catalysts and reaction conditions have been employed to convert waste polymers
into hydrocarbon mixtures.
Previous catalytic cracking research has focused primarily on polyolefin feedstocks
because these polymers are the most abundant in plastic wastes. In one of the first poly-
mer catalytic cracking studies, Uemichi and co-workers reported the use of silica–alumina,
activated carbon, Pt/silica–alumina, and Pt/alumina catalysts for poly(ethylene) (PE)
cracking [1–4]. Several years later, Takesue and co-workers reported that PE cracking
under mild conditions with a silica–alumina catalyst could be used to shorten polymer
chains and increase chain branching [5–8]. In 1989, Beltrame and Carniti compared alu-
mina, silica, HY, REY, and silica–alumina catalysts and reported results from PE catalytic
cracking in a batch reactor at reduced pressures [9]. Using activation energy calculations,
they found that the zeolite catalysts (HY and REY) were the most effective of those
46 R.L. WHITE
tested. Ivanova et al. described the effects of Lewis acid catalysts on PE cracking in 1991
[10]. They found that volatile product selectivity could be varied by changing the catalyst
acidity. For example, when PE was cracked by AlCl3 , 41% of the volatile products were
C4 hydrocarbons. C4 hydrocarbon yield increased to 85% when MgCl2 •AlCl3 catalyst was
employed. During the early 1990s, several groups became interested in using catalysts to
reform PE thermal decomposition products [11–15]. In these studies, PE was thermally
cracked and the resulting polymer fragments were subjected to catalytic reforming. The
number of published reports pertaining to PE cracking increased substantially in the past
six years [16–57]. Most of this research has focused on the effects of catalyst structure
on cracking products with emphasis on finding conditions that maximize production of
hydrocarbon mixtures that could be used as fuels.
Compared with PE, fewer reports of poly(styrene) (PS) catalytic cracking have been
published. In 1976, Yamamoto et al. reported that heating PS in the presence of a sil-
ica–alumina catalyst yielded large amounts of benzene, cumene, and toluene [58]. Five
years later, Pukanszky and co-workers reported that addition of Lewis acids to PS melt
resulted in chain shortening and formation of double bonds [59]. In 1990, Audisio et al.
reported the use of silica, alumina, silica–alumina, HY, and REY catalysts for cracking
PS under vacuum at temperatures between 200 and 550◦ C [60]. In 1997, Sedran and
co-workers used a fluidized-bed reactor to crack PS [61, 62]. More recently, PS cracking
by zeolites, mesoporous MCM-41 and amorphous silica–alumina were compared [63]
and metal-supported carbon catalysts were used to crack PS in decalin [64]. Guoxi et al.
tested the effects of various metal powders on PS thermal decomposition [65]. They found
a correlation between activity for styrene production and metal electronegativity.
The use of a wide variety of reactor designs and operating conditions with catalysts
having different properties to crack waste polymers have led to reports of cracking product
distributions that on the surface appear to vary significantly. In addition to the primary
products that result from interactions between polymer and catalyst, secondary reactions
can lead to additional substances in the product slate. The amount and identities of these
additional substances are dependent on reactor design and operating conditions. In order to
compare and contrast polymer cracking reaction processes and to associate reaction path-
ways with specific polymer–catalyst interactions, it is necessary to design experiments so
as to keep reaction conditions as constant as possible and to employ reactors that minimize
secondary reactions. This can be achieved by using samples containing low polymer-to-
catalyst ratios, employing low cracking temperatures, and designing experiments so that
volatile products are efficiently removed from catalyst surfaces.
2 POLYETHYLENE CRACKING
Although a wide variety of catalysts have been employed to crack PE, zeolites have
proven particularly effective. For example, Garforth et al. reported that activation ener-
gies (Ea ) measured when PE was catalytically cracked by HZSM-5, HY, and MCM-41
were much lower than when no catalyst was present. [66] They concluded that HZSM-
5 and HY have similar activities and that both of these zeolites were more effective
than MCM-41. Manos and co-workers found that catalytic cracking of PE by HZSM-5
and HY was effective in producing gasoline size hydrocarbons in a laboratory semi-
batch reactor [67, 68]. Mordi and co-workers reported that H-Theta-1 and H-Mordenite
ACID-CATALYZED CRACKING OF POLYOLEFINS 47
zeolites, which have pore diameters that are comparable to those for HZSM-5 and HY,
were relatively ineffective in producing gasoline size hydrocarbons from PE cracking
[69]. Clearly, catalyst pore size and acidity are important factors in polymer catalytic
cracking.
Most PE catalytic cracking studies have been performed by heating reactor vessels con-
taining catalyst and polymer and subsequently collecting and analyzing the products. This
batch processing approach provides no information regarding the order in which prod-
ucts form. In addition, if sealed reaction vessels are employed, initial reaction products
may react with catalyst to form secondary products. Recently, repetitive injection GC/MS
has been used to characterize the volatile products generated by polymer cracking. This
evolved gas analyzer facilitates real-time separation, identification, and quantification of
volatiles generated by heating solid samples [70]. A diagram of this apparatus is shown
in Figure 2.1. Thermal analyzer effluent (TA effluent) is the purge gas exiting from a
thermogravimetric analyzer or a tube furnace in which the sample is heated. A ther-
mogravimetric analyzer is employed when weight loss information is desired. Volatile
polymer cracking products are separated by a small gas chromatograph which can be
heated rapidly (300◦ C/min) and cooled rapidly (600◦ C/min) in order to facilitate rapid
capillary gas chromatography separations employing column temperature ramps. Repet-
itive gas chromatographic injections are made by using an eight-port valve to divert
effluent trapped in the injection loop onto the gas chromatographic column. The end of
Injection Sample loops

valve
Splitter
GC valve
injector
To ion
source
Strip
TA
heater
effluent
GC
column
Figure 2.1 Apparatus used for repetitive injection gas chromatography analysis of
volatile polymer decomposition products. (Reproduced from the Journal of Chromato-
graphic Science by permission of Preston Publications, a Division of Preston Industries,
Inc)
48 R.L. WHITE
the fused silica capillary gas chromatography column is attached to the ion source of
a quadrupole mass spectrometer for detection and analysis of eluting volatile products.
By using this apparatus, product trapping is not required. Instead, volatile products are
removed from catalysts with an inert purge gas and then analyzed on-line. This approach
was used to study the primary reaction processes when PE is cracked by HZSM-5, HY,
and MCM-41 aluminosilicate catalysts [71]. Because these three acid catalysts possess
different acid strengths and pore structures, information regarding the effects of pore size
and acid strength on cracking processes were obtained by comparing volatile product
evolution profiles.
Figure 2.2 shows repetitive injection GC/MS chromatograms obtained while heating
PE-catalyst samples at 2◦ C/min in a helium atmosphere. The tick marks on the x-axes in
Figure 2.2 denote PE-catalyst sample temperatures at which evolved gases were injected
into the gas chromatograph. Twenty-five successive gas chromatograms were obtained
for each of the PE-catalyst samples. Purge gas effluent was analyzed at 5- min inter-
vals, which corresponded to 10◦ C sample temperature increments. Figure 2.2 shows that
the temperature range over which volatiles were produced depended on the choice of
cracking catalyst. The maximum volatile product evolution rate for the PE-HY sample
4000
TIC
2000
0
150 250 350
(a)
6000
TIC
3000
0
150 250 350
(b)
6000
TIC
3000
0
150 250 350
Temperature (°C)
(c)
Figure 2.2 Evolved gas chromatograms obtained by repetitive injection GC/MS for
(a) PE-HZSM-5, (b) PE-HY, and (c) PE-MCM-41. (Reproduced by permission of John
Wiley & Sons Ltd)
occurred at the lowest temperature (220◦ C), followed by the PE-MCM-41 (260◦ C), and
PE-HZSM-5 (280◦ C) samples. After comparing the shapes of successive chromatograms
in Figure 2.2(a), it is apparent that volatile product distributions changed significantly
for the PE-HZSM-5 sample above 290◦ C. The dominant volatile species detected above
310◦ C were alkyl aromatics. Similar variations are apparent in the PE-HY chromatograms.
Although volatile product slates for the PE-MCM-41 sample also changed with temper-
ature, no alkyl aromatic species were detected in the repetitive injection chromatograms
for this sample.
Chromatograms obtained while heating the three PE-catalyst samples show catalyst-
dependent differences in volatile product distributions. Figure 2.3 shows the gas chro-
matograms obtained at the temperatures corresponding to the maximum volatile product
evolution rates for each PE-catalyst sample. Figure 2.3 clearly shows that relative hydro-
carbon product yields depended on which catalyst was employed. For the PE-HZSM-5
sample, many isomeric hydrocarbons were detected, most of which were low molecular
weight substances with short retention times. Volatile product diversity is less evident
4000
TIC
2000
0
0 1 2 3
(a)
6000
TIC
3000
0
0 1 2 3
(b)
6000
TIC
3000
0
0 1 2 3
(c)
Retention time (min)
Figure 2.3 GC/MS chromatograms obtained at sample temperatures corresponding

to maximum volatile product evolution for: (a) PE-HZSM-5 (280◦ C), (b) PE-HY (220◦ C);
(c) PE-MCM-41 (260◦ C). (Reproduced by permission of John Wiley & Sons, Ltd)
50 R.L. WHITE
4000
Integrated TIC
C4 (1)
C5 (1)
2000
C6 (3)
C7 (1)
0
200 300 400
Temperature (°C)
(a)
C3 (1)
C4 (3)
12000
C5 (4)
Integrated TIC
C6 (6)
6000
C7 (4)
C8 (3)
0
200 300 400
Temperature (°C)
(b)
4000 C1-Ph (1)

Integrated TIC
C2-Ph (3)
2000 C3-Ph (2)

C4-Ph (2)
0
200 300 400
Temperature (°C)
(c)
Figure 2.4 Species-specific evolution profiles for: (a) paraffin; (b) olefin; (c) alkyl aro-
matic products obtained when a PE-HZSM-5 sample was heated. (Reproduced by
permission of John Wiley & Sons, Ltd)
in the PE-HY chromatogram. The volatile product slate generated by heating the PE-
MCM-41 sample was similar to that obtained for the PE-HZSM-5 sample, except that
low-molecular-weight products were not as abundant.
Figure 2.4 shows species-specific evolution profiles for paraffin, olefin, and alkyl aro-
matic volatile products formed by heating the PE-HZSM-5 sample. The numbers in
parentheses denote the number of isomers detected. The volatile product slates for the
PE-HZSM-5 sample reflect that C3 –C5 hydrocarbons were the dominant species formed.
The temperature corresponding to the maximum paraffin and olefin evolution rates was
280◦ C, whereas alkyl aromatic evolution maximized at 310◦ C. Below 200◦ C, volatile
product mixtures were composed entirely of paraffins. Mass spectra for paraffin prod-
ucts were consistent with branched rather than straight-chain structures. The only C4
and C5 paraffins detected were isobutane and isopentane. Above 200◦ C, many different
olefin isomers were detected in volatile mixtures. In addition to paraffin and olefin prod-
ucts, substantial quantities of alkyl aromatics were detected for the PE-HZSM-5 sample.
Figure 2.4(c) shows that aromatics with C1 –C4 alkyl groups were detected and that C2 -
substituted aromatics (xylenes and possibly ethyl benzene) were the dominant aromatic
products.
Species-specific evolution profiles for the PE-HY sample are shown in Figure 2.5.
Unlike the PE-HZSM-5 results, volatile mixtures were primarily composed of C4 –C8
paraffin rather than olefin products. Evolution profiles for paraffins and olefins had similar
shapes with maximum evolution rates occurring at 230–240◦ C. Like the paraffin evolution
profiles for the PE-HZSM-5 sample, isobutane and isopentane were significant paraffin
products and no straight-chain isomers were detected. Alkyl aromatic yields for the PE-HY
sample were much lower than for the PE-HZSM-5 sample.
Species-specific evolution profiles for the PE-MCM-41 sample are shown in Figure 2.6.
Like the PE-HZSM-5 sample, olefin yields were much greater than paraffin yields for the
PE-MCM-41 sample. Paraffin evolution profiles in Figure 2.6(a) mostly represent single
isomers. In contrast, many olefin isomeric species were detected. C4 –C6 olefins com-
prised the largest fraction of volatile mixtures. Unlike the PE-HZSM-5 sample, propene
was a minor volatile product. Alkyl aromatic products were not detected for this sample.
Volatile products derived from cracking PE with solid acid catalysts can be rational-
ized by carbenium ion mechanisms. Under steady-state conditions, hydrocarbon cracking
processes that yield volatile products can be represented by initiation, disproportionation,
β-scission, and termination reactions [72, 73]. Initiation involves the protolysis of PE with
Brönsted acid sites (H+ S− ) to yield paraffins and surface carbenium ions:
Cn H2n+2 + H+ S− → Cm H2m+2 + Cn−m H+ 2(n−m)+1 S−
Propagation reactions involve disproportionation between feed molecules and surface

carbenium ions to yield paraffins:
Cn H2n+2 + Cm H+ 2m+1 S− → Cm+x H2(m+x)+2 + Cn−x H+ 2(n−x)+1 S−
When a surface carbenium ion undergoes β-scission to form olefin products, smaller
carbenium ions are left on the catalyst surface:
Cn H+ 2n+1 S− → Cx H2x + Cn−x H+ 2(n−x)+1 S−
When sufficiently small, olefins may desorb from catalyst surfaces. Surface olefins
may also be protonated to form new carbenium ions. Termination reactions involve the
destruction of surface carbenium ions. For example, surface carbenium ions may desorb
to produce olefins and regenerate Brönsted acid sites:
Cn H+ 2n+1 S− → Cn H2n + H+ S−
52 R.L. WHITE
C4 (2)
10000
Integrated TIC
C5 (1)
C6 (3)
5000
C7 (3)
C8 (5)
0
200 300 400
Temperature (°C)
(a)
3000 C3 (1)
Integrated TIC
C4 (3)
2000 C5 (3)
C6 (2)
1000
C7 (2)
0
200 300 400
Temperature (°C)
(b)
1000 C2-Ph (2)

Integrated TIC
C3-Ph(2)
500
0
200 300 400
Temperature (°C)
(c)
Figure 2.5 Species-specific evolution profiles for: (a) paraffin, (b) olefin; (c) alkyl aro-
matic products obtained when a PE-HY sample was heated. (Reproduced by permission
of John Wiley & Sons, Ltd)
These chain reactions describe how paraffin and olefin cracking products are formed, but
do not explain residue or aromatic product formation. Like the other reactions, aromatic-
and coke-forming reactions involve surface carbenium ions. Carbenium ion thermal crack-
ing can result in olefin ions, which may undergo dehydrogenation and cyclization reactions
that are suspected to be the source of aromatic products from straight-chain paraffin feeds.
When unsaturated ions are protonated, di-ions are produced. Doubly charged ions can also
be formed by disproportionation reactions between adjacent surface carbenium ions. Mul-
tiply charged ions are strongly bound to surface conjugate base sites and are less likely
to participate in reactions with feed than singly charged carbenium ions. Consequently,
C4 (1)
Integrated TIC
4000 C5 (1)
C6 (1)
2000 C7 (2)
C8 (1)
0
200 300 400
Temperature (°C)
(a)
30000 C3 (1)
C4 (3)
Integrated TIC
20000 C5 (4)
C6 (5)
C7 (6)
10000
C8 (5)
C9 (1)
0
200 300 400
Temperature (°C)
(b)
Figure 2.6 Species-specific evolution profiles for: (a) paraffin; (b) olefin products
obtained when a PE-MCM-41 sample was heated. (Reproduced by permission of John
Wiley & Sons, Ltd)
catalyst sites occupied by polyions are unavailable for further reaction. Catalyst acidity
and pore size dictate the relative rates of protolysis, disproportionation, β-scission, and
termination reactions, which determine the abundance of volatile paraffin, olefin, aromatic,
and nonvolatile hydrocarbon products.
Disproportionation reaction rates depend on carbenium ion reactivities, which are deter-
mined by catalyst site acid strength. Carbenium ions produced at strong acid sites are
less likely to undergo β-scission or desorption. Compared with HY, the smaller pores
in HZSM-5 inhibit bimolecular disproportionation reactions. In contrast, the low paraf-
fin/olefin volatile product ratio for the PE-MCM-41 sample is likely due to the low
acidity of the catalyst. Although the MCM-41 pore size is large enough to facilitate
disproportionation, catalytic site acidity is too low for this reaction pathway to be dom-
inant.
Aromatic products were detected at temperatures above those at which paraffin and
olefin evolutions maximized. The shift in alkyl aromatic evolution profiles to higher
temperatures relative to paraffins and olefins is consistent with a mechanism in which
unsaturated surface ions are precursors for alkyl aromatic formation. Alkyl aromatic
yields decrease in the order: PE-HZSM-5 > PE-HY > PE-MCM-41, which follows a
trend in increasing pore size. Steric restrictions on reaction volume afforded by HY
54 R.L. WHITE
and HZSM-5 promote aromatic ring formation from conjugated unsaturated polymer seg-
ments. The smaller pore HZSM-5 is significantly more effective at forming alkyl aromatics
than HY.
Unsaturated residue formed during catalytic reactions that produced paraffins and olefins
is the source of alkyl aromatics and nonvolatile residue. When HZSM-5 catalyst is
employed, aromatic alkyl chain sizes are restricted to C4 or smaller. The pores of HZSM-5
are large enough to allow formation of small alkyl aromatics by cyclization and dehy-
drogenation of surface species, but formation of fused unsaturated coke precursors are
inhibited. Unlike HZSM-5, larger HY pores facilitate the formation of larger nonvolatile
unsaturated coke precursors.
Trends in volatile paraffin/olefin ratios and alkyl aromatic yields observed when poly-
ethylene is cracked by aluminosilicate catalysts cannot be correlated with catalyst acidity
or pore size variations alone. Instead, product slate differences occur because relative
rates of specific carbenium ion reactions are affected by the combined effects of catalyst
acidity and pore size.
3 POLYSTYRENE CRACKING
Radical depolymerization of neat PS samples produces large quantities of monomer

(styrene) and chain-end backbiting yields substantial amounts of dimer and trimer. Poly-
mer decomposition proceeds by entirely different processes when a catalyst is present.
Repetitive injection GC/MS was employed to investigate the primary reaction processes
that occur when PS is cracked by silica–alumina, sulfated zirconia, and HZSM-5 [74].
These catalysts exhibit a wide range of acidity, but only the HZSM-5 catalyst has a
regular pore structure. The most abundant volatile species detected from PS-catalyst sam-
ples was benzene. About 30% of the volatile material produced from the PS-Si/Al and
PS-ZrO2 /SO4 samples was benzene. For PS-HZSM-5, the relative yield of benzene was
over 50%. Other volatile products detected from the PS-catalyst samples in substan-
tial yield included: alkyl benzenes, indanes, and naphthalenes. The relative yields of
alkyl benzenes were greatest for the samples containing Si/Al and ZrO2 /SO4 catalysts. In
contrast, PS-HZSM-5 produced fewer alkyl benzenes, but significantly larger quantities
of indenes.
Figure 2.7 contains plots of repetitive injection GC/MS chromatographic peak areas
(integrated total ion current) as a function of sample temperature for benzene and styrene
as well as selected products representing alkyl aromatics (ethyl benzene), indanes (methyl
indane) and indenes (indene) evolved from PS-catalyst samples. The plots show that
benzene is by far the most abundant volatile product. All of the PS-catalyst samples pro-
duce alkyl benzenes and indanes, however samples containing HZSM-5 catalyst generate
significantly lower relative yields of these products.
The formation of the primary PS catalytic cracking volatile products can be explained
by initial electrophilic attack on polymer aromatic rings by protons [60, 75]. Protons
preferentially attack the ortho and para ring positions because the aliphatic polymer
backbone is an electron-releasing group for the aromatic rings. Most volatile products
can be derived from mechanisms beginning with ring protonation. Thermal decompo-
sition of ortho-protonated aromatic rings in the polymer chain (1) can lead directly to
700 700
600 180
Benzene integrated TIC

500 150
Integrated TIC
400 120
300 90
200 60
100 30
0 0
120 200 280 360 440 520
Temperature (°C)
(a)
150
600
500 120
Integrated TIC
400 Benzene
Enthyl Benzene 90
300 Styrene
Indene 60
200 Methylindane
30
100
0 0
120 200 280 360 440 520
Temperature (°C)
(b)
600
105
500
90
75
Integrated TIC
400
60
300
45
200
30
100 15
0 0
120 200 280 360 440 520
Temperature (°C)
(c)
Figure 2.7 Species-specific evolution profiles for various PS-catalyst samples:

(a) PS-Si/Al, (b) PS-ZrO2 /SO4 ; (c) PS-HZSM-5. The left axis scale represents benzene
chromatographic peak areas and the right axis scale represents all other peak areas.
(Reproduced by permission of John Wiley & Sons, Ltd)
56 R.L. WHITE
the liberation of benzene, the primary catalytic cracking product, or may result in chain
shortening.
CH2 CH CH2 CH CH2 CH CH2
(2)
CH2 CH CH2 CH CH2 CH CH2 CH2 CH CH2 CH CH3 CH CH2

H
H +
(1) (3) (4)
CH2 CH CH2 CH2 CH3 CH CH2
(5) (6)
Benzene cannot be obtained directly from para-protonated aromatic rings in the poly-
mer. However, para-protonated rings can react with neighboring polymer chains to yield
the same chain scission products that are formed by ortho-protonation.
The macro cation remaining after benzene evolution (2) may undergo chain shortening
β-scission to produce (3) and an unsaturated chain end, rearrange to form an internal
double bond and protonate a neighboring aromatic ring (either by intra- or intermolecular
proton transfer), cyclize to form an indane structure, or abstract a hydride to produce a
saturated chain segment. The substantial quantities of indanes obtained by PS catalytic
cracking suggests that cyclization of (2) to form indane structures is a favored process.
This is supported by Nanbu et al., who reported that benzene and indane structures were
the only products detected when PS was cracked by using a strong acid catalyst at 50◦ C
[75]. A consequence of chain unsaturation resulting from (2) might be the formation
of conjugated polyene segments that may subsequently cyclize to form naphthalenes. A
minimum of three conjugated double bonds must be created in polymer chains before
naphthalenes can be formed. As a result, naphthalene evolution is delayed relative to
the evolution of alkyl benzenes and indanes, which can be formed from polymer seg-
ments without conjugated unsaturation. This is illustrated by Figure 2.8, which shows
the temperature-dependent yields of methyl indane (open circles) and naphthalene (open
squares) derived from analysis of the PS-ZrO2 /SO4 sample.
Decomposition of (3), which might be formed from (1) or (2), can result in the forma-
tion of styrene or may lead to chain end unsaturation and neighboring ring protonation.
Hydride abstraction by (3) would result in a saturated chain end. The lack of significant
styrene production from any of the PS-catalyst samples suggests that β-scission of (3) to
form styrene is not a dominant decomposition pathway at low temperatures. Chain end
unsaturation derived from (3) may result in formation of indenes, which were detected
in substantial amounts only when HZSM-5 catalyst was present. The restricted volume
220 16
200
14
Methylindane integrated TIC
Naphthalene integrated TIC

180
160 12
140 10
120
8
100
80 6
60 4
40
2
20
0 0
200 230 260 290 320 350

Temperature (°C)
Figure 2.8 Species-specific evolution profiles for methyl indane (open circles) and naph-
thalene (open squares) derived from a PS-ZrO2 /SO4 sample. (Reproduced by permission
of John Wiley & Sons, Ltd)
of the HZSM-5 channels apparently inhibits hydride abstraction pathways for (3), which
results in increased production of indenes and styrene for PS-HZSM-5.
Protonation of aromatic rings adjacent to methyl-terminated chain ends (4) can result
in the formation of alkyl benzenes, propene, and benzene, depending on how the macro
cation decomposes.
CH3 CH CH2 R CH3 CH CH3
+ R
(4)
CH3 CH CH2 + R
H+
b − scission
CH3 CH CH2 R CH3 CH
H
+ CH3 CH CH2 R H + CH3 R
CH3 CH2 CH2 R
CH3 CH2 CH3 CH2
+ CH2 R
(6)
58 R.L. WHITE
Macro cation (6), which can be formed from (1), (4), or (5), can undergo β-scission to
form styrene, rearrange to form a tertiary benzyl cation (7), or may abstract a hydride to
form (4).
CH2 CH CH2 CH R CH2 CH CH2 CH R CH3 CH CH2 CH R

b − scission H
+
(6) (6) (4)
CH3 C CH2 CH R
(7)
The tertiary benzyl cation (7), which would be preferentially formed by hydride abstrac-
tions in addition to rearrangement of (6), may be a precursor for chain unsaturation and
for the formation of indenes.
R1 C CH2 CH R2 CH R2
b − scission R1 C CH2
+
(7) (3)
R3 CH R4
R1 C CH2 CH R2 R1 C CH CH R2 R3 CH R4
H
H + H
(1)
R1 C CH CH R2
H
H
R1 C CH CH R2 R1 C CH
CH R2
H Indenes
+
If rearrangement of (7) results in chain unsaturation and intramolecular ring protonation,

volatile indenes ultimately result. If intermolecular ring protonation occurs, macro cation
(1) would likely be formed.
Figure 2.7(b) shows that benzene can be obtained by PS catalytic cracking at temper-
atures as low as 130◦ C. The fact that the temperature at which volatile decomposition
products were detected from PS-catalyst samples was dependent on the catalyst acidity
suggests that the rate-limiting step in the acid catalyzed decomposition of PS was aro-
matic ring protonation. For all PS-catalyst samples, benzene was the first volatile product
detected when samples were heated, which suggests that processes leading to benzene
liberation were favored over those that resulted in the products detected at higher tem-
peratures. This is consistent with the reaction schemes shown here, which suggest that
benzene can be easily formed from (1), but that formation of other volatile decompo-
sition products is more difficult and may require macro cation rearrangement, hydride
abstraction, or successive protonations.
Although acid catalyzed PS cracking appears to involve many different parallel reactions
and is quite complicated, the following general reaction scheme can be used to represent
the primary reaction pathways. The initial step in PS cracking is protonation of polymer
aromatic rings, which may result in chain shortening, yielding a chain end cation and
a saturated chain end. Ortho-protonation can readily lead to benzene evolution and the
formation of a secondary macro cation, which may subsequently cyclize to form an indane
structure. The fact that Nanbu et al. [75] detected only benzene and indane structures
from acid catalyzed PS cracking at 50◦ C suggests that reactions that form these species
are favored and that ortho ring protonation is the rate limiting step for the evolution
of benzene. Hydride abstraction appears to be an important reaction pathway for chain
end cations, except when the catalyst restricts the movement of polymer chains (e.g.
HZSM-5). Saturated chain ends are the likely source of alkyl benzenes, which can be
formed after protonation of chain end aromatic rings. Rearrangements and β-scissions of
macro cations can lead to chain unsaturation, or, for chain end cations, the formation
of unsaturated volatile products such as styrene and indenes. Conjugated polyene chain
segments resulting from macro cation rearrangements can backbite to form naphthalenes.
Indanes
Sat'd chain segment
chain unsaturation
H−
Benzene + Macro cation
Napthalenes
PS + H+ alkenes
H−
Sat'd chain end + Chain end cation
H−
Alkyl benzenes Chain unsaturation

indanes
styrene
60 R.L. WHITE
4 HYDROCRACKING PROCESSES
The yield of unsaturated catalytic cracking products can be reduced by the addition of
hydrogen to cracking atmospheres. Dufaud and Basset demonstrated this by employing a
zirconium hydride Ziegler–Natta catalyst to crack PE in a hydrogen atmosphere [25]. Ding
et al. studied the hydroconversion of PE with sulfided Ni and NiMo silica–alumina and
compared these catalysts with HZSM-5 [76]. They found that Ni/silica–alumina produced
higher quality liquid products (i.e. more isoparaffins and fewer aromatics). Walendziewski
et al. studied PE hydrocracking in autoclaves and reported that the addition of catalysts
decreased the boiling range and unsaturation of liquid products compared with thermal
and catalytic cracking [40, 48].
Although most previous reports focus on correlating variations in product slate with
catalyst properties, some studies have attempted to compare catalyst activation energies
obtained by using thermal analysis techniques. Garforth et al. used activation energies
derived from thermogravimetry (TG) measurements to compare the cracking properties
of ZSM-5, HY, and MCM-41 [22]. They found that coking was most significant for HY
and that MCM-41 exhibited the lowest cracking activation energy. In a similar study,
Fernandes et al. compared the TG derived activation energy for PE thermal decompo-
sition with that for HZSM-5 catalytic cracking and found that the catalyst reduced the
activation energy by more than a factor of two [23, 77]. Lin and co-workers character-
ized the deactivation of US-Y zeolite by monitoring changes in the TG properties of
polymer/catalyst mixtures [21].
A detailed study of PE hydrocracking by PtHZSM-5, PtHY, and PtHMCM-41 bifunc-
tional aluminosilicate catalysts was recently reported [78]. Repetitive injection chro-
matogram mass spectra were employed to identify class-specific fragment ions for use
in effective activation energy calculations. By comparing selected ion profiles with total
ion current chromatograms, it was determined that m/z 57, 55, and 91 could be used to
represent paraffins, olefins, and alkyl aromatics, respectively. Virtually all of the mass
spectrometer m/z 91 ion signal could be attributed to alkyl aromatics. Unfortunately, the
m/z 57 and 55 ion signals could not always be attributed solely to paraffins and olefins,
respectively. To assess the ‘selectivity’ of these ions for their respective product classes,
a selectivity value was calculated by computing the ratio of the ion signal contribution
from the desired class to the total ion signal for the target m/z value. This calculation
was repeated for each repetitive injection chromatogram to obtain selectivity profiles as
a function of sample temperature.
4.1 PE-PTHZSM-5
Figure 2.9 shows the species-specific evolution profiles for: (a) paraffin; (b) olefin; and
(c) alkyl aromatic volatile products for the PE-PtHZSM-5 sample heated in hydrogen.
As expected, paraffins dominated the hydrocracking volatile product slate and olefin and
alkyl aromatic yields were greatly reduced compared with results obtained when the
same sample was heated in helium. The paraffin profile for the PE-PtHZSM-5 sample
heated in hydrogen exhibited two maxima. Below 200◦ C, volatile product mixtures were
composed entirely of paraffins. As the sample temperature increased, a wide range of
C3
C4 (2)
90000
C5 (2)
Integrated total
ion current
C6 (3)
60000
C7 (3)
C8 (3)
30000 >C8 (6)
0
120 140 160 180 200 220 240 260 280 300 320 340
Temperature (°C)
(a)
15000
C6 (1)
Integrated total
ion current
10000 C7 (3)
C8 (3)
>C8 (3)
5000
0
120 140 160 180 200 220 240 260 280 300 320 340
Temperature (°C)
(b)
9000
Integrated total
Benzene
ion current
6000 Toluene
C2-Pheny (3)
3000 C3-Pheny (2)
0
120 140 160 180 200 220 240 260 280 300 320 340
Temperature (°C)
(c)
Figure 2.9 Evolution profiles for: (a) paraffins; (b) olefins; (c) alkyl aromatics for a
PE-PtHZSM-5 sample heated in hydrogen. (Reproduced by permission of John Wiley &
Sons, Ltd)
C3 –C10 volatile paraffins were formed, with C5 and C6 paraffins being the most abundant
volatile products detected.
Figure 2.10(a) shows class-specific effective activation energy Ea versus temperature
plots generated for the evolution of paraffins (m/z 57), olefins (m/z 55), and alkyl aromatics
(m/z 91) when the PE-PtHZSM-5 sample was heated in helium. The selectivity of m/z 57
for paraffins was about 90% between 140 and 240◦ C. Paraffin evolution Ea values above
240◦ C were not included in Figure 2.10(a) because the m/z 57 selectivity for paraffins
decreased dramatically above this temperature due to increased contributions to the m/z
57 ion signal from olefins. The selectivities of m/z 55 for olefins and m/z 91 for alkyl
62 R.L. WHITE
aromatics were at least 99% for the values plotted in Figure 2.10(a). Olefin Ea values
below 250◦ C were not included in Figure 2.10(a) because the m/z 55 selectivity for olefins
was significantly reduced due to contributions to the m/z 55 ion signal from paraffins.
Figure 2.10(b) shows the paraffin-specific effective Ea versus temperature plot for the
PE-PtHZSM-5 sample heated in hydrogen. The m/z 57 ion signal selectivity for paraffins
was 99%. Smaller error bars in Figure 2.10(b) compared with Figure 2.10(a) reflect the
fact that paraffins were by far the dominant volatile product when the PE-PtHZSM-5
sample was heated in hydrogen. As a result, the m/z 57 ion signals were larger than those
detected in helium and the m/z 57 selectivity for paraffins was much greater when the
sample was heated in hydrogen.
50
Effective EA (kcal/mol)
40
30
20
10
120 140 160 180 200 220 240 260 280 300 320 340
Sample temperature (°C)
(a)
50
40
30
20
10
120 140 160 180 200 220 240 260 280 300 320 340
(b)
Figure 2.10 PE-PtHZSM-5 effective activation energy profiles for: (a) paraffins (trian-
gles), olefins (squares), and alkyl aromatics (full circles) in helium; (b) paraffins (triangles)
in hydrogen. (Reproduced by permission of John Wiley & Sons, Ltd)
18000 C4 (2)
C5 (2)
12000 C6 (4)
C7 (4)
Integrated total ion current

6000 C8 (4)
>C8 (17)
0
(a)
900
C7 (1)
600
C8 (1)
300
0
120 140 160 180 200 220 240 260 280 300 320 340
Temperature (°C)
(b)
Figure 2.11 Evolution profiles for: (a) paraffins; (b) olefins for the PE-PtHY sample
heated in hydrogen. (Reproduced by permission of John Wiley & Sons, Ltd)
4.2 PE-PTHY
Figure 2.11 shows species-specific evolution profiles for: (a) paraffin; and (b) olefin
volatile products for the PE-PtHY sample heated in hydrogen. Seventeen different paraf-
fins with at least nine carbon atoms dominanted the volatile products. Volatile alkyl
aromatic yields were insignificant compared to the paraffin and olefin yields.
Figure 2.12(a) shows the Ea versus temperature profiles for paraffin and alkyl aromatic
evolutions when the PE-PtHY sample was heated in helium. The m/z 57 and m/z 91
ion signal selectivities for paraffins and alkyl aromatics were at least 99%. The alkyl
aromatic Ea value calculated for the PE-PtHY sample heated in helium was 10 kcal/mol
lower than that for the PE-PtHZSM-5 sample. Figure 2.12(b) shows the paraffin Ea ver-
sus temperature profile for the PE-PtHY sample heated in hydrogen. The m/z 57 ion
signal selectivity for paraffins was at least 99%. The Ea value for paraffin formation was
38 kcal/mol at 230◦ C and decreased to 28 kcal/mol by 300◦ C. The initial paraffin Ea
value for the PE-PtHY sample heated in hydrogen was 10 kcal/mol higher than the Ea
value for the same sample heated in helium.
4.3 PE-PTHMCM-41
Figure 2.13 shows species-specific evolution profiles for paraffin volatile products for
the PE-PtHMCM-41 sample heated in hydrogen. Volatile paraffins with more than eight
carbon atoms dominated the product slate. Volatile alkyl aromatic products were not
detected for the PE-PtHMCM-41 sample heated in either helium or hydrogen.
Figure 2.14(a) shows the olefin evolution Ea versus temperature plot for the PE-
PtHMCM-41 sample heated in helium. The m/z 55 ion signal selectivity for olefins was
64 R.L. WHITE
50
40
30
20
10
120 140 160 180 200 220 240 260 280 300 320 340
(a)
50
40
30
20
10
120 140 160 180 200 220 240 260 280 300 320 340
(b)
Figure 2.12 PE-PtHY effective activation energy profiles for: (a) paraffins (triangles) and
alkyl aromatics (full circles) in helium; (b) paraffins (triangles) in hydrogen. (Reproduced
by permission of John Wiley & Sons, Ltd)
99%. Figure 2.14(b) shows the paraffin Ea versus temperature plot for the PE-PtHMCM-
41 sample heated in hydrogen. The m/z 57 ion signal selectivity for paraffins was 99%
for the data plotted.
The hydrocracking effect on PE decomposition is clearly evident in the make-up of the
volatile product slates for the three bifunctional catalysts. As expected, olefin and alkyl
aromatic yields diminished and paraffin yields increased substantially when hydrogen
was added to the cracking atmosphere. The most dramatic change to the paraffin/olefin
ratio was found for the PtHMCM-41 catalyst. The presence of hydrogen also signifi-
cantly reduced the quantity of residue remaining after catalytic cracking. These effects
Integrated total ion current

150000 C3
C4(2)
100000 C5(2)
C6(4)
C7(4)
50000 C8(4)
>C8(20)
0
180 200 220 240 260 280 300 320 340
Temperature (°C)
Figure 2.13 Paraffin evolution profiles for the PE-PtHMCM-41 sample heated in hydro-
gen. (Reproduced by permission of John Wiley & Sons, Ltd)
50
40
30
20
10
120 140 160 180 200 220 240 260 280 300 320 340
(a)
50
40
30
20
10
120 140 160 180 200 220 240 260 280 300 320 340
(b)
Figure 2.14 PE-PtHMCM-41 effective activation energy profiles for: (a) olefins (squares)
in helium; (b) paraffins (triangles) in hydrogen. (Reproduced by permission of John
Wiley & Sons, Ltd)
66 R.L. WHITE
are well-known consequences of hydrocracking with bifunctional catalysts containing
platinum [79–81].
Paraffin evolution profiles for the PtHZSM-5 catalyst in helium and hydrogen exhibited
bimodal features. The presence of two maxima in paraffin evolution profiles suggests that
there were two PE cracking pathways leading to volatile paraffins and that these pathways
were available in helium and hydrogen. If the first evolution maximum is associated
with cracking outside of catalyst pores, the second maximum might be due to additional
cracking that occurs when the zeolite pores became accessible to polymer melt. Above
180◦ C, short polymer segments could more easily enter zeolite channels. In contrast to the
paraffin profiles, the evolution profiles for olefins in helium and hydrogen exhibit only a
single maximum with much lower yields at low temperature. Evidently, low-temperature
carbocation disproportionation reactions, which yield paraffins, occur more readily than
β-scission reactions, which are thought to be responsible for most olefin products [72].
The substantial reduction in alkyl aromatic yields in hydrogen compared to helium is
evidence that formation of conjugated unsaturation in the polymer melt was hindered by
the hydrogenation activity of the bifunctional catalyst.
Paraffin effective activation energy plots for the PtHZSM-5 catalyst reflect the bimodal
nature of the evolution profiles The increase in activation energy may be due to increased
steric hindrance for cracking reactions that take place within HZSM-5 channels.
The temperature range for alkyl aromatics evolution for the PtHY catalyst in helium
was similar to that for the PtHZSM-5 catalyst. However, the effective activation energy
for alkyl aromatics evolution was about 10 kcal/mol lower for PtHY compared with
PtHZSM-5. The higher activation energy for PtHZSM-5 may have been due to the smaller
channels of HZSM-5 compared with HY. Although the HZSM-5 channels may facilitate
conjugated bond cyclization reactions, the smaller HZSM-5 channels may also hinder the
release of aromatic products from the catalyst. The larger zeolite channel diameter of
HY is also likely responsible for the fact that the most abundant PtHY aromatic products
in helium were C3 -phenyl species whereas C2 -phenyl products dominated the PtHZSM-
5 product slate. The PtHY volatile paraffin and olefin evolution profiles in hydrogen
are narrower and shifted to higher temperature by about 50◦ C compared with the profiles
obtained in helium. This is consistent with the higher paraffin evolution effective activation
energies in hydrogen compared with helium. Increased effective activation energies for
catalytic hydrocracking compared with catalytic cracking have been reported previously
[82, 83].
The primary volatile products of PE cracking in helium by the PtHMCM-41 cata-
lyst were olefins. Unlike the other catalysts, alkyl aromatics were not detected for the
PtHMCM-41 catalyst. The effect of hydrogenation on the catalytic cracking ability of
PtHMCM-41 was dramatic. Volatile paraffins were the sole products detected in hydro-
gen and only 5% of the initial polymer mass remained as residue. The reduced catalytic
cracking capacity of PtHMCM-41 arising from its lower acidity resulted in the dominance
of large paraffins (>C8 ) in the hydrocracking product slate.
Hydrocracking effective activation energy plots for the three catalysts used in this
study all exhibit a decrease with increasing temperature above 240◦ C. The magnitude of
the drop in activation energy follows the trend: PtHMCM-41 > PtHY > PtHZSM-5. It
has been previously reported that the strength of olefin adsorption on catalyst surfaces
determines the kinetics of platinum-catalyzed hydrogenation[84]. The strength of olefin
adsorption would be expected to decrease with an increase in catalyst temperature, which
would explain the observed decrease in activation energy for each catalyst. The activation
energy decrease is much greater for PtHMCM-41 than the other catalysts. The attraction of
olefins to PtHMCM-41 catalyst surfaces would be expected to be much less than the other
catalysts because of its relatively low acidity. Apparently, interactions between olefins
and PtHMCM-41 catalyst surfaces diminish more rapidly with increased temperature
than the other catalysts. Hydrocracking reactions dominated when poly(ethylene) was
catalytically cracked in the presence of hydrogen. The length of volatile paraffins was
found to depend on the catalyst pore size and acidity and followed the trend: PtHMCM-
41 > PtHY > PtHZSM-5. Volatile product slate and effective activation energy trends
cannot be explained by a single catalyst characteristic. Instead, the combined influence
of acidity, pore size, and preferred cracking mechanism(s) for each volatile product must
be considered.
5 CONCLUSIONS
The reaction pathways involved in acid-catalyzed cracking of PE and PS are numerous.

Subtle changes in catalyst structure or operating conditions can significantly alter which
reaction pathways are favored. Catalytic reactor design can further affect relative prod-
uct yields by facilitating secondary reactions. The results described here were obtained
by using samples containing a large excess of catalyst. Because polymer–catalyst sam-
ples contained much more catalyst than polymer, results primarily reflect innate catalyst
activities and any effects from catalyst deactivation processes were minimal. The primary
reaction pathways described here will serve as benchmarks for understanding the dynam-
ics of steady-state reactor performance, which will indeed be a challenging endeavor. To
fully explain steady-state reactor processes, the effects of secondary reactions and cata-
lyst deactivation must also be considered. A full understanding of practical applications
of plastic waste catalytic cracking will be even more difficult because reaction pathways
for multiple polymer types must be simultaneously considered.
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3
Catalytic Upgrading of Plastic

Wastes
J. AGUADO, D. P. SERRANO AND J. M. ESCOLA
Rey Juan Carlos University, Escuela Superior de Ciencias Experimentales y Tecnologı́a
(ESCET), c/Tulipán s/n, 28933, Móstoles Spain
1 INTRODUCTION
Upgrading of plastic wastes by catalytic cracking is a subject of growing interest in the last
years as a feasible way for promoting the feedstock recycling of these residues towards
either raw chemicals or fuels [1]. According to 2002 data, the total plastic consumption
in Western Europe accounts for 38.1 million tonnes while the amount of plastic wastes
collected was around 20.4 Mt [2]. This growing amount of residues has raised a deep
public concern due to the depletion of landfills, their effect in our life quality and the loss
of potentially valuable raw materials. In 1994, the European Union launched the 94/62/CE
directive on waste packaging that established minimum rates of recycling per material
(15%). Since then, the percentages of recycling and energy recovery have increased to
14.8 and 23% respectively (2002 data). Nevertheless, 62 wt% of plastic wastes are still
being disposed of by landfilling in Western Europe.
A great proportion of plastics end its lifetime as a part of the overall solid waste stream
where they represent roughly 10 wt%. The typical distribution of plastics in household
wastes is shown in Figure 3.1 [3]. The main components are polyolefins: low-density
polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethy-
lene (HDPE) and polypropylene (PP), accounting for about 67% of the total amount
of plastic wastes. Other important components in plastic wastes are polystyrene (PS),
poly(vinyl chloride) (PVC) and poly(ethylene terephthalate) (PET).
Pyrolysis treatments are interesting regarding the aforementioned plastic refuse makeup.
Other successful treatments for feedstock recycling of condensation polymers (PET, ABS,
etc.), that allows for the depolymerization and recovery of their constituent monomers
(e.g. hydrolysis, alcoholysis, methanolysis, etc.), cannot be applied for polyolefin plastics
recycling. In contrast, pyrolysis of polyolefins yields valuable hydrocarbon mixtures of
74 J. AGUADO ET AL.
5.3% 4.2%
10.3% PET Others
PVC
13.3%
PS
66.9%
HDPE, LDPE
LLDPE, PP
Figure 3.1 Typical distribution of plastics in household wastes in Europe [3]
different composition, depending on the operating conditions [4, 5]. For the particular
cases of some plastics (e.g. the thermal cracking of PMMA), wherein depolymerization
really occurs on heating, the original raw monomer (MMA) can be obtained with high
yields (up to 97%) [6]. Catalytic cracking can be considered as an advantageous treatment
in regard to other competing procedures for feedstock recycling of plastic wastes such as
gasification towards synthesis gas (CO + H2 ) [7–9] and its recent use as coke substitute
in steel making industry [2]. Unlike them, catalytic cracking is a versatile process since a
variety of valuable products can be attained through a proper choice of both the process
conditions and catalysts. Moreover, it does not require the construction of large-capacity
plants to be profitable as it is the case for gasification. However, most industries have
remained reluctant to employ catalytic cracking of plastic wastes due to the limitations
posed by the heterogeneous nature of plastic wastes (presence of heteroatoms, additives
and other wastes) and their high viscosity and low thermal conductivity. This situation has
started to change, with several plants in operation in Poland [10] and Japan [11] based
on the use of catalytic cracking processes for converting plastic wastes into fuels. This
progress can be considered a result of the development of better sorting procedures [12],
increasing public opinion cooperation, the modification of plastic product design in order
to promote their separation, identification and recycling [13] and the regulation pressure.
Recently, a life-cycle assessment of plastic waste catalytic cracking process has been
published showing the environmental and economic benefits that can be derived in regard
to other waste management alternatives [14]. In addition, a large number of scientific
papers and patents have appeared in recent years upon plastic catalytic degradation and
considerable scientific advances have been performed, so many technical problems have
already been overcome. In this regard, the present work is aimed at reviewing the main
scientific breakthroughs produced in the field of catalytic cracking and conversion of
plastic wastes.
1.1 CATALYTIC VERSUS THERMAL CRACKING
Thermal and catalytic treatments of plastic wastes present meaningful differences. In

terms of mechanism, thermal degradation proceeds according to a radical chain reaction
CATALYTIC UPGRADING 75
pathway comprising hydrogen transfer steps along with the progressive breaking of the
polymer backbone. The detailed mechanism can be found elsewhere and involves the
classical initiation, propagation and termination steps [4, 15]. In general terms, the ini-
tiation reactions comprise the homolytic cleavage of a carbon–carbon bond by either
random or end chain scission giving rise to the appearance of two radicals. This may
be followed by intramolecular/intermolecular hydrogen chain transfer reactions forming
more stable secondary radicals. Additionally, these intermediate radicals may undergo
C–C bond rupture by β-scission to produce olefins (ethylene and propylene) and new rad-
icals. Finally, termination reactions such as disproportionation towards different olefins
and alkanes or bimolecular coupling between radicals might take place. One important
feature of thermal cracking reactions stems from their radical nature since no radical rear-
rangement reactions occur which restricts the number of potential products to be attained.
In this regard, branched products may only be formed as a result of either the inter-
action between two secondary radicals or between a secondary and a primary radical.
As a consequence of this mechanism, thermal cracking of polyethylenes leads towards a
broad distribution of hydrocarbons within the C5 –C80 range, each fraction being mainly
formed by the corresponding diene, 1-olefin and n-paraffin, as it can be appreciated in the
gas chromatogram shown in Figure 3.2. At high temperature, hydrogen is also formed in
significant amounts [15]. The products of thermal cracking of polyolefins are of limited
commercial value, being mainly applied as fuels. In some cases, the heavy fraction has
been proposed to be applied as a wax [16]. A different approach for the thermal conver-
sion of plastic wastes is the one based on steam cracking processes at high temperatures
and low residence times, which leads to the production of light hydrocarbons (ethylene,
propylene, butenes) [17].
C10
2.0
C15 C20
1.5
Mcounts
C30
1.0
C35
0.5
0.0
10 20 30 40 50 60
Time (min.)
Figure 3.2 GC analysis of the products obtained in the LDPE thermal degradation.
(Reproduced with permission from Elsevier)
76 J. AGUADO ET AL.
In contrast, catalytic cracking takes place following a carbocationic mechanism [18, 19]
although the simultaneous occurrence of thermal degradation reactions is usually observed,
whose relative extent depends mainly on the temperature. In fact, many of the reported
procedures for catalytic cracking of plastics are indeed a reforming of the products coming
from a previous thermal cracking [20]. In most systems, the catalytic cracking mechanism
proceeds with the formation of a carbocation, either by hydride abstraction on a Lewis site
or by generating a carbonium ion over a Brönsted acid site. In addition, polymers usually
present some double bonds (e.g. vinylidene moieties resulting from the polymerization
process) and branchings that are more reactive points for the carbocation formation. Sub-
sequently, the polymer is fragmented by β-scission and disproportionation reactions, the
former leading to olefins. Unlike the previously commented radical pathway for thermal
cracking, skeletal isomerization occurs simultaneously with the cracking reactions giving
rise to branched products. Additionally, oligomerization, cyclization and aromatization
reactions may proceed together with the cracking. The adequate choice of the catalyst
allows the cracking and reforming reactions to be addressed towards a limited range of
products, as it may be appreciated in the gas chromatogram shown in Figure 3.3, corre-
sponding to the catalytic cracking of low-density polyethylene over HZSM-5 zeolite with
a high catalyst loading. In this case, many of the components are aromatic hydrocarbons,
whereas linear compounds, typical of the thermal degradation, are present in negligible
amounts.
The following advantages can be envisaged for catalytic cracking processes compared
with simple thermal treatments:
• lowering of the reaction temperature, which leads to a decrease of the energy consumed
in the process;
2 1. Benzene (6.62 min)

2.0 2. Toluene (9.94 min)
3. Ethyl benzene (12.96 min)
4. o, m, p-xylene (13.18 – 13.3 min)
5. Styrene (13.91 min)
1.5 6. Propyl benzene (15.77 min)
7. 1 ethyl – 2 methyl benzene
Mcounts
4 1 ethyl – 3 methyl benzene (15.9 – 16.5 min)

1 ethyl – 4 methyl benzene
1.0 8. 1,2,3 trimethyl benzene (16.85 min)
9. Naphthalene (22.01 min)
1
5
0.5
8
3 7
9
6
0.0
10 20 30
Time (min.)
Figure 3.3 GC analysis of the products obtained in the LDPE catalytic cracking over
HZSM-5 zeolite. (Reproduced with permission from Elsevier)
• the cracking reactions proceed faster, bringing about shorter residence times and lower
reactor volumes;
• selectivity may be tailored towards different valuable products by a judicious choice
of both the catalyst and process conditions;
• in the case of polyolefins, the products derived from the catalytic cracking contain
mainly cyclic, branched and aromatic hydrocarbons, which increase the quality of the
potential fuels;
• inhibition of the formation of undesired products (e.g. chlorinated hydrocarbons),
which is a feature especially interesting in the presence of PVC. It has been observed
that catalysts based on some metals (aluminium, zinc, iron) and metal oxides with large
ionic radius (ferric oxide and titanium oxide) reduce the temperature of hydrochlori-
nation onset by attracting chlorine [21].
However, along with the reported advantages of the catalytic processes, there are also
some important drawbacks, stemming mainly from the heterogeneous makeup of the plas-
tic waste mixtures. Thus it must be pointed out that most of the studies on plastic cracking
have been carried out using virgin plastics as raw materials. The situation is completely
different when real polymer wastes are to be degraded. On the other hand, the above men-
tioned presence of chlorine from polyvinylchloride (PVC) may cause corrosion problems
as well as the formation of toxic chlorine containing compounds. Additionally, other het-
eroatoms such as nitrogen, coming from acrylonitrile–butadiene-styrene plastics (ABS)
(among other sources), and sulphur, from oils, rubber and some additives, are usually
present in plastic wastes. Both nitrogen and sulphur compounds are known poisons for
acid solids catalysts and decrease their activity to a large extent [22]. In this regard, the
use of previous separation steps in order to eliminate the source of these heteroatoms (e.g.
flotation stage) and/or the heteroatom in the process itself (e.g. a dechlorination stage)
must be considered. On the other hand, acid solid catalysts can be deactivated by coke
deposition and by the occurrence of different cross-linking reactions favoured by the pres-
ence of some plastics, as it is the case of ethylene–vinylacetate copolymers [23]. Finally,
plastics are bulky macromolecules, which usually present steric/diffusional hindrances to
access to the internal acid sites of conventional microporous acid catalysts such as zeo-
lites [24]. However, all these bounds constitute a challenge for the development of more
active and deactivation resistant catalytic systems.
1.2 PLASTICS SUSCEPTIBLE TO UPGRADING BY CATALYTIC CRACKING
Catalytic cracking has been extensively applied to polyolefinic plastics (HDPE, LDPE,
PP) and PS, mostly because of their abundance and similar elemental composition. For
other plastics, there are currently competing successful recycling process for the recovery
of the original plastic (Vinyloop process for PVC) or the monomers (PETCORE process
for PET) [25], so the cracking route seems not to be a recommended way. The number
of publications devoted to the study of the catalytic cracking of other pure plastics (EVA,
PET, ABS) [23, 26, 27] and their mixtures with polyolefins [23] has increased in the
last years, although the latter are mostly addressed to ascertain the influence exerted by
these minor components present in the plastic waste stream upon the catalyst cracking
performance.
78 J. AGUADO ET AL.
Thus, the catalytic cracking of PET has been recently a subject of interest [26]. Several
acid solids (zeolites 4A and 13X and alumina) as well as metal salts (CuCl2 , MgCl2 and
Zn, Sn, Mg, Mn acetates) have been tested as catalysts at 400–500◦ C. Copper chloride
has been found as the most effective catalyst, reducing the degradation time by almost
3.5 times in regard to the thermal treatment and minimizing the amount of carbonaceous
residues.
Thermal and catalytic cracking of ABS has been studied by Brebu et al. [27] over
silica–alumina and three silica–alumina/iron oxide combinations. The introduction of
iron into the catalyst formulation allows for degrading the heavy nitrogen-containing
compounds into light aliphatic nitriles that can be eliminated from the oils simply by
distillation. Thus, the concentration of the most abundant nitrogen-containing compound
(4-phenylbutyronitrile) was reduced from 17.5 to 1.7 wt%. This example highlights the
importance of the catalyst formulation not only for the degradation of the polymer, but
also for the removal of heteroatoms.
1.3 PRODUCTS DERIVED FROM THE CATALYTIC CRACKING
The products obtained in the catalytic cracking of plastics depend on numerous experi-
mental variables. The possible products derived from the cracking of a polyolefin plastic
wastes mixture over acid solid catalysts are summarized in the mechanism depicted in
Figure 3.4 [28]. Depending mostly on the acid strength of the catalyst, cracking proceeds
mainly by either random (medium or weak acidity) or end-chain scission (strong acidity)
giving rise to waxes and middle distillates (gasoil, gasoline) or light hydrocarbons (C3 –C5
olefins), respectively. These primary cracking products can be removed from the reac-
tion medium or undergo secondary reactions (oligomerization, cyclization, aromatization).
The relative extent of these reactions is bound up with the acid and textural properties
of the catalysts, but also with the employed experimental variables (e.g. reactor type,
temperature, residence time, etc.).
From the aforementioned products, light olefins are potentially valuable feedstocks,
especially the C3 –C5 fractions [29], which may be used as raw chemicals while the
paraffin components may be used as a fuel. In addition, they can be easily separated as
the number of isomers in these low carbon number fractions is fairly low. In contrast,
End-chain cracking H-transfer

(C3 –C5) Light paraffins
olefins Ol (C3 – C5)
igo
H-transfer
me
Cy riz
Polyolefins cliz ati
ati on
on
Random cracking
Waxes Gasoil Aliphatic Aromatic
(C13 –C40) hydrocarbons hydrocarbons
(C6 – C12) (C6 – C9)
Figure 3.4 Mechanism of catalytic cracking of polyolefins over acid solid catalysts [28].
(Reproduced by permission of the American Chemical Society)
middle distillates fractions (C6 –C40 ) are usually of limited applicability because of the
huge number of isomers obtained obliges them to be used solely as fuels. In this case,
the catalyst is usually tailored in order to obtain better quality fuels such as gasoline and
diesel. However, some catalysts have been developed in order to attain high selectivities
towards specific raw chemicals, e.g. BTX (benzene, toluene, xylenes).
2 CATALYTIC SYSTEMS
Both homogeneous and heterogeneous systems have been used in the literature for study-
ing the catalytic cracking of polymers. In general, heterogeneous catalysts are the preferred
choice due to their easy separation and recovery from the reacting medium.
2.1 HOMOGENEOUS CATALYSTS
Homogeneous catalysts used for polyolefin degradation have mostly been classical Lewis
acids such as AlCl3 , metal tetrachloroaluminates melts and more recently, new catalytic
systems based on organic ionic liquids.
Ivanova et al. [30] degraded polyethylene catalytically with AlCl3 and electrophilic
complexes at 370◦ C giving rise to higher yields of gaseous compounds (88.2 wt%) than
thermal cracking of this same polymer (40 wt% of gases at 400◦ C). The main gaseous
compounds obtained in the catalytic cracking were isobutane (42.5%) and isobutene
(21.8%) and the amount of hydrocarbons heavier than C5 was practically negligible.
Tetrachloroaluminate melts M(AlCl4 )n (M = Li, Na, K, Mg, Ca, Ba; n = 1–2), which
constitute ionic media, were also applied as catalysts for polyethylene cracking leading
to 90–95% of C4 hydrocarbons.
Catalytic systems over ionic liquids are gaining increased attention worldwide as benign
solvents for green chemistry processes due to their low volatility and ease of product sep-
aration. Recently, catalytic cracking of polyethylene (HDPE, LDPE) has also been carried
out using organic ionic liquids, such as 1-ethyl-3-methylimidazolium chloride-aluminum
(III) chloride [31]. Light alkenes (C3 –C5 ), such as isobutene, and branched and cyclic
alkanes were the major product components. The reported working temperatures are mean-
ingfully lower (90–250◦ C) than those used over conventional heterogeneous catalysts
although times of 1–6 days of reaction were needed to obtain yields of 60–95 wt%.
2.2 HETEROGENEOUS CATALYSTS
A wide variety of heterogeneous catalysts have been tested for the catalytic cracking of
polyolefins and polystyrene, which can be summarized as follows:
• conventional acid solids used in the catalytic cracking of hydrocarbon feedstocks:
zeolites, silica–alumina, aluminas, fresh and spent FCC catalysts [32–42];
• mesostructured catalysts: MCM-41, FSM-16, Al-SBA-15 [5, 43–48];
• aluminium pillared clays [49–51];
• nanocrystalline zeolites (n-HZSM-5) [52];
80 J. AGUADO ET AL.
• superacid solids (ZrO2 /SO4 2− ) [53];

• gallosilicates [54, 55];
• metals supported on carbon [56, 57];
• basic oxides (BaO, K2 O, etc.), mainly for polystyrene cracking [58, 59].
Among the above-mentioned solids, zeolites have been certainly the most studied cat-
alysts for polyolefin cracking. Zeolites are crystalline microporous aluminosilicates of
groups IA or IIA elements (mainly sodium, potassium, magnesium, calcium) whose chem-
ical composition may be represented by the following formula [60]:
M2/n O.Al2 O3 .ySiO2 .wH2 O
where 2 < y < 10, n is the cation valence and w represents the amount of water.
The zeolite framework is built from the combination of SiO4 and AlO4 tetrahedra linked
by sharing oxygen atoms which extend tridimensionally. The presence of aluminium into
the framework brings about the appearance of a negative net charge which must be
balanced by an extra-framework cation. This charged nature of zeolites provides them
with the capacity for ion exchange as well as acid properties when the extra-framework
cation is a proton. The required acidity may be tuned by a proper choice of the zeolite
structure as well as their aluminium content [60]. Zeolites may exhibit a mono-, bi- or
tridimensional channel network with pore sizes of definite dimensions (below 1.0 nm)
and even interconnected microporous cavities depending on their topology. In this regard,
zeolites are considered as molecular sieves since their pore dimensions are close to those
of many molecules (usually 0.4–1.0 nm) showing the property called ‘shape selectivity’
which allows them to discriminate among different reactants, transition states or products.
At present more than 100 zeolitic structures (both natural and synthetic) have been
reported and their number grows annually as new structures are continuously being dis-
covered which opens up a wide range of possible applications [61, 62]. However, from a
practical viewpoint, only a few zeolites are used as industrial catalysts such as Y, ZSM-5,
Beta and mordenite (Table 3.1), mainly due to the cost and difficulties inherent to their
preparation [60]. When zeolites are applied for the catalytic cracking of polymers, their
microporous structure causes important diffusional and steric hindrances for the access of
the bulky plastic molecules to the internal acid sites [5, 24].
Amorphous silica–alumina (SiO2 –Al2 O3 ) has been also tested for the catalytic cracking
of polyolefins [36, 37, 43]. This acid solid is featured by having a broad distribution of
pore sizes, which is determined by the synthesis procedure. Moreover, the occurrence of a
bimodal pore size distribution (e.g. meso-macroporous) is usually present. The aluminium
Table 3.1 Structural features of common zeolites used as catalysts in

plastic cracking
Zeolite Structure Pore size (nm) Si/Al ratio

ZSM-5 MFI 0.53 × 0.56, 0.51 × 0.55 10–1000
Y FAU 0.74 1.5–3
Beta BEA 0.64 × 0.76, 0.55 × 0.55 8–1000
Mordenite MOR 0.65 × 0.7 5
content of these materials can be varied within a broad range (0.1–30 wt%) and their acid
strength is of medium type, lower than that of the majority of zeolites, containing acid
sites of both Brönsted and Lewis nature. Amorphous silica–alumina is also employed as
a component of the formulation of FCC catalysts for the cracking of heavy feedstocks as
these macromolecules can enter through the large meso/macropores of this material.
Both fresh and especially spent FCC catalysts have been the object of recent attention
for polymer cracking [41, 42]. Although they are less active than silica–alumina or meso-
porous catalysts [41], spent FCC catalysts still maintain enough activity to be considered
as a good choice regarding the fact that their cost is basically zero and they are contin-
uously being disposed of from FCC units. In addition, it has been proved [42] that the
unavoidable metal contamination coming from their accumulation after the processing of
heavy feedstocks (mostly Ni and V in amounts within 3000–6000 ppm) catalysts did not
affect the obtained products over spent FCC catalysts. These same authors carry out an
economic evaluation of a catalytic system based on used FCC catalysts, concluding that
the cost seems comparable to that of a commercial thermal cracking plant.
The design of catalysts capable of overcoming steric hindrances by having more acces-
sible acid sites located either into larger pores (mesoporous catalysts, pillared clays) [5,
43–51] or over the external surface (nanozeolites) [52] have been successfully tested for
the cracking of polyolefins. The first mesoporous aluminosilicates (M41S) were discov-
ered in the early 1990s by Mobil Oil researchers [63]. These aluminosilicates show a
uniform mesopore size which can be tailored within the 1.5–10.0 nm range by a suitable
choice of synthesis conditions (template, temperature and medium composition). Their
BET surface areas are around 1000 m2 g−1 and their pore volumes about 0.8 cm3 g−1 .
MCM-41, which exhibits a hexagonal array of unidimensional mesopores, has been the
most studied catalyst of the M41S family. Other mesoporous aluminosilicates such as
FSM-16 have also been tested for the catalytic cracking of polyethylene. FSM-16 shows
textural properties close to those of MCM-41 materials in terms of BET surface area
and pore size, the main difference residing in that a layered silicate (kanemite) is used
as silica source in its synthesis [46]. Both MCM-41 and FSM-16 have shown activity
for the cracking of polyethylene even in their pure silica form [46, 47, 64]. Recently,
another mesoporous silicate (SBA-15) was synthesized with BET surface areas around
600–800 m2 g−1 and uniform mesopores of dimensions adjustable within the 3.0–30.0 nm
range [65]. SBA-15 has the advantage of its wider pore walls (>2.0 nm), that provides
this material with higher hydrothermal and thermal stability compared to MCM-41, an
important feature from the point of view of the catalyst regeneration. Catalytic cracking of
polyethylene over Al-SBA-15 has also been carried out, yielding similar results in terms of
product distribution to those of Al-MCM-41 catalysts [48]. Figure 3.5 shows the transmis-
sion electron micrographs of both Al-MCM-41 and Al-SBA-15 wherein their respective
hexagonal array of mesopores is clearly appreciated. All the reported mesoporous alumi-
nosilicates possess amorphous pore walls and a medium acid strength distribution, quite
similar to that of silica–alumina.
Both natural clays and their aluminium oxide pillared analogues have also been tested
for the catalytic cracking of polyethylene [49–51]. The clays investigated include mont-
morillonite and saponite. They possess a layered structure which can be converted into
a two-dimensional network of interconnected micropores by intercalation of molecular
moieties. In the case of aluminium pillared clays, these materials show a mild acidity
82 J. AGUADO ET AL.
Figure 3.5 TEM micrographs of MCM-41 (a) and SBA-15 (b) mesoporous materials
and an accessible pore size structure. The consideration of pillared clays as possible cat-
alysts for plastic cracking is mainly supported by the fact that their acidity is weaker
in strength than that of zeolites. Accordingly, they show a lower cracking activity, but
also the catalyst deactivation by coke formation takes place to a lower extent compared
with zeolitic catalysts. Moreover, the liquid products obtained over the clay catalysts are
heavier, as the strong acidity of zeolites is responsible for plastic overcracking reactions
with the production of light hydrocarbons. Likewise, the mild clay acidity leads to a
lower occurrence of hydrogen-transfer reactions compared with US-Y zeolite, which in
turn causes the formation of alkenes as the main products of the polyethylene cracking
over clay catalysts.
Nanocrystalline zeolites, mainly HZSM-5, have also shown remarkable activity for
polyolefin cracking [52]. These materials are zeolites synthesized by procedures leading
to nanometer crystal size (<100 nm), which provides them with a high share of external
surface area fully accessible to the whole of the bulky polymer macromolecules. For
instance, nanocrystalline HZSM-5 (n-HZSM-5) with a crystal size around 60 nm presents
an external surface area of 82 m2 g−1 (almost 20% of the total surface area) and con-
sequently, a high amount of external acid sites. This catalyst has shown a high activity
in the cracking of polyolefins, even when working at temperatures as low as 340◦ C and
high plastic/catalyst ratios (P/C = 100).
Catalytic degradation of a standard polyolefin mixture made up of LDPE (46.5%),
HDPE (25%) and PP (28.5%) was performed in a semi-batch reactor over a variety of acid
solids, differing both in textural properties and acid strength distribution [43]. The conver-
sions and the selectivities by groups and carbon atom number obtained in the cracking of
the polyolefin mixture at 400◦ C for 0.5 h and using a plastic/catalyst mass ratio (P/C) of
50 are illustrated in Figures 3.6, 3.7 and 3.8, respectively. The highest conversions were
obtained in the following order: n-HZSM-5 > HBeta > HMCM-41 > HZSM-5. How-
ever, the acid strength of the catalysts decreased as follows: HZSM-5 > n-HZSM-5 >
HBeta > HMCM-41 > HY ∼ SiO2 − Al2 O3 . The high performance of HMCM-41 was
ascribed to both its large surface area and mesopore size while for the case of zeolite
HBeta, its relatively large micropore size and medium acid strength are the main reasons
to explain its good catalytic behaviour. It is noteworthy to observe the huge differences
between the conversions obtained over the micrometer-size (HZSM-5) and nanocrystalline
n -HZSM-5
Hβ
HMCM-41
SiO2 – Al2O3
Crossfield
HZSM-5
HY
Thermal cracking
0 20 40 60 80 100
Conversion (wt%)
Figure 3.6 Conversions obtained in the catalytic cracking of a model polyolefin mixture
(semi-batch reactor, P /C = 50; T = 400◦ C, t = 30 min) [43]. (Reproduced by permission
of the American Chemical Society)
80
HMCM-41
70 Hβ
n -HZSM-5
60
50
Selectivity (wt%)
40
30
20
10
0
C1–C4 C2–C4 C5–C12 C6–C9 C13–C30
paraffins olefins aromatics
Figure 3.7 Selectivities by groups obtained in the catalytic cracking of a model poly-
olefin mixture (semi-batch reactor, P /C = 50; T = 400◦ C, t = 30 min) [43]. (Reproduced
by permission of the American Chemical Society)
84 J. AGUADO ET AL.
35
HMCM-41
30 Hβ
n -HZSM-5
Selectivity (wt%) 25
20
15
10
0 5 10 15 20 25 30
Carbon atom number
Figure 3.8 Selectivities by carbon atom number obtained in the catalytic cracking of
a model polyolefin mixture (semi-batch reactor, P /C = 50; T = 400◦ C, t = 30 min) [43].
(Reproduced by permission of the American Chemical Society)
(n-HZSM-5) zeolites, which have been directly related with the higher accessibility of
the acid sites in this last material. The selectivity by groups and atom carbon number
distribution of the products (Figures 3.7 and 3.8, respectively) are mainly related to the
catalyst acid strength. The stronger the acid sites, the higher the amount of gaseous C1 –C4
formed by the end chain scission mechanism (mainly C3 –C4 ). In contrast, the amount of
C5 –C12 hydrocarbons increases over catalysts with medium acid strength as they promote
random scission reactions of the polymer backbone.
Super acid solids (ZrO2 /SO4 2− ) have been tested [53] in the catalytic cracking of HDPE
using a thermogravimetric equipment (TG). These solids present higher acidity than 100%
sulphuric acid and it is also superior to that of zeolites. The results obtained pointed out
the following reactivity order: ZrO2 /SO4 2− > zeolite HZSM-5 > silica-alumina, with a
high share of volatile hydrocarbons, mainly C4 –C5 alkenes, being obtained.
A different approach was followed by Uemichi et al. [56] that used metals (Pt, Fe, Mo,
Zn, Co, etc.) supported over activated carbons as catalysts for the catalytic degradation of
polyethylene at 300◦ C towards aromatic compounds (mostly benzene). The most effective
metals being Pt, Fe and Mo that produced around a 45% yield of aromatics. The role
played by the metals was the hydrogen desorption while its abstraction occurs primarily
over the carbon sites. In line with the same target products (aromatics), gallosilicates were
also employed for the catalytic cracking of polyethylenes at 425◦ C [54]. The catalyst was
actually an HZSM-5 zeolite with Ga incorporated into the framework as heteroatom
(Si/Ga = 25) instead of aluminium, and proved to be highly effective for the production
of aromatics (BTX yields ∼ 50%).
3 REACTORS
The low thermal conductivity of the molten polymers and their extremely high viscosity
are the major problems for the catalytic cracking reactor design. The most widely used
reactor systems have been:
• batch/semi-batch;
• fixed bed;
• fluidized bed;
• spouted bed;
• screw kiln.
Apart from these reactors, thermogravimetric techniques (TG) have been widely applied
for the study of the thermal and catalytic cracking of several plastics over different
acid solids, determining relative activity of the catalysts and kinetic parameters under
both isothermal and dynamic conditions [45, 66–69]. Thus, Figure 3.9 illustrates the TG
curves corresponding to the degradation of a commercial EVA copolymer by just thermal
treatment or when mixed with a MCM-41 catalyst at two different heating rates [45]. It is
observed that the catalytic cracking starts at lower temperatures than the thermal process.
In fact for a heating rate of 10◦ C/min, the catalytic cracking has gone to completion
at 450◦ C, whereas the thermal degradation requires a temperature of around 490◦ C to
obtain total plastic conversion. TG experiments have been shown to be a fast method
Sample 1
100
80
Weight loss (%)
60 10ºC/min-8.90% MCM-41
10ºC/min-absence of MCM-41
40
40ºC/min-9.10% of MCM-41
20 40ºC/min-absence of MCM-41
0
500 550 600 650 700 750 800 850
Temperature (K)
Figure 3.9 TG analyses of EVA polymer degradation by both thermal treatment and
catalytic cracking over a MCM-41 material [45]. (Reproduced with permission from
Elsevier)
86 J. AGUADO ET AL.
for evaluating the activity of different catalysts or to study the catalyst deactivation,
although the results must be carefully interpreted as they are not carried out under realistic
conditions, whereas no information about the product distribution is usually derived.
3.1 BATCH/SEMI-BATCH REACTORS
The literature is full of studies that use either a batch or a semi-batch reactor for the
catalytic cracking of plastics provided (but not always) with a stirring device [28, 38, 41,
55, 70]. The main reason is the ease of their design and operation. However, there is a
significant difference between them. The semi-batch reactor is swept by a continuous flow
of an inert gas (usually nitrogen) that removes the volatile products from the medium at
the reacting temperature. The removal of the volatile compounds causes the secondary
reactions of the primary cracking products (e.g. oligomerization, cyclization and aroma-
tization) to take place only to a little extent. This does not occur in batch reactors where
secondary reactions are supposed to be promoted [54].
One recent example of the use of a stirred semi-batch reactor for the catalytic degra-
dation of plastics wastes (HDPE, LDPE, PP and PS) over spent FCC catalysts has been
reported by Lee at al. [70]. The yields of liquid products at 400◦ C obtained with the dif-
ferent plastics follows the order: PS > PP > PE (HDPE, LDPE), with values in all cases
above 80%. The amount of solids deposited over the catalysts was below 1 wt% except for
PS (about 5%). In the last case, small cyclic intermediate precursors are first formed, which
subsequently polymerize leading towards the observed solid residues. These authors also
studied the composition of the liquids coming from the cracking of the different plastics
by PONA analysis (paraffins, olefins, naphthenes, aromatics). Figure 3.10(a, b) compares
the composition of the liquids obtained in the cracking of HDPE and LDPE, respec-
tively. Olefins were the main components of the liquids obtained with both polyolefins,
especially in the case of HDPE (>80%), while this share dropped with LDPE below
60%. The observed high selectivity towards olefins (primary products) and the lower one
towards the remaining products agrees well with the initially reported features of this
stirred semi-batch reactor.
3.2 FIXED-BED REACTORS
The fixed bed is likely the most classical catalytic reactor. However, its usage with plastics
as feed is not straightforward since the high viscosity and low thermal conductivity of
plastics pose serious problems for being loaded into the reactor. In some systems, the
molten polymer is introduced into the reactor through a capillary tube from a pressurized
tank [71]. The most usual technical solution is to carry out a previous thermal cracking
of the plastic. Then, the liquid or gaseous compounds resulting from the thermal process
can be fed easily into the fixed bed [72–75].
According to this concept, Masuda et al. [75] studied the catalytic cracking of the
oil coming from a previous thermal pyrolysis step of polyethylene at 450◦ C in the
bench-scale fixed-bed reactor shown in Figure 3.11. The catalysts employed were dif-
ferent zeolite types: REY (rare earth exchanged zeolite Y), Ni-REY (nickel and rare earth
100
80
60
Fraction (%)
Paraffin
Olefin
Naphthene
Aromatic
40
20
0
0 50 100 150 200
Lapse time (min.)
(a)
100
Paraffin
Olefin
80 Naphthene
Aromatic
60
Fraction (%)
40
20
0
0 50 100 150 200 250 300
Lapse time (min.)
(b)
Figure 3.10 Fractions of paraffins, olefins, naphthene and aromatic products from the
catalytic degradation of plastics over spent FCC catalyst in a semi-batch reactor (400◦ C,
P /C = 10, N = 200 rpm): (a) HDPE; (b) LDPE [70]. (Reproduced with permission from
Elsevier)
88 J. AGUADO ET AL.
Feed oil
Tape heater
Zone for pre-heating steam
N2
N2
Water
Syringe pump
Gas pack
Ni-REY Condenser
Glass beads
Ice+water
Reactor
673.2 K
Furnace
Figure 3.11 Bench-scale fixed-bed reactor used for the catalytic reforming of products
coming from the thermal degradation of polyethylene [75]. (Reproduced with permission
from Elsevier)
metal exchanged Y-type zeolite) and HZSM-5. The reactions were carried out under a
steam or nitrogen atmosphere at 400◦ C. Nickel was included in the catalyst formulation
in order to promote the transport of hydrogen atoms by spillover from steam to adsorbed
olefinic hydrocarbons over the acid sites. When steam is used as the carrier, the strong
acid sites of the catalysts are partially covered by hydrogen. As these strong acid sites are
responsible for the formation of coke, catalyst activity is maintained for a longer time.
Optimum nickel level in Ni-REY zeolite was about 0.5%. Conversions above 70% of the
heavy oil and selectivities towards gasoline close to 80% were attained and maintained
constant over Ni-REY after five sequences of reaction and regeneration. When HZSM-
5 zeolite was used as catalyst, a fast deactivation was observed as a consequence of a
dealumination process caused by the steam presence.
3.3 FLUIDIZED-BED REACTORS
Fluidized-bed reactors are featured by presenting both temperature and composition homo-
geneity. This is a remarkable advantage for the cracking of polymers due to their low
thermal conductivity and high viscosity that usually lead to the appearance of temperature
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Figure 3.12 Flow scheme of a fluidized-bed reactor (Hamburg process) [76]. (Repro-
duced by permission of Wiley VCH)
gradients in other reaction systems wherein heat is not as properly transferred. One of
the best known process for pyrolysis of plastic wastes is the Hamburg process developed
by Kaminsky et al. [76] which is depicted in Figure 3.12. The fluidized bed consists of
a 154 mm diameter, 670 mm height tube of stainless steel filled with 9 kg of sand and
a gas distributor at the bottom formed by a steel plate with 108 tubes. The reactor is
heated by 5 kW filaments and the input material is fed into the reactor by two screw
90 J. AGUADO ET AL.
conveyors. The products obtained are separated in several stages comprising a cyclone,
coolers and electrostatic separators. Initially, this system was exclusively applied for the
thermal cracking of polymer wastes using as fluidizing agent nitrogen or preheated steam.
Thus, by pyrolysing at 510◦ C a mixed plastic waste mainly formed by polyolefins, a 90
wt% conversion towards oil and waxy products was attained while at higher tempera-
tures (690–735◦ C) an oil consisting of 40% of BTX (benzene, toluene and xylenes), was
obtained [77]. When PS and PMMA were used as feed, actual depolymerization towards
the constituting monomers took place since they were obtained with high selectivity (61%
of styrene and 97% of methyl methacrylate). On the other hand, if steam was used as
fluidizing agent at 700–750◦ C, high yields of light olefins such as ethylene (21–29%),
propylene (16–21%) and butadiene (5.6–6.6%) are achieved [17].
Mertinkat et al. [78] modified the Hamburg process for performing the catalytic crack-
ing of the polymers by using as fluidizing medium an FCC catalyst instead of the inert
sand or quartz employed in the thermal process. The amount of catalyst and plastic fed to
the reactor was roughly 1 kg h−1 each and the residence time was varied within 3–12 s.
Catalytic cracking of polyethylene at 450–515◦ C yielded gases (50%) and aliphatic
oils (40%), while for polystyrene degradation, the main products were ethylbenzene
(18–26%) and benzene (9–22%), with a significant reduction in styrene share (1–7%).
Other researchers have also studied the catalytic pyrolysis of PS over HZSM-5 zeolite [79]
and of different polyolefins over several acid solids using fluidized beds [80–82].
3.4 SPOUTED-BED REACTORS
One of the firstly proposed approach for the feedstock recycling of plastic waste was to
merge them with standard FCC feedstocks and to submit them to cracking directly in
FCC refinery units. According to this idea, a new reaction system denoted as spouted bed
or riser simulator was proposed that allows for reproducing the conditions existing in an
actual FCC unit [83–85]. The feed is usually a blend of 5–10 wt% plastic (PE, PP, PS)
in an oil such as light cycle oil (LCO), vacuum gas oil (VGO) or even pure benzene. The
scheme of the reactor is shown in Figure 3.13. It is an internal recycle reactor which can
operate at low contact times (1–10 s) and with a suitable catalyst/oil ratio (e.g. C/O = 6).
As inferred from Figure 3.13, the catalyst is placed in a basket and the gases are impelled
Shaft
Seal
Cooling jacket
Impeller
Gasket
Heater cartridge
Injection Catalyst
Riser Porous plate
simulator
Ideal riser
Figure 3.13 Scheme of a riser simulator reactor for plastic conversion [83]. (Reproduced
by permission of Javier Bilbao)
by a turbine located in the upper part, circulating through the basket. At zero time, the
feed is injected and when the reaction is completed, a valve is open, releasing the products
into a vacuum chamber, being subsequently analysed.
The cracking of PE/LCO and PP/LCO blends over HZSM-5 zeolite catalysts in the
riser simulator at 450◦ C led towards mainly a C5 –C12 hydrocarbon fraction of aromatic
nature and a low yield of C1 –C2 gases and coke.
3.5 SCREW KILN REACTORS
Recently, a new reaction system has been designed for the thermal and/or catalytic degra-
dation of plastics and plastics–oil mixtures [86–88]. The reactor is named screw kiln
reactor and its design reminds that of the extruders widely applied for polymer process-
ing. The scheme and a photograph of this system are shown in Figure 3.14. Basically,
the reactor is provided with a hopper wherein the plastics or plastics–oil mixtures are fed
and heated at temperatures within 250–300◦ C by two external furnaces under a nitrogen
atmosphere (at slightly higher pressure than atmospheric). The melted reacting mixture is
subsequently fed into the reactor by means of a screw located inside a 52-cm-long stain-
less steel tube with 2 cm internal diameter, which is the actual reaction zone. The tube
is heated externally by two furnaces whose temperature can be adjusted independently,
the reactor being divided effectively into two heating sections (denoted as T1 /T2 ). Tem-
perature is continuously controlled by a set of built-in thermocouples through the reactor
in order to avoid the appearance of cold spots and the subsequent plastics solidification.
Screw speed can be varied within 0.5–25 rpm, thereby changing the residence time of
the plastics. The small diameter of the screw assures that the radial temperature profiles
are practically negligible. The catalyst is mixed up with the plastic at the hopper in order
to attain a homogeneous reacting mixture and it follows the same flow as the polymer
through the whole system, being recovered at the outlet simply by filtration.
As an example, catalytic cracking of pure LDPE was carried out in the screw kiln reactor
over mesoporous Al-MCM-41 (plastic/catalyst mass ratio of 50) at T1 /T2 = 400/450◦ C,
respectively. The reported yields of hydrocarbons within the gasoline range (C5 –C12 )
amounts to 80% with a high content of C7 –C8 hydrocarbons, stemming likely from
the occurrence of secondary catalytic oligomerization reactions affecting to the initially
formed C3 and C4 fractions.
Unlike other reacting systems, this reactor is not bound by the usual viscosity problems
of polymers as the extruder is used to displace the plastics, so pure plastics can be fed
without any flow trouble. This is a significant advantage with regard to conventional
fixed-bed reactors as in most of them the plastics just fall by gravity or the feed is indeed
the product coming from a previous thermal pyrolysis, not the polymer itself. Compared
with a conventional batch reactor, the screw kiln reactor leads to a lower formation of
gaseous products and reduces the overcracking of the heavier fractions. These results
were ascribed to secondary reactions occurring in the reactor due to the intimate contact
of the primary cracking products (mostly light gases) and the partially cracked plastics,
since no selective removal of the volatile hydrocarbons takes place inside the reactor, as
it occurred in the semi-batch reactors. Moreover, all the hydrocarbon fractions present
similar residence times within the screw kiln reactor, which also leads to a narrow product
distribution.
92 J. AGUADO ET AL.
Load of LDPE Nitrogen feed
T1 T2
Motor
Coolant
Ice Screw
(a)
(b)
Figure 3.14 Screw kiln reactor for the conversion of plastic and plastic-oil mixtures [87]:
(a) scheme; (b) photograph of a laboratory reactor. (Reproduced by permission from
Elsevier)
4 INFLUENCE OF THE MAIN OPERATION VARIABLES
Both the activity and selectivity of the catalysts heavily depend on the following reaction
variables:
• temperature;
• catalyst amount;
• time;
• plastic composition.
Henceforth, their respective effect over the catalytic cracking of plastics is described:
4.1 TEMPERATURE
Temperature is likely the most important variable affecting the catalytic cracking of plas-
tics. Reaction temperatures are usually in the range 300–450◦ C. In general, a temperature
increase leads towards a parallel activity enhancement of the catalysts. Nevertheless, it
must be taken into account that at high temperatures the simultaneous occurrence of
thermal cracking reactions is favoured, which may modify the product selectivity.
Additionally, the temperature affects in a different way the reactions involved in the
carbocationic chain pathway (initiation, propagation, termination) as they can be either
mono or bimolecular, also changing the selectivity attained. Several studies have been
performed reporting the effect of temperature in the catalytic cracking of plastics [28, 35,
89]. Sharratt et al. [35] observed, in their catalytic cracking experiments of high-density
polyethylene (HDPE) over HZSM-5 zeolite in a fluidized bed within the 290–430◦ C
range, that as temperature rises, the yield of lighter hydrocarbons increases as well as that
of BTX and coke. In addition, these authors observed a decrease of the olefin/paraffin ratio
in the gaseous fraction from 5.4 to 3.6. In another study performed in a semi-batch reactor,
the influence of the temperature on the catalytic cracking of a model plastic mixture
(46.5% LDPE, 25% HDPE and 28.5% PP) over both nanocrystalline HZSM-5 and Al-
MCM-41 was also studied in the range 375–450◦ C [28]. The conversion increased with
temperature leading to total conversion at 450◦ C for a plastic/catalyst mass ratio of 100.
However, the share of heavier hydrocarbons augmented with temperature (see Figure 3.15
80
T = 375°C T = 400°C
70 T = 400°C 35 T = 450°C
T = 425°C
T = 450°C
30
60
25
50
Selectivity (wt%)
20
40
15
30
10
20
5
10 0
0
C1– C4 C2– C4 C5– C12 C6– C9 C13– C22 C23– C40 0 5 10 15 20 25 30 35 40
Paraffins olefins Aromatics Carbon atom number
(a) (b)
Figure 3.15 Product distributions obtained in the catalytic cracking of a polyolefin

mixture over HMCM-41 at different temperatures (P /C = 100; t = 30 min): (a) selectivity
by groups; (b) selectivity by carbon atom number [28]. (Reproduced by permission of
the American Chemical Society)
94 J. AGUADO ET AL.
for the products obtained over Al-MCM-41), which was ascribed to the larger extent of
thermal cracking reactions and also to the vaporization of these heavier compounds at the
highest reacting temperature, leaving subsequently the reaction medium. In addition, for
nanocrystalline HZSM-5, a decrease in both C4 and C5 selectivity, while C3 remained
almost constant, was observed on going from 400 to 450◦ C, which was explained in
terms of the higher extent of direct scission reactions at the end of polymer chains instead
of previous rearrangements. Similar results were appreciated by Ishihara et al. [89]; at
low temperature, the main products of polyethylene degradation were both isobutane
and isobutene, but at higher temperature, propylene begins to be formed in meaningful
amounts.
4.2 CATALYST AMOUNT
Sharratt et al. [35] investigated the catalytic cracking of HDPE over HZSM-5 zeolite
varying the polymer-catalyst mass ratio from 1:10 to 1:1 at 360◦ C in a fluidized-bed
reactor. The obtained conversions were always above 90%. However, some differences
were appreciated regarding the product distribution. The increase in polymer/catalyst mass
ratio led towards higher yields of gaseous C1 –C4 hydrocarbons (61–69%) and coke. This
is an expected result since primary cracking reactions leading towards the formation
of C3 –C4 are favoured as the amount of catalyst is increased, whereas the secondary
reactions involving these olefinic gases occur in a minor extension, due to the really short
residence time in the fluidized-bed reactor.
On the other hand, the catalytic cracking of a model plastic mixture (46.5% LDPE,
25% HDPE and 28.5% PP) at 400◦ C in a semi-batch reactor was carried out varying the
plastic/catalyst mass ratio (P/C) from 200 to 4 [28]. When nanocrystalline HZSM-5 zeolite
was employed as catalyst, the selectivity towards gases (C1 –C4 ) and gasoline (C5 –C12 )
was always within 45–50%, irrespective of the P/C ratio used. However, the composition
of both gaseous and gasoline fractions changed significantly. The paraffin/olefin proportion
in gaseous hydrocarbons increased on diminishing the plastic/catalyst mass ratio. The
same trend was observed for the aromatic content in the gasoline fraction, as shown in
Table 3.2. These results suggest that secondary reactions involving the olefins produced
directly from the plastic cracking take place in a growing extent as the amount of catalyst
is increased.
Table 3.2 Aromatic hydrocarbon content in the gasoline fraction resulting from the cracking of
a polyolefin mixture at 400◦ C over n-HZSM-5 zeolite at different P/C ratios [28]
P/C ratio Benzene Toluene Ethylbenzene Xylenes Trimethylbenzenes

(w/w) (%) (%) (%) (%) (%)
200 0.33 0.41 0.25 0.91 0.64
100 0.60 0.34 0.28 0.99 0.44
50 0.81 0.87 0.54 3.39 0.23
10 0.98 3.46 1.28 6.90 0.81
4 1.03 5.32 1.74 9.19 2.28
Both examples illustrate clearly the influence of the catalyst amount in the product
selectivity. Therefore, an adequate tuning of both primary/secondary reactions is required
to achieve the desired product distribution.
4.3 TIME
Changes in the performance of catalysts with time are directly related to their deactivation
kinetics. However, work aimed at studying the catalyst deactivation in the cracking of
polymers is scarce in literature. Lin et al. [90] have investigated the deactivation of USY
zeolite in the catalytic cracking of HDPE using thermogravimetric analyses (TG). These
authors observed that USY zeolite was deactivated by coke deposition and established
a exponential relationship between the activity decay and the measured coke content.
Similar conclusions were drawn by Uemichi et al. [91] in their study of the deactivation
of several zeolites (HZSM-5, HY, H-mordenite) and silica–alumina in the cracking of
LDPE in a fixed bed. The plastic, previously melted at 310◦ C, was fed into the cat-
alytic bed by capillary pressure. Catalyst deactivation was studied within the temperature
range 375–526◦ C using a space time (W/F) of 7–23 g catalyst min g−1 of polyethylene.
HZSM-5 was observed to be the most effective catalyst for degrading the plastic into
gasoline range hydrocarbons rich in isoparaffins and aromatics with very low deactiva-
tion by coke deposition during the time on stream. However, the mordenite and Y zeolites
suffered of strong deactivation, leading to a fast fall in liquid production, probably due
to the pore blockage by coke. In contrast, silica–alumina retains a good performance
over time, probably due to their large pore size. The authors also studied the catalyst
deactivation in polystyrene degradation. In this case, a strong deactivation was appre-
ciated over all the catalysts because of the formation of unsaturated and polyaromatic
compounds (indane and naphthalene derivatives) that were converted to coke, in keeping
with previous observations [92].
4.4 PLASTICS WASTE COMPOSITION
The composition of the raw plastic wastes may have a huge influence on the performance
of the catalysts. Hence, catalysts leading to high conversions for the cracking of pure
polymers have often been observed to lose their activity to a large extent when cracking a
real mixture of plastic wastes. In addition, plastic wastes makeup varies largely, depending
on the origin of the waste, making difficult to foresee in a general way the performance
of the different catalysts. This fact was observed in the cracking of plastic film waste
coming from Spanish greenhouses [93]. Apart from the influence of non plastic compo-
nents (additives, dirt, etc.), it was proven that the presence of a 4 wt% of EVA copolymer
in LDPE decreases the activity of mesoporous catalysts (Al-MCM-41, Al-SBA-15) to
values close to those of thermal cracking. Owing to these facts, several works have been
recently published dealing with the cracking of standard mixtures of several plastics, in
order to ascertain their influence on the cracking activity and product distribution. Yanik
et al. [94] studied the catalytic degradation of polymer mixtures made up of PVC/PE,
PVC/PP and PVC/PS (8:2 mass ratio) at 430◦ C. The tested catalysts were red mud (a
96 J. AGUADO ET AL.
waste from alumina production formed by a mixture of iron, aluminium, silicon, calcium,
sodium, etc.) and a combination of silica–alumina and y-Fe2 O3 (chlorine adsorbent). Red
mud and iron oxides showed good properties for chlorine fixation although it was con-
cluded that the catalyst promotes the formation of some organic chlorinated compounds,
whose amount was markedly lower for thermal cracking.
Likewise, Tang et al. [95] have investigated the catalytic cracking of mixtures of several
polyolefins and PVC (PP/PVC, PE/PVC, PS/PVC) at 360–380◦ C over a novel Al-Zn
composite. These authors observed that the composite accelerated the degradation of the
plastic mixtures and retained the chlorine resulting from PVC degradation.
5 PROCESSES
Initially, processing of plastic wastes was proposed to be carried out directly through their
incorporation into the streams of oil refineries, since their main components (polyolefins)
present several advantages that convert them into a desired feedstock for the different
refinery units. These plastics possess a high hydrogen/carbon ratio (around 2) with a low
tendency to form coke due to its aliphatic composition, showing also a reduced metal
content. However, it was obvious fairly soon that this choice presented several important
drawbacks coming from the own working specifications of the refinery [3], the main ones
are quoted as follows:
• halogen content should be below 20 ppm;
• feed must be pumped as an oil or gaseous stream, free from solids;
• absence of filler materials, which may foul heat exchangers and plug pipes or other
conduits;
• absence of condensable additives;
• Heavy metal content below 0.1 wt% to avoid deposits, coking and catalyst fouling.
During the last decade, there have been a significant increase in the number of patented
processes that use catalytic cracking technologies for the upgrading of plastic wastes
and/or the oils derived from a previous pyrolysis treatment. The number of patents has
grown especially in the Asian countries, wherein the depletion of available landfills caused
by the overpopulation has triggered a huge regulation pressure.
From a technical point of view, the great majority of the patented processes based
on catalytic pyrolysis of plastic wastes are mainly addressed towards the preparation of
different grade fuels (gasoline, kerosene, diesel). Two groups can be easily envisaged
within these patented processes. The first one will be made up by those processes that
cracked the plastic wastes directly, without any previous thermal treatment for precracking
them and/or releasing unwanted products (e.g. hydrogen chloride from PVC). The only
thermal step before the catalytic cracking is the melting of the plastic for feeding it
continuously inside the catalytic reactor. The second group comprises those processes in
which plastic wastes are first thermally cracked in a previous step. After the removal of
undesired compounds (such as hydrochloric acid), the products resulting from the thermal
treatment are fed to the catalytic stage, where they undergo a catalytic upgrading towards
more valuable products so as to improve the whole economy of the process.
Additionally, some particular catalytic cracking processes for recovering specific raw
chemicals from plastic wastes can be found in the literature. This is the case of the process
patented by Mazda Motor for the recovery of phthalic anhydride from plastic materials
(mainly PVC), containing phthalate ester as plasticizer [96]. The process comprises three
main steps: (a) heating at temperature below 350◦ C to vaporize the desired product;
(b) catalytic cracking over a solid acid (preferentially alumina); and (c) recovery of the
obtained phthalic anhydride. The process also considers the recovery of the hydrogen
chloride released on heating the PVC-containing plastic waste material.
5.1 DIRECT CATALYTIC CRACKING
In addition to requiring just one reactor, direct catalytic cracking of plastic wastes presents
several advantages, mostly in terms of energy efficiency, with regards to the two stage
processes (thermal degradation and subsequent catalytic reforming). Both residence time
and reaction temperature might be lowered by the use of catalysts, which reduces energy
costs significantly. Additionally, the nature of the obtained products might be tailored
by a judicious choice of the catalysts, making unnecessary the use of a second catalytic
reactor for reforming them.
However, this technology suffers of different limitations, the main one being related
to the catalyst performance along the time on stream. The catalysts should be resistant
to the heterogeneous nature of the plastic waste stream as well as to the presence of a
large variety of additives. Additionally, the possibility of repeated regeneration cycles of
the catalyst should be deeply regarded in the design of the process so as to achieve a
better profitability. In the light of these facts, fluid catalytic cracking technology seems
to be an interesting choice, provided that the specific fluidodynamic issues related to the
macromolecular nature of plastic waste can be properly solved.
Despite these inconveniences, there can be found in the literature some patented pro-
cesses for plastic waste cracking based on direct catalytic cracking in stirred semi-batch
reactors [98, 99]. Corma et al. [98] designed a process of direct catalytic cracking of either
pure or waste polyolefins (polyethylene, polypropylene, polystyrene), their mixtures and
including also halogen-containing polymers. Both catalyst and waste plastics are put into
contact in a stirred semi-batch reactor under a continuous gas flow (nitrogen and/or steam)
at temperatures within 300–550◦ C. The volatile products at the reaction temperature leave
the reactor, being separated and collected afterwards. Fresh FCC catalysts, balanced FCC
catalysts or their mixtures can be used in the process. The reported conversions varied
within the 30–96 wt% range, depending on the experimental conditions (amount of cata-
lyst, time and temperature). High selectivities towards gasoline (70–80 wt%) are attained,
with 10–20 wt% of diesel and fairly low amounts of gases (<10 wt%). The authors claim
that the profitability of the whole process is improved by the use of spent FCC catalysts,
which are meant to be a refuse from FCC units to be disposed of. Spent FCC catalysts
still retain enough activity for promoting the catalytic cracking of the plastic wastes and
are available in huge amounts after FCC shutdown.
An alternative process based on two sequential catalytic cracking stages aimed at obtain-
ing gasoline and diesel from waste plastics or heavy oil/waste plastics mixtures is shown
in Figure 3.16 [99]. The catalyst employed in the first step is made up of powder alu-
mina, waterglass and HZSM-5 zeolite and is mixed up directly with the waste plastics
in a screw reactor preferably at 600–700◦ C. The second catalytic step consists in a fixed
98 J. AGUADO ET AL.
bed containing zeolite ZSM-5, zeolite REY and flokite as major components, being oper-
ated at temperatures within the 300–600◦ C range to increase the output of gasoline and
diesel. As inferred from Figure 3.16, the first catalyst is previously heated in a combustion
chamber up to 600–700◦ C and thereafter, loaded into the first cracking reactor along with
the waste plastics stream continuously fed by a screw extruder. The loaded materials are
decomposed into gaseous hydrocarbons and an inorganic residue. The gaseous hydrocar-
bons are fed to a fixed bed to be decomposed into smaller molecules which are separated
afterwards in a fractionation column into gasoline and diesel. On the other hand, both
the residues and the first catalyst are collected at the bottom of the vaporizer and sepa-
rated in two successive stages. The coke deposited over the first catalyst is finally burnt
off in the combustion chamber before being added again into the first catalytic reactor.
The yields obtained indicate that for a starting feed of 1400 kg of waste plastics formed
by PP (25%), PS (25%) and PE (50%), 630 kg of gasoline (RON = 93.5; 48% olefins
and 19.9% paraffins, 9.9% aromatics), 420 kg of diesel (cetane value = 52; 55% olefins,
10% aromatics), 140 kg of inorganic residues and 210 kg of flammable gas are attained.
However, no data are provided about the effect of the heteroatoms content in the feed
and their influence on the catalyst behaviour.
In agreement with the concept of using several catalytic stages, Kwak et al. [100]
recently designed a method for converting waste plastics into gasoline, kerosene and
Cyclone
Combustion
chamber
Oil
Catalyst
Fractionation
Waste plastics Fixed column
bed
reactor
Heavy oil
Screw Vaporizer
reactor
Separator
Figure 3.16 Scheme of a process for the direct catalytic cracking of plastic wastes in
two steps [99]
diesel by means of a three-step catalytic process. In the first step, melted plastic wastes are
subjected to a simultaneous dehydrogenation and decomposition treatment over a nickel-
based catalyst at temperatures around 350–370◦ C for roughly 20 min. This treatment
enables a reduction in the molecular weight between 1/8 and 1/12 of their starting values.
The second catalytic step is carried out in a fluid catalytic cracking pipe at 500–550◦ C
using a silica–alumina catalyst. Subsequently, steam is introduced to remove heavy oils
present on the catalyst surface. The cracked products are separated by distillation into
three fractions: gasoline, kerosene and diesel oil. The third catalytic step is solely applied
to the gasoline fraction in order to reform it towards a higher quality product by contacting
with an acid catalyst such as HCl, AlCl3 and SbCl3 .
Another approach for overcoming the problems posed by conventional cracking cata-
lysts has been disclosed recently by Reverso et al. [101]. In this case, direct cracking is
performed by using as catalyst a molten bed of pure metal or a metal mixture (mainly
lead, zinc, tin) at a temperature of 460–550◦ C wherein the waste polymer is loaded inside
the reactor at a certain depth. The authors point out that the products are indeed a result
of the combination of both thermal and catalytic cracking. The catalyst composition may
also include some acidic component such as metal silicates, metal carbonates and their
mixtures. The process can be applied to pure and mixed polymers (PE, PET, PP, PVC),
as well as to the plastic fraction of municipal solid wastes.
5.2 THERMAL DEGRADATION AND SUBSEQUENT

CATALYTIC UPGRADING
This type of process is the preferred choice for treating plastic wastes containing a high
proportion of components that may affect negatively the catalyst performance. The occur-
rence of a previous thermal step allows for the removal of many of these components
previously to the catalytic treatment.
Figure 3.17 illustrates the flow sheet of the process developed by the company Nippon
Steel Corporation, being applied in Japan on a commercial scale [102]. The process may
use as raw materials any kind of plastic wastes, including chlorine contents from PVC
and limited amounts of nonplastic components, such as paper, fibres and aluminium foil.
It includes a pretreatment to remove undesired materials (metals, paper, etc.). Then, the
crushed plastic wastes are loaded by a screw conveyor into a mixing tank, being melted
at 300◦ C. In this stage, PVC is thermally decomposed and more than 90% of chlorine is
removed in the form of hydrogen chloride. The melted plastics are fed into the thermal
cracking vessel operating at 400◦ C and pressures close to atmospheric. The gas stream
derived from the thermal degradation is first purified from additional HCl, released in
the thermal treatment, and subsequently reformed by contacting with a catalyst in a fixed
bed reactor, leading to oils useful as fuel. The carbon residue precipitated in the thermal
cracking reactor is discharged out of the process continuously by using a centrifugal
separator and finally burnt at about 1100◦ C within an incinerator. Several pilot and semi-
commercial plants are being setting up in Japan based on this technology.
Although the great majority of the aforementioned processes for giving added value to
the product of a previous thermal cracking have been addressed towards the production of
higher quality fuels, other alternatives have been proposed yielding completely different
100 J. AGUADO ET AL.
PRETREATMEN SYSTEM
Bag
Machinery Magnetic Wind
Waste plastics crusher Crusher
separator separator separator
(opener)
LIQUEFACTION SYSTEM
HCL removal HCL removal Catalytic cracking

equipment tower tower
Extruder
Product
M oil
Mixing Thermal
tank cracking
tank
Heating
furnace
Centrifugal
separator
Carbon residue
Figure 3.17 Flowsheet of a waste plastic liquefaction plant based on thermal cracking
and subsequent catalytic reforming [102]. (Reproduced by permission of the International
Solid Waste Association (ISWA))
products. In this regard, the upgrading of a polyethylene waste by its conversion into
lubricating oils with high viscosity index has been patented by Chevron [103]. The process
starts with the thermal conversion of pure or waste HDPE at 600–700◦ C giving rise to
a mixture of n-paraffins and 1-olefins (25–75 wt%). The heavy fraction in this mixture
(boiling point above 650◦ C) is separated and then passed through a hydrogenation zone
to remove the N, S and O heteroatoms that might deactivate subsequently the dewaxing
catalysts. Finally, the effluent of the hydrogenation zone is isomerized using a typical
dewaxing catalyst such as an intermediate pore size molecular sieve (e.g. ZSM-22, ZSM-
23, SSZ-32, SAPO-11). According to this patent, the lubricating oils obtained show pour
and cloud points below −9.5◦ C and −3.9◦ C respectively, the oil yields being above
50 wt%.
Other interesting products that can be obtained from waste plastics using combined
thermal and catalytic processes are alkylaromatic compounds, which possess industrial
applications as automatic transmission fluids (ATF), detergents (linear alkyl benzenes,
LAB), and improvers of cetane number in diesel fuels [104]. The process uses as raw
material the olefins generated in a previous step of thermal and catalytic cracking, which
represent a cheaper source of olefins alternative to the currently existing ones. No special
details about the conditions applied for the olefin production are indicated, the emphasis
being focused on the alkylation step. Alkylation catalysts comprise conventional Lewis
acids (AlCl3 , FeCl3 , TiCl4 , ZnCl2 , etc.) and solid acids such as pillared clays, natural and
synthetic zeolites (ZSM-5, ZSM-12, ZSM-23, USY), amorphous silica–alumina, etc.
6 RELATED TECHNOLOGIES: COPROCESSING
In addition to the above-mentioned catalytic processes, there are some other related tech-
nologies wherein the catalytic cracking of plastic wastes is combined with the coprocessing
of other substances, mainly coal and petroleum feedstocks (lube oil, LCO, VGO) or even
a solvent. Hereafter, these technologies are explained more in detail.
6.1 COAL
Coprocessing of plastics with coal in order to convert both of them into fuels is another
promising option deeply studied by different authors [105–109]. The different chemi-
cal nature of plastics (mainly aliphatic due to its polyolefin character) and coal (aro-
matic) affect to the choice of a solvent, as well as of the reaction conditions, for their
joint processing. To circumvent this bound, a two stage process was proposed by Luo
et al. [106] for the coprocessing of commingled waste plastics and coal, which is depicted
in Figure 3.18. The use of two separate stages allows for a better selection of the reac-
tion conditions and catalysts so higher yields of the desired boiling points products were
attained.
In the first step, the plastics mixture (either a model one made up of 50% HDPE, 30%
PET and 20% PS or an actual mixture formed primarily of HDPE and PP) was catalytically
degraded at 440◦ C under 2.8 MPa of H2 over different catalysts (HZSM-5 zeolite and
First stage: Waste plastics
Second stage: Coal

Gas Volatiles
Gas Volatiles
Plastics Plastics oil

Step 1
reaction
IOM THF <100°C

solubles <200°C
Coal Step 2 Simulated <300°C
reaction distillation <400°C
<500°C
>100°C
IOM Left on GC column
Figure 3.18 Scheme of a two-stage process for waste plastics and coal coprocess-
ing [106]. (Reproduced with permission from Elsevier)
two commercial catalysts). The products resulting from the first stage were a gaseous
hydrocarbon fraction, a liquid fraction soluble in hexane (plastics oil), other liquid fraction
soluble in tetrahydrofuran (THF) and an inorganic matter insoluble fraction (IOM) formed
mostly by ash. Conversions in this first stage was around 85–95% over all the studied
catalysts, the highest amount of hexane-soluble oils compounds from the model plastic
mixture being attained over zeolite HZSM-5 (75%). The hexane soluble fraction was
used as solvent for the second stage wherein coal was hydrotreated at 400◦ C for 30 min
under 5.6 MPa of H2 using several slurry hydrotreating catalysts such as Mo naphthenate,
Fe naphthenate (500–1000 ppm) or their combination plus sulphur (6000 ppm). Coal
liquefaction is affected by the reactions conditions of the first stage that determine the
composition of the produced solvent. These authors observed that the combination of
HZSM-5 in the first stage and Mo-naphtenate and sulphur in the second one yielded both
the highest conversion and production of hexane soluble fraction.
6.2 PETROLEUM CUTS
The possibility of cofeeding plastic wastes with petroleum cuts such as vacuum gas oil
(VGO) [110], Arabian light petroleum residues [111], light cycle oil [84], lube oils [88]
or even raw chemicals such as benzene [85] has been widely investigated in the literature.
The underlying aim is to reduce the high viscosity of the molten plastics. However, there
is a limit since the maximum amount of plastics in the mixture to achieve a convenient
rheological behaviour must be at most within 5–10 wt%.
In this way, Ng [110] reported the catalytic cracking of blends made up of vacuum gas
oil (VGO) and 5–10 wt% of high-density polyethylene in a fixed bed reactor at 510◦ C over
a FCC catalyst. High conversion of HDPE was obtained although using large catalyst/oil
mass ratios (in the range 2–6). The gasoline yields depended on the polyethylene content
of the starting blend as well as on the operation conditions. The gasoline obtained with a
5% HDPE blend appears to be subsequently decomposed into gas and coke by secondary
cracking reactions while with the 10% HDPE blend, a higher gasoline yield was attained
(>50%).
Arandes et al. [84] studied the catalytic degradation of several plastics (polypropylene,
polystyrene, polystyrene–polybutadiene) dissolved in a light cycle oil (LCO) in a riser
simulator of a FCC unit using both a fresh and an equilibrated FCC catalysts. Similarly,
De la Puente [85, 112] studied the catalytic degradation of styrene-based polymers dis-
solved in benzene streams in the same riser simulator. Although the reported results are
promising, oil refiners are reluctant regarding the inherent risks for the normal operation
of the refinery units.
Another alternative that has been recently reported considers the use of spent lube oil
as cofeed in the catalytic cracking of plastics [88]. At present, there could be a bound
because of the available amounts of used lubricating oils are lower than those necessary
to reach the aforementioned limit of 5–10 wt% plastic content for an adequate viscosity
of the mixture. However, the use of a screw kiln reactor has allowed LDPE–lubricating
oil base mixtures with compositions ranging from 40/60 to 70/30 (%, w/w) to be cracked
catalytically. This is a remarkable advantage, as plastic–lubricating oil mixtures with
compositions more in line to those actually occurring in the market may be degraded.
H2
4
6 5 2 H2
H
HH H 1
Pd H H H H 3 HH H Pt 7
Carbon
Coke
Figure 3.19 Reaction model of styrene based polymers over a carbon supported
metal catalyst [57]: (1) Dehydrogenation on carbon; (2) dehydrogenation on metal;
(3) hydrogen transfer; (4) hydrogenation on metal; (5) hydrogenation on carbon;
(6) hydrogen desorption from metal; (7) hydrogen desorption with coking. (Reproduced
by permission of Springer-Verlag GmbH)
Additionally, these authors also found that the presence of lube oil decreased the activity
of the catalysts due to the presence of both sulphur- and nitrogen-containing compounds
(4000 ppm of sulphur and 85 ppm of nitrogen) that poisoned the acid sites. Consequently,
higher temperatures (450–500◦ C) should be employed to obtain complete conversion in
the catalytic cracking of the LDPE-lubricating oil mixture over Al-MCM-41 and nanocrys-
talline HZSM-5 catalysts.
6.3 SOLVENTS
The use of solvents with hydrogen transfer properties offer interesting possibilities in
the cracking of polymers. This was observed by Matsumoto [57] in the catalytic crack-
ing of styrene-based polymers (polystyrene, poly-(4-methylstyrene), poly-(4-butylstyrene),
poly-(α-methylstyrene) over metal supported carbon using decalin as solvent. Decalin
possesses hydrogen transfer properties so the olefinic products derived from the catalytic
cracking are thoroughly hydrogenated to the saturated form by hydrogen transfer reactions
from the solvent, which is transformed into tetralin and naphthalene with simultaneous
release of hydrogen (Figure 3.19). Plastic cracking in the presence of solvents with hydro-
gen donor ability allows for suppressing coke formation, being an advantageous choice
for aromatic function-containing polymers.
7 CONCLUDING REMARKS
Catalytic cracking and conversion of plastics wastes is currently a field of intense research
and open to innovative technologies to be discovered and applied. Significant advances
have been carried out in recent years, with several commercial plants being already in
operation based on the use of catalytic cracking for the plastic waste conversion into
valuable products. However, there is still room for further developments. In this regard,
the following fields of research can be foreseen in the next years:
• development of new catalysts capable of dealing with the heterogeneity of the plastic
waste makeup and the diffusional/steric hindrances posed by their bulky nature;
• design of reaction systems appropriate to the high viscosity and low thermal conduc-
tivity of the plastics;
• study of the influence of the different additives and components in the performance
of the catalytic process, regarding the diversity in origin of plastics wastes (urban,
agriculture, etc.);
• improvement of the currently existing catalysts in order to achieve the preparation of
specific and valuable raw chemicals (e.g. light olefins, aromatics, etc.) so as to get a
better profitability of the whole plastic recycling system.
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4
Thermal and Catalytic Conversion

of Polyolefins
JERZY WALENDZIEWSKI
Faculty of Chemistry, Department of Fuels Chemistry and Technology Wroclaw
University of Technology, ul. Gdańska 7/9, 50-344 Wroclaw, Poland
1 INTRODUCTION
Pyrolysis and cracking of waste polyolefins (plastics) can be categorized as the tertiary
mode of recycling. Application of this type of recycling is reasonable especially in case of
polyolefins when their further using in primary recycling (conversion into products similar
in nature to the original product) and secondary recycling (conversion into products of
different shape for less demanding products) is impossible. Pyrolysis and cracking are con-
sidered as alternative methods of the final processing of waste plastics such as polyolefins.
In comparison with incineration, known as the quaternary mode of recycling, the tertiary
mode of recycling is generally accepted. In thermal or catalytic cracking the main products
of processing are gas, naphtha, both light and heavy gas oil fractions, and solid residue
similar to coke. The main product of high-temperature pyrolysis process, 600–800◦ C,
is C2 –C4 olefins containing the gaseous fraction. Besides cracking and pyrolysis, other
modes of the tertiary recycling can be applied: hydrolysis, ammonolysis or methanolysis
for condensation polymers (polyethylene terephthalate, PET and polyurethane, PU) while
gasification, hydrocracking, coking and visbreaking for additive polymers such as poly-
olefins, i.e. mainly polyethylene (PE), polypropylene (PP) and polystyrene (PS). Waste
plastics cracking and pyrolysis can be especially profitable in the case of continuous
increase in landfill taxes and the world cost of crude oil. This section presents some
results of literature data on thermal and catalytic processing of waste polyolefins, types of
applied processes, design of reactors and catalysts as well as possible products and their
application and finally some economic considerations.
112 J. WALENDZIEWSKI
2 GENERAL SCHEME OF WASTE POLYOLEFIN PROCESSING
Similarly to crude oil cracking the products of the waste polyolefin cracking process
are hydrocarbon fractions. According to the process conditions different shares of gas,
gasoline, light and vacuum gas oil fractions as well as solid residue (coke) can be obtained.
The unsaturated character of these products makes the further treatment, i.e. hydrorefining
or application as the feed in cracking or hydrocracking processes, necessary. Light gaseous
fractions can be used as the source of C2 –C4 olefins for polymerization or fuels for
power generation. High-temperature processing of polyolefins, pyrolysis, similar to the
petrochemical process can give gaseous olefins and liquid fractions composed of aromatics
such as BTX fraction. Diverse applications of cracking products of waste plastics treatment
proposed by BP are presented by Kastner and Kaminsky [1]. A modified scheme of waste
polyolefin treatment is presented in Figure 4.1. According to the proposed technological
scheme the prepared waste plastics (after selecting, washing if necessary and granulating)
are submitted to the cracking process and the products obtained can be used with naphtha
as feed for a steam cracker or with vacuum gas oil as feed for fluid catalytic cracking.
Gasoline and light gas oil fractions can be delivered to a hydrorefining unit and processed
with similar refinery fractions.
Chemical composition of waste plastic cracking products depends on shares of the
individual polymers (PE, PP, PS) in the feed and process parameters. This fact decides
the technological application of the final products. Important products of the cracking
process, both petroleum fractions and waste plastics, are coke residues. Coke residue
yield increases considerably, up to 10 wt%, in cracking of municipal and industrial waste
plastics since they contain various inorganic impurities and additives. It can be applied as
solid fuel, like brown coal. In the fluid cracking the solid residue is continuously removed
from the process by combustion in a regenerator section.
By-products
Polyolefines pro- Polyolefines Steam
ducts consumption production cracker
Naphtha
Waste Polymer cracking Storage

Pre-treatment
polyolefines & purification & testing
Vacuum FCC
Hydrorefining
Gas product gas oil unit
Solid residue Hydrorefined

product liquid (solid) Refinery
hydrocarbon products
fractions
Figure 4.1 Cracking and pyrolysis of waste polyolefin processing, main products and
their application [1]. (Reproduced by permission of Hydrocarbon Processing)
CONVERSION OF POLYOLEFINS 113
Waste plastics potentially can also be processed in hydrocracking process as an addi-
tional feed stream in mixture with vacuum gas oil or crude oil residues. Careful plastic
segregation is then necessary since inorganic additives and impurities of plastics can foul
the hydrocracking catalyst. Noncatalytic high-temperature olefin pyrolysis (700–800◦ C)
and coking are insensitive to fouling.
3 WASTE PLASTICS SUITABLE FOR CRACKING AND PYROLYSIS
Cracking and pyrolysis are the suitable processes for the tertiary recycling of additive
polymers such as polyolefins, mainly polyethylene (PE), polypropylene (PP), polybutadi-
ene (PBD) and polystyrene (PS). Small admixtures of other plastics, such polyethylene
terephthalate (PET), polyvinyl chloride (PVC), less than two 2%, are admissible yet not
desirable. Taking into account the total share of polyolefins in plastics production (∼70
wt% including PS) they are the highest environmental problem. Their chemical composi-
tion (carbon and hydrogen) close to crude oil is the reason that this type of waste plastic
can be processed simply by the refinery medium-temperature methods such as thermal
and catalytic cracking, visbreaking or coking (temperature generally lower than 500◦ C) or
high-temperature noncatalytic processes (600–800◦ C), i. e. pyrolysis. The relatively low
density of PE, PP, PS in comparison with PVC and PET is the basis of water separation.
Commingled post-consumer or municipal waste plastics selected for cracking or pyrol-
ysis also contain other elements such as oxygen, nitrogen, sulphur and about ten metals
such as Al, Ca, Na (>100 ppm each) and Sb, Ba, Cr, Co, Cu, Fe, Pb, Mg, P, Zn, generally
below 50 ppm each. Inorganic compounds in waste plastics are contained in the different
types of additives and impurities (product remains). The total content of mineral com-
ponents in waste plastics (approximate analysis) attains value 0.5–1 wt% (ash) [2, 3]. In
our waste cracking experiments studies some PE samples selected from municipal wastes
contained ∼0.6 while PS even more than 3 wt% of inorganic components [4]. Theoretical
hydrogen content in PP and PE (C2 H2 )n is 14.28 wt%. The reduced hydrogen content
in waste plastics, e.g. 13.7 wt% [2, 3] is a result of some oxygen or nitrogen content
(admixture of PET or PA), inorganic components or PS (7.69 wt% H2 content). Depend-
ing on the origin the hydrogen content in crude oil is 11–14 wt% [5]. Therefore from the
cracking efficiency point of view, PE and PP are excellent feeds, better than PS since in
the cracking processes they give a lower coke yield. In the course of cracking inorganic
impurities and additives in waste plastics are deposited in coke (solid carbon residue).
The high yield of coke in the cracking process diminishes the yield of light hydrocarbon
fractions and complicates the process since it deactivates the catalyst and deposits over
heat exchange surface of the reactor.
4 MECHANISM OF CRACKING PROCESSES
The main task of thermal and catalytic cracking is decomposition of large (long) hydrocar-
bon molecules into smaller ones. High-molecular feedstock, such as paraffin hydrocarbons
and plastic chains produces lower molecular paraffins and α-olefins [5]:
R–CH2 –(CH2 )x –CH2 –CH3 → R–(CH2 )m –CH3 + CH3 –(CH2 )n –CH=CH2

Cracking of primary products, olefins, give higher molecular hydrocarbons by poly-
merization or tar and coke:
CH2 =CH2 + CH3 –CH=CH2 → CH3 –CH2 –CH2 –CH=CH2
R–CH2 –CH=CH2 + R –CH2 –CH=CH2 → tar, coke
It is generally accepted that thermal cracking is a free radical chain reaction (a free
radical is an atom or group of atoms with an unpaired electron). Free radicals react with
hydrocarbons and produce new hydrocarbons and new free radicals:
R–CH2 –CH2 –CH2 –CH3 + CH3 • → R–CH2 –CH2 –CH2 –CH2 • + CH4
Free radicals can decompose by giving olefins and new radicals [6]:
• •
CH2 –CH2 –CH2 –CH –CH2 –CH2 – → R–CH=CH2 + CH3 –CH2
The mechanism of thermal cracking and pyrolysis is discussed by Buekens et al. [7].
They proposed four types of pyrolysis reaction. In the case of PE, PP and PS cracking
only two type of the mechanisms were stated:
1. End-chain scission or depolymerization – production of monomers (stated for PS,
polyethylstyrene, polyisobutene);
2. Random-chain scission, randomly cutting into fragments of various length (stated for
PE, PP, PS, polyisobutene, polybutadiene).
In the PS cracking process both mechanisms are possible and therefore ∼60 wt% of
monomer can be recovered. Cracking of PP, PE and other polyolefins occurs by random-
chain scission and therefore a broad hydrocarbon spectrum is produced.
At higher cracking temperature other reactions, i.e. cyclization and dehydrogenation of
naphthenes and hydrocarbon pyrolysis with production of benzene and ethylene, butadiene
and hydrogen are also possible.
Since cracking rate increases with molecular weight of the feed (average number of
carbon atoms) then the rate of long-chain polyolefin cracking should be considerably
higher in comparison with the typical cracking feeds (vacuum gas oils, 20–30 carbon
atoms in chain) [6]. At the same cracking parameters, 500◦ C and presence of cracking
catalyst, conversion of n-pentane attained a value less than 1 while conversion of n-
hexadecane was 42 wt%.
The presence of catalyst is necessary in the catalytic cracking process. Acid cracking
catalysts produce carbonium ions by protons addition to olefins or abstracting of hydride
ions from hydrocarbon molecules:
R1 –CH2 –(CH2 )x –CH=CH–CH2 –R2 + H+

→ R1 –CH2 –(CH2 )x –+ CH–CH2 –CH2 –R2
R1 –(CH2 )x –CH2 –CH2 –CH2 –CH2 –R2 + R+
→ R1 –CH2 –(CH2 )x –+ CH–CH2 –CH2 –CH2 –R2 + RH
+
H2C
H3C + H3C
CH3 CH3
Figure 4.2 Intramolecular reaction between carbonium ions and double bond, cyclization
Polymer chains can be cracked through so called β-scission:
R1 –CH2 –(CH2 )x –+ CH–CH2 –CH2 –CH2 –R2

→ R1 –CH2 –(CH2 )x –CH=CH2 + + CH2 –CH2 –R2
This is a mechanism of polyolefin cracking. The main polymer chains are reduced by
reaction with protons or other carbonium ions, followed by chain scission giving C30 –C50
oligomeric hydrocarbons [7]. As a result of further, secondary cracking reactions by β-
scission of C30 –C50 hydrocarbons, gas and lower-molecular liquid C10 –C25 hydrocarbons
are produced. Other reactions are double bond and saturated hydrocarbon isomerization
as well as methyl ‘group shift’.
Production of carbonium ions gives the possibility to produce different hydrocar-
bons molecules, e.g. cycloparaffins and aromatics by cyclization and dehydrogenation
reactions (Figure 4.2). In the first step presumably intramolecular reactions between car-
bonium ions and double bonds take place.
In the next step dehydrogenation reactions give aromatic derivatives. The application
of cracking catalyst not only lowers the cracking temperature and increases the reaction
rate, but also results in higher production of iso-alkanes and aromatics.
5 WASTE PLASTICS PROCESSING

5.1 CATALYTIC AND THERMAL CRACKING PROCESSES: TYPICAL
PRODUCTS
The most exhaustive studies on waste plastics processing by cracking and pyrolysis meth-
ods were carried out at Hamburg University by Kaminsky and co-workers [ e.g. 1, 8]. As a
result of these studies various variants of the process were worked up. They used different
types of the feed compositions and process parameters, starting from the low-temperature
coking and cracking parameters (temperature lower than 500◦ C) and liquid and wax frac-
tion as the main products up to pyrolysis parameters (600–700◦ C) and C2 –C4 olefins and
aromatic derivatives as the main products. The fundamental advantage of these studies
is a continuous flow system and a fluidized-bed type of reactor (1–3 kg of waste plastic
pellets per hour). Thermal cracking of PE in a fluidized-bed reactor gives higher-boiling
products in comparison with PP cracking (50 and 70 wt% of <500◦ C boiling products,
respectively). One can observe almost linear change of fraction product composition:
gas, <500◦ C and >500◦ C boiling fractions when PP content in the feed changes from
0 to 100%. Small addition of PS to PP, PE or PE/PP mixture does not change product
composition appreciably.
Other results obtained at Hamburg University [9] pointed out the advantages of appli-
cation of spent FCC catalyst in the cracking process. It was found that processing of PS
in the temperature range 370–515◦ C in the presence of FCC catalyst gives high yield
of coke (up to 20%) and relatively low styrene yield. On the other hand a noncatalytic,
thermal process gives above 60% styrene yield, accompanied by trace quantity of coke.
At typical FCC cracking temperature (515◦ C) processing of PE results in almost 50%
C1 –C4 gaseous fraction yield, high shares of branched hydrocarbons and ∼10 wt% of
coke. Thermal PE cracking allows one to obtain low gas and coke yields (<2 wt%) while
liquid and wax fractions reach over 97 wt%.
Efficient thermal or catalytic cracking of waste polyolefins can be realized in tube
reactor with an internal mixer [10]. Depending on the type of raw material (commercial
PE, PP and PS) application of this reactor system in thermal process makes it possible to
obtain 85 wt% of liquid, semi-solid or solid product, 0.6–10 wt% gaseous product (mainly
C1 –C5 hydrocarbons) and 1–5 wt% of solid residue. In waste plastics cracking, yields of
carbon residue and gas can increase up to 5–10 wt%. The main liquid products (or solid
at ambient temperature) are characterized by high olefins content, bromine number more
than 50 g Br2 /100 g and freezing point above 40◦ C for the feed with high PE content.
The increase in PS and PP content in the feed is accompanied by lowering in freezing
point of the main products, even below −15◦ C. High shares PP containing cracking feeds
are especially suitable for production of light oil fractions of low freezing temperature
(even −25◦ C) and high octane index (>50). Solid, coke-like residue, depending on the
feed contains as much as 30–50 wt% of mineral components, including catalyst if used,
and its calorific value, similar to brown coal, attains value ∼20 MJ/kg.
The main difference between two types of the process, catalytic and thermal is in the
different conversion levels and products yields. High gas (∼50 wt%) and gasoline yields
(∼15 wt%) as well as low yield of gas oil and 10 wt% coke were found in the catalytic
processes (commercial catalysts). On the other hand the thermal cracking processes give
low gas, gasoline and light gas oil yields in connection with very high yield of waxes
(over 87 wt%) and small yield of coke [9]. Low coke yield in thermal process is the result
of the low cracking level of the polymer feed.
The high influence of cracking catalyst on PE conversion was confirmed by Aguado
et al. [11] in a continuous screw kiln reactor. The application of a sophisticated laboratory
Al-MCM-41 cracking catalyst and process temperature of 400–450◦ C led to 85–87%
yield of gas and gasoline fractions (C1 –C12 ). Besides olefins and n- and iso-paraffins
some quantity of aromatics, 5 wt% was determined in the process products. In the same
reactor system with a noncatalytic process the gas yield was halved while similarly as
in case of the fluid reactor system yields of gas oil and heavy waxes fraction (C13 –C55 )
attained values of ∼62% (compared with 4 wt% in catalytic process) [12].
The considerably lower activity of other catalysts in PS cracking process, HZSM-5 and
Al2 O3 -SiO2 of higher acidity is explained by hydrocarbon cross-linking and heightened
carbon residue yield. Similarly to the fluidized-bed process [9], the thermal PS cracking
results mainly in styrene while HMCM-41 catalyzed process produces mainly benzene and
ethyl benzene. Alkaline materials, e.g. magnesium or barium oxide, in PS cracking present
high activity and selectivity to styrene [13]. This suggests quite different reaction mech-
anisms, i.e. that thermal cracking proceeds through a free radical chain mechanism while
carbenium and anionic ions are involved in acid and alkaline catalysis cracking processes.
Increase in thermal process temperature up to 685–715◦ C in a fluidized-bed system
(Hamburg University Pyrolysis Process-HUPP) and application of a mixture of municipal
plastic wastes resulted mainly in gaseous products, over 41 wt%, of which olefins con-
stituted 15%, and aromatic (BTX)-containing liquid products [14]. Considerably better
results from the point of view of C2 and C3 olefins yield were obtained in other experi-
ments. The application of steam as fluidization agent instead of circulation pyrolysis gas
enabled an increase of C2 –C3 olefins yield from 48 to 60%, accompanied by decrease in
BTX yield from 24 to 11 wt% [15].
Analogous results were achieved in the fluidized-bed system by Williams et al. [16].
They found out that raising the PE pyrolysis temperature from 500 to 700◦ C gives an
increase in gas yield from 11 to 71% and that C2 –C4 olefins content increases from ∼7
to above 53%. Hydrogen content in the gaseous fraction attained a level of 1%. At the
same time oil and wax yields were diminished from 89 to 28.5 wt% in which 25% was
identified as mono- and polyaromatic hydrocarbons. Noticeable quantities of aromatics
(∼2.5 wt%) in the products of the process at ∼600◦ C were determined (Table 4.1).
Process temperature, as well as waste polyolefin composition and type of catalyst used
are then the most important process parameters. It is evident that a process temperature
below 500◦ C is the most suitable range for refinery fractions while 600◦ C and higher are
appropriate for olefins production.
According to Bockhorn et al. [17], cracking of waste plastics can be carried out ther-
mally in a three-step reactor cascade at laboratory scale in a reactor filled with special
moving steel spheres. At the lower temperature (330◦ C) quantitative PVC dechlorination
takes place, at 380◦ C polystyrene is decomposed with high styrene yield and 440◦ C is
suitable for PE cracking into paraffins and olefins. The molecular weight of the cracking
products obtained is a function of residence time of the feed in the reactor zone. In the
presence of PE (or PVC) cracking PS gives ethylbenzene as a result of the hydrogen
transfer from PE chains to styrene during the process.
In the range of higher temperatures, 475–525◦ C, commingled waste plastics conversion
increased in laboratory autoclaves from 79 to 99.5%, gas oil yield decreased from 48 to
19% while yield of cracking gas increased from 32 to 66%. It is visible that increase in
primary and secondary plastic conversion takes place. At the highest gas production the
yield of coke attained 8%. Even at the lowest process temperature, i.e. 475◦ C almost total
plastics conversion was attained in 15 min and the main cracking products were light and
heavy gas oils at 1–2% coke and 20% gas yields. On the basis of kinetics analysis the
authors concluded that cracking of polymers such as PE occurs to a greater extent near
the end of the polymer chain rather than in the middle of it [2].
Table 4.1 Influence of process temperature on product yields from fluidized bed pyrolysis of
LDPE [16]. (Reprinted from Journal of Analytical and Applied Pyrolysis, 1999: 51: 107, P Williams
& E Williams with permission from Elsevier)
Process products Process temperature, (◦ C)

500 550 600 650 700
Gas (wt%) 10.8 21.4 24.2 40.1 71.4
Oil (wt%) 43.9 43.2 51.0 47.8 24.6
Wax (wt%) 45.3 35.4 24.8 12.1 4.0
Olefins in gas (wt%) 6.9 16.5 17.43 31.0 53.1
Comparative studies of thermal and catalytic PP cracking indicate a strong influence
of catalyst on total conversion in the temperature range 340–380◦ C as well as gas and
gasoline yield [18]. The results also point out the possibility of applying an equilibrium
FCC catalyst [19]. Similar studies were carried out in other laboratories [7, 20]. The effect
of the application of cracking catalyst, including equilibrium FCC catalyst is the increase
in plastics conversion level, higher gas and liquid product yields as well as lower boiling
temperature range and density of the liquid cracking products obtained. This seems to be
a good solution. However, one has to remember that equilibrium FCC catalysts contain
heavy metals (mainly V and Ni) and they are classified as environmentally dangerous
materials. In the course of the cracking process they are collected in coke residues which
have to be utilized.
High conversion level of waste plastics can be also attained in hydrocracking pro-
cess with using of NiW-HY zeolite-based catalyst [20]. The main process products are
good-quality gasoline fractions, with small olefins content. The basic drawback of hydro-
cracking is the necessity of using hydrogen, expensive catalysts and increased pressure
(high cost of reactors and other plant equipment). Hydrocracking catalysts are also exposed
to deactivation by mineral components in the plastic feed. Bergius – Pier hydrogenation
technology was adopted by VEBA company for hydrocracking vacuum residue (waste
plastics mixture at 450–490◦ C and pressure 150–250 bar, 40 000 tons per year output).
The applied process catalyst and parameters gave ∼90 wt% conversion [21].
Sophisticated catalysts, such as ZSM-5 or HZSM-5 [22] and other zeolites are also sug-
gested in numerous papers, e.g. REY [23], HY and H-mordenite [24], Re-zeolite-based
Engelhardt FCC commercial catalyst [25], and steamed commercial zeolite catalyst [26].
These investigations are mainly devoted to fundamental studies and the correlation bet-
ween feed composition, catalyst properties, process parameters and efficiency connected
with product distribution. Iron supported on silica–alumina, mesoporous silica and active
carbons serves as the next example of materials applied in the waste plastics crack-
ing [27, 28]. On the other hand, according to some results [29] application of cracking
catalysts such as Zn-13X, Fe-5A and CoMo-HY are ineffective in waste plastics cracking.
The appropriate solution seems to be the application of cheap quartz, alumina and
activated clays in this process [30, 31]. In some patents [e.g. 31] and papers [7] platinum
or reforming catalysts are suggested as suitable for this process.
It is surprising that small-pore zeolites (pore size lower than 1 nm) are so frequently
proposed as components of the catalysts of large-molecule waste polyolefin cracking [e.g.
22–24]. The very difficult transport of the melted plastics material into the catalyst pores
is the fundamental problem with catalytic cracking of waste plastics. Therefore, cracking
of long hydrocarbon chains can occur mainly at the external surface area of the catalyst
grains while products of these primary reactions can be further cracked in the catalyst
pores (secondary reactions). This is especially true in the case of PS with side phenyl
groups in the polymer chain that create steric hindrance. Serano et al. state that this
obstacle can be overcome by using large-pore materials such as (H)MCM-41 [12].
It seems that, from a practical point of view, equally or even more important than a type
of potential cracking catalyst are impurities in real waste plastics. Only sparse research
work has been devoted to problems such as possible PVC and heavy metals content in
the cracking feeds. In the course of segregation and preparation of the feed some PVC
can be included and then the cracking products obtained will contain chlorine or its
compounds. According to Kaminsky et al. [14] and Simon et al. [32] gaseous cracking
or pyrolysis products are free of chlorine if HCl is removed, e.g. by calcium carbonate,
liquid products can contain up to 15 ppm chlorine while the largest quantity of chlorine is
concentrated in tars or solid residues and mineral fluidization mediums. Relatively large
quantities of chlorine can be concentrated in water (if present in the cracking products).
At longer residence time or high process temperature chloroorganic compounds are totally
decomposed into HCl and hydrocarbons. Heavy metals, such as Na, K, Cr, Mn, Zn, Cd,
Sb derive from product residues and auxiliary agents used in polyolefins processing, such
as stabilizers or plasticizers and others. They are mainly concentrated in soot or other solid
residues, e.g. Zn content in soot attains even more than 1 wt %, while the oil fraction can
contain about 20 ppm Zn [32].
5.2 COPROCESSING OF WASTE PLASTICS WITH OTHER RAW MATERIALS
Lubrication oil wastes and waste plastics are very similar materials from a chemical
composition point of view; they are of organic origin and are composed mainly of carbon
and hydrogen. Both feeds can be utilized by thermal or catalytic cracking or pyrolysis
process. One of the differences is that annual waste oils amounts are considerably lower
and account for about 15–20% of annual waste plastics amounts [33, 34]. Relatively
high melting temperature, high viscosity and low thermal conductivity of waste plastics
can cause difficulties in their direct feeding with the typical equipment. Mixing and
diluting of waste plastics with waste oils and cracking is an optional method of common
processing. Due to rheological properties, according to Lovett et al. [35], the maximum
content of waste plastics in waste oils in commercial scale should not be higher than
10%. The further studies of Serrano et al. [34] showed that application of laboratory kiln
reactor and thermal cracking temperature 450–500◦ C enables one to obtain over 95%
degradation of LDPE–waste oil mixture (70/30–40/60) and gives mainly C13 –C22 and
C23 –C40 fractions (n-paraffins and 1-olefins). It is evident that only partial waste oil
conversion was attained (C28 –C41 hydrocarbons), since it is more thermally stable than
LDPE. They obtained much better results by using HZSM-5 and Al-MCM-41 cracking
catalysts at the same temperature range and 70 wt% LDPE content in waste oil. In
this case 65 and 50% selectivity to C5 –C12 fraction was determined for Al-MCM-41
(mainly olefins) and HZSM-5 (olefins and aromatics), respectively. Kargöz et al. carried
out similar experiments, but they applied municipal waste plastics and vacuum gas oil
mixture under hydrogen pressure [36].
Light cycle oil, a highly aromatic FCC product (e.g. 67% aromatics content) can be used
as solvent for PS and PS-BD (polystyrene–butadiene) mixture, component of synthetic
rubber. Arandes et al. [37] proved that this feed can be further successfully thermally or
catalytically cracked, giving mainly gasoline fractions. They contain a high quantity of
valuable components for petrochemistry, styrene and C4 olefins.
Gebauer et al. [38] suggest visbreaking of waste plastics with vacuum residue. This is
a thermal process, applied in refineries in order to convert partially atmospheric vacuum
residue and decrease viscosity and melting temperature. According to the authors, addition
of 5% of waste plastics in laboratory tests does not influence noticeably the process
parameters and final products properties. As in the case of LCO and VGO fractions the
application of vacuum residue and mixture of waste plastics is applicable in refineries.
It is worthy mentioning two other possibilities of waste plastics processing, both based
on gasification. In the first case, co-gasification of plastics and biomass, gives the possibil-
ity to utilize wastes accompanied by the control of hydrogen content in the synthesis gas
produced [39]. According to Fink and Fink [40], synthesis gas from waste plastic gasi-
fication can be ‘put in’ pre-selected crude oil wells. These wells should be located near
the gasification plant and the main goal of this method is to enhance crude oil recovery
in the future.
Co-coking of waste plastics and coal-tar pitches in the temperature range 200–400◦ C
yields reaction pitches which can be further applied as additives to coal blends and as a
consequence improve their coking properties [41]. A quantity of lower-boiling products
can be obtained as a result of the coking process. A similar process is presented in
a German patent [42], but in the presence of granular calcium oxide in the temperature
range 600–1400◦ C and at CaO: waste plastics ratio 1:1–3. The main products are calcium
carbide and a gaseous fraction which can be used for power generation.
Some inventors suggest conversion of waste polyolefins and the waxy Fischer–Tropsch
fraction into lube base oils in relatively mild thermal conditions, i.e. at 150–350◦ C and
short residence time [43]. Both raw materials are submitted to pyrolysis and after thermal
treatment the heavy liquid fractions can be hydrotreated and isodewaxed in order to obtain
high viscosity index lubrication base oils while medium fractions after isodewaxing can
be applied as the components of diesel or jet fuels. Polyolefins can be thermally or
catalytically processed (Mn, V, Cu, Cr, Mo or W compounds as active phase) with natural
or synthetic rubbers, paraffin or lignite waxes or other polymers [44]. Mixtures of PP and
PE can be applied as good-quality feed for production of microcrystalline waxes [45].
At relatively low temperature, i.e. 350–430◦ C cracking is completed with partial melt
recycling and destructive distillation (under normal pressure or vacuum).
6 REACTOR DESIGN
For acceptable efficiency waste polyolefin cracking process should be realized in con-
tinuous mode. For the same reason, as well as due to high coke and mineral residue
yields, construction of reactor for waste plastics cracking has to enable continuous coke
removal. The best solution is a fluidized-bed process, known in refineries as fluid catalytic
cracking (FCC) in crude oil processing with cracking catalyst or fluid thermal cracking
with coke or mineral grains as the fluidization medium [5]. In refinery implementations
the coke-covered cracking catalyst (or inert material) is transported to a regenerator and
after regeneration it is returned to the cracking reactor. Part of the deactivated catalyst
is discharged from the system and the same quantity of fresh catalyst is put into the
reactor. A thermal and catalytic fluid cracking reactor was applied in extensive studies by
Kaminsky et al. [1] yet without catalyst regenerator operation.
According to a US patent [46], cracking or liquefaction of waste plastics is realized
in a sequential three- or four-screw extruder system with increasing process temperature.
Similarly, the catalyst (if used) is discharged with coke and mineral residue. At the end of
the process, the distillable hydrocarbon fraction is separated from solid residue and coke.
In another US patent, [47], polyolefins and tires scrapes mixture is fed to the batch
reactor equipped with a special mixer. A screw extruder or other device is used for feed
supply. In this semi-continuous reactor raw material is fed to the reactor for some time and
the main products are gaseous and liquid fractions as well as a mixture of soot, mineral
impurities and coke. At the end of the production cycle the process is stopped and the
direction of mixer rotation is reversed. In this cycle mixer arms are scraping coke from
the reactor walls. The main disadvantage of this solution is a semi-continuous working
mode, relatively low output and problems with application of the cracking catalyst.
In the next reactor design [48] mixer arms have exactly the same dimensions and shape
as the internal reactor part and in the course of the run coke residue is scraped by mixer
arms from the heated reactor walls. Scraped coke falls down and is collected at the bottom
of the reactor and removed with part of the reaction mixture by a suction pipe. The main
process products are the gas fraction (used for heating purpose), gasoline and light gas
oil and paraffin fractions.
A batch-type reactor equipped with a screw feeder and mixer is offered by US
patent [49]. A special grate is mounted inside the reactor, above the cracked melted waste
plastics mixture. Scraped waste plastics which are submitted to the cracking reactor melt
at the grate and fall down to the reaction mixture. As in the case of previous patent
description, in the course of cracking process a mixer of a special construction scrapes
coke form the reactor walls and then coke is removed from the specially shaped reactor
bottom by a screw transporter. The process temperature attains level of 450◦ C.
Gasification of waste plastics in a plasma reactor and the application of the high calorific
gas produced for production of electricity, followed by using waste heat from the turbine
for steam generation, has been presented by German inventors [50]. There is no informa-
tion about process efficiency and the main advantage of the solution is the possibility of
using various feed compositions.
According to Polish inventors [51], semi-continuous reactor operation can be secured
by special reactor construction equipped with an exchangeable heating coil. The heating
coil, fired by flue gases, melts, heats and cracks waste plastics and as a result of the
cracking process it becomes covered by solid carbon residue. The special construction of
the cracking reactor enables it to coke remove by coil vibration. The heating coil can be
easily dismantled and exchanged after stopping the process.
Because of inorganic components in waste plastics, thermal, noncatalytic processes
present some advantages. In order to obtain high conversion Chinese inventors [52] pro-
pose a two-step process: thermal cracking in the first step in order to obtain partial
cracking of waste plastics and to separate inorganic components, and in the next step
catalytic cracking of the product over a fixed-bed catalyst.
Numerous cracking reactor constructions have been patented by Japanese and Chi-
nese inventors. Similar cracking reactor construction is presented in two patents [53, 54].
Waste plastics are fed using a screw extruder followed by a parallel-shaped tube reac-
tor with internal conveying and mixing divided sequentially for melting, cracking and
evaporating zones. Japanese inventors have developed a tube cracking reactor with screw
mixing and transport device [55]. Although the design idea of these reactors is not easily
comprehensible it is evident that an important advantage of these cracking reactors is
removal of coke, carbon residue, and catalyst (if used) from the reactor interior. There is
no information about output of the reactor systems.
A tubular reactor of special design internal screw mixer has been developed at Wro-
claw University of Technology [56, 57]. The melted plastics from a screw extruder are
passed to the multi tube-cracking reactor where they are cracked in the temperature range
420–500◦ C. The role of the specially shaped internal mixer is to mix the melted plastics,
to scrap coke from the internal surface of the tube reactor and to remove coke from the
reactor. The removed coke grains drop down to the coke receiver at the end of the reactor
tube while hydrocarbon vapor mixture flows sequentially to air and water coolers and
next to the gas–liquid separators. Experiments carried out in the laboratory (0.3–2 kg)
and pilot-scale plants with 20–30 kg per hour capacities showed that this type of reactor
can find commercial application in the continuous process. Its basic advantage is contin-
uous coke removal from the reactor tubes. It is planned that at the end of 2005 the first
reactor unit of a commercial plant of ∼2000 tons annual output will start its activity. The
cracking reactor unit will be composed of 6 or more tubes with internal mixers and it
will enable both thermal and catalytic cracking of waste polyolefins.
It seems that fluid-bed cracking reactor (thermal or catalytic) is the best solution for
industrial scale. However, regeneration and circulation of so-called equilibrium cracking
catalyst is possible for relatively pure feeds, for instance crude oil derived from vacuum
gas oils. Municipal waste plastics contain different mineral impurities, trace of products
and additives that can quickly deactivate the catalyst. In many cases regeneration of
catalyst can be impossible. Therefore in waste plastics cracking cheap, disposable catalysts
should be preferably applied. Expensive and sophisticated zeolite and other molecular
sieves or noble-metal-based catalysts will find presumably limited application in this kind
of process. The other solution is thermal process, with inert fluidization agent and a coke
removal section or multi-tube reactor with internal mixers for smaller plants.
7 PILOT PLANTS AND COMMERCIAL PLANTS
Thermal or catalytic cracking are the typical refinery processes and therefore BP Chem-
icals built a fluid cracking plant for waste plastics at the Grangemouth refinery in Eng-
land [58–60]. This was a pilot plant of 100 kg/h capacity for cracking of commingled
waste plastics composed of 80% PE and PP, 15 wt% of PS, 3 wt% of PET and 2% of
PVC. Sand was used as fluidizing agent and the process temperature was varied in the
range 400–600◦ C, close to FCC temperature or higher, i.e. olefin pyrolysis. According
to the pilot plant data the BP process is highly effective from the point of view of light
C2 –C4 olefins yield (∼60%). The other process products are gasoline and coke yet there
is no information about their yields. It was foreseen in 1993 that refinery plant of 500 000
ton per year output would be built in 2000 or even later. This would be local plant for
cracking of waste plastics from the area of about 10 000 km2 . A two-stage variant of this
technology was pursued by BASF in Germany [21, 62]. In the first step a low-temperature
reactor dechlorination of PVC was realized and next the semi-product obtained was sub-
mitted to a thermal cracking reactor. Oil fraction was the main product; gaseous fraction
product could be catalytic cracker feed while HCl from the dechlorination stage could
be recycled to PVC production. It was planned in the 1990s to build a plant to process
300 000 tons of waste plastics per year.
A similar idea of waste plastics utilization was developed by Shell Research in Amster-
dam. It was foreseen that a two-step thermal cracking plant for processing of ca 100 000
tons of wastes per year should be the receiver of waste plastics for local agglomera-
tion [60]. There is no information about commercial implementation.
Various fluidized-bed processes were based on the discussed earlier HUPP design [1].
On the base of vast laboratory studies the fluid cracking pilot plant was built in Ebenhausen
near Ingolstadt. This was a fluidized-bed process with ∼8-m high cracking reactor and
capacity of 800 kg per hour as well as sand and pyrolitic gas as fluidizing agents, working
in the temperature range 500–800◦ C. It was feasible to crack PS at 515–540◦ C in order to
obtain styrene monomer and to pyrolyse PE at 780◦ C with C2 –C4 olefins and mono- and
polycyclic aromatics as the main products [58]. When PVC was a component in the waste
plastic feed it was possible to add calcium oxide to wastes in order to remove hydrogen
chloride or gaseous ammonium to fluidizing gas and remove HCl as ammonium chloride.
According to the author’s opinion waste plastics cracking in a fluid-bed reactor should
be economically viable at a capacity of ∼40 000 tons per year. Tiltmann in his book [62]
presents two experimental plants based on rotary kiln and fluidized bed reactors. Up till
now there is no information on their application in industrial scale.
ZSM-5 based catalyst and continuous cracking process are the main features of the
Fuji Process. In the temperature range 420–450◦ C and 80% polyolefins and polystyrene
mixture as feed, gasoline and gas oil fractions are the main products. The special reactor
design, similar to the H-Oil hydrocracking reactor with boiling catalyst bed and partially
liquid product recycling, enables continuous catalyst exchange and regeneration [63].
The largest cracking plant for waste plastics processing in Poland (ca 10 000 tons waste
plastics per year) is operated by Agrob Eko Company (Zabrze). The cracking reactors
(six units, each ∼20 m3 ) with mixers and internal heat exchangers are operated in the
temperature range of 380–460◦ C. The feed for the plant is spent lubrication and technical
oils as well as waste plastics (50 wt%), cracking products are liquid hydrocarbon fractions,
bp< 400◦ C, gas 7–8 wt% and coke 10–12 wt% [64]. Reactor construction allows for
semi-continuous operation. After cracking of ∼60 tons of wastes reactor operation is
stopped for cooling, and for vapor and coke removing (scrapping) from the internal
surface of the cracking reactor. Six cracking reactors make continuous plant operating
possible. It is a catalytic cracking process with silica–alumina as catalyst.
Although the idea of thermal or catalytic cracking or liquefaction of waste plastics
seems to be simple and profitable, no successful and widely licensed technology is pre-
sented in the technical literature. Even if there is some press information about pilot-scale
technology and its efficiency there is no further information about industrial implementa-
tion and/or transferring of the technology to other companies. The reason for is that up till
now there has been no good and profitable commercial process. Any thermal processing
of waste plastics, similarly to cracking or coking of heavy naphtha fraction, produces
a considerable quantity of coke. It deactivates cracking catalyst in fixed beds and coke
deposits on the surface of heat exchangers makes long-term operation of the process
impossible. Therefore, as in case of refinery cracking processes the best solution is the
application of the fluidized-bed operation. This type of process presents numerous advan-
tages in large-scale crude oil fraction processing of hundreds thousands of tons per year
or more. Continuous dosing of catalyst and continuous coke removal, together with the
spent catalyst, accompanied by simultaneous catalyst regeneration and recycling ensures
efficient process exploitation. This is not possible, or it is too expensive and commercially
unaccepted, in the small plants. On the other hand the application of the other type of
reactor, e.g. a batch one with mixers, can be exploited only semi-continuously. A few days
working period has to be followed by a cleaning and coke removal period. A continuous
mode of exploitation is possible in tube reactors with internal mixers and screw extruder
feeding. However, this type of reactor can be exploited in rather small scale with waste
plastic cracking output of 10 000 tons per year.
8 ECONOMIC ASPECTS
According to the Packaging Research Foundation (USA), costs of tertiary waste plastics
recycling (fuel fractions or monomer production) can not be recovered with an oil price
of ∼25–30 USD per barrel. Subramanian [65] comments on advanced, chemical plastics
recycling in the USA (glycolysis, ammonolysis and pyrolysis). At the same time he also
states that polyolefins are high-calorific solid fuels, similar to fuel oil and that 114 waste-
to-energy (WTO) facilities were working in 32 states in the USA. In any economically
viable recycling process the costs of collecting, sorting and washing should be repaid
by reclaiming products from the collected wastes. There is no doubt that waste plastics
have to be utilized. Then the main problem is whether they should be combusted in WTO
facilities or pyrolyzed or cracked in order to obtain monomers or gaseous, liquid and solid
hydrocarbon fractions. It is evident that from an economic point of view prices of waste
plastics cracking products (gasoline, light gas oil and heavy wax fractions) have to be
correlated with the crude oil world price. It is necessary to add that waste-plastics-derived
products are sulfur-free, composed mainly of gasoline and light gas oil fractions, suitable
for fuel production. For instance when the price of crude oil amounted $30 US per barrel,
i.e. ∼$0.197 US per kg, Polish refineries offered a price equivalent to $0.35 US per kg
for the liquid product of waste plastics cracking. This is almost as high as the crude oil
price. This is possible since in Poland the economy of the utilization plants is aided by
tax relief and lowering in excise duty as well as by ‘product payment’, i.e. obligatory
payments for plastics package reclamation by their producers.
The results obtained by VEBA in a high-pressure hydrogenation plant [21] indicated
an almost four times higher price of fuels from waste plastics than current fuel market
prices. At the beginning of 1990s on the basis of pilot-plant-scale hydrogenation process
the UK researchers stated that this process is not economically viable and they foresaw
that it would not be available commercially until after 2000.
Economic efficiency of waste plastics processing depends on the methods of their selec-
tion and preparation for processing as well as the cost of thermal or catalytic treatment,
i.e. the cost of investment and exploitation of the cracking plant. For instance the main
characteristic of fluid-bed reactors is the possibility of exploitation of large-scale units
(at least 50 000 tons or more per year), low cost of exploitation, but accompanied by
large investment and feed delivery costs. And on the other hand, smaller reactors can be
built on a smaller scale, a few thousand tons per year output, lower investment costs and
lower feed deliveries (processing of local wastes in limited area), but operated with larger
exploitation costs.
Finally, economic efficiency of waste plastics processing (tertiary recycling) can be
influenced by state tax policy, e.g. by lowered income taxes and excise duty in the case
of fuels produced from waste material. It will also be strongly influenced by continuous
increasing of landfill costs and local legislation (local taxes lowered for waste plastics
utilizing companies) as well as obligatory payments for package reclamation by their
producers.
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5
Thermal and Catalytic Degradation

of Waste HDPE
KYONG-HWAN LEE
Clean Energy Research Department, Korea Institute of Energy Research,
71-2 Jang dong, Yusong ku, Daejeon 305–343, Korea
1 INTRODUCTION
This chapter describes the thermal and catalytic degradation of waste high-density
polyethylene (HDPE) in order to recover the fuel oil from waste plastics. Among waste
plastics, the polyolefinic type that is a material of high potential for alternative oil
production is more than 70% of the total plastic content in municipal solid waste (MSW).
Waste HDPE in polyolefinic plastic is a difficult material in the pyrolysis process by
treatment at high temperature, because of its high degradation temperature and high
viscosity products such as low-quality wax.
In recycling methods, the thermal and catalytic degradation may provide a suitable
means of recycling, of great interest both economically and environmentally [1, 2]. The
advantage of this process is the low energy consumption, the handling of waste plastic
that cannot be efficiently recycled by alternative means, and also the operation without the
need for air or admixtures of hydrogen. This method has been studied by many researchers
to recover valuable oil.
Thermal degradation is a simple process in which polymers at high temperature are
melted and broken down to smaller molecules [3]. However, these products have a low
practical use due to their low quality. Thus, the interesting method of polymer utiliza-
tion is the catalytic degradation process. This is to convert the melted polymer to light
carbon-derived materials with high-quality components, whereas the addition of catalyst
in the pyrolysis process is accompanied by an increase in cost and also the development
of a highly technical process. Moreover, the catalysts are deactivated during the process
by the deposition of carbonaceous residues and other products, such as Cl and N com-
pounds. For this reason, a pretreatment process is required to remove all the components
130 K.-H. LEE
that can negatively influence the catalyst. Catalytic degradation process enable lowering
of reaction temperature, fast reaction with low activation energy and also a low boil-
ing temperature range product with high quality such as branched, cyclic and aromatic
structures, compared with the thermal degradation process. The product distribution over
the catalytic degradation can be controlled by the selection of a suitable catalyst and its
modification. As an example of the cracking catalyst, spent fluid catalytic cracking (FCC)
catalyst is thrown away from the commercial FCC process in Korea as a few ten thousand
tonnes per year, although it has high activity. This catalyst can be economically used in
the liquid-phase cracking process for waste plastics into oil recovery, due to its low cost.
On the other hand, the combination of pyrolysis and catalytic process can be a more
efficient method for processing large amounts of waste plastics [4]. This method reduces
the viscosity of the mixture products and enables the separation of unwanted components.
Also, in thermal and catalytic degradation of waste HDPE the influence of experimental
variables, such as reaction temperature, catalyst type and other plastic addition, etc. is
described in this chapter. Thus, the discussion focuses on waste HDPE as a reactant and
the influence of various experimental variables and also a comparison of the thermal and
catalytic degradation in detail.
2 THEORY OF PLASTICS PYROLYSIS
The decomposition of plastics can be considered as depolymerization of polymer into

low-molecular product. The general reaction mechanism for the thermal degradation is
described with the following steps, and also shown in Figure 5.1.
• Initiation may occur at random or end-chain positions.
• Depropagation is the release of olefinic monomeric fragments from primary radicals.
• Hydrogen chain transfer reaction, which may occur as intermolecular or intramolecular
processes, leads to the formation of olefinic species and polymeric fragments. More-
over, secondary radicals can also be formed from hydrogen abstraction through an
intermolecular transfer reaction between a primary radical and a polymeric fragment.
• β-cleavage of secondary radicals leads to an end-chain olefinic group and a primary
radical.
• Termination takes place either in a bimolecular mode with the coupling of two primary
radicals or by disproportion of the primary macroradicals.
The decomposition of plastics depends on the plastic type, with different reaction mech-
anisms of plastics proposed with four types [5].
• End-chain scission; the polymer is broken up from the end groups successively yield-
ing the corresponding monomers. When this polymer degrades by depolymerization,
the molecules undergo scission to produce unsaturated small molecules (monomers)
and another terminal free radicals. (Polymethylmethacrylate, polytetrafluorethylene,
polymethacrylonitrile, polyethylstyrene, polystyrene, polyisobutene)
• Random-chain scission; the polymer is broken up randomly into smaller molecules
of varying chain lengths, producing a volatile with or without a double bonds.
(Polystyrene, polyisobutene, polyethylene, polypropylene, polybutadiene)
DEGRADATION OF HDPE 131
Initiation
Random scission : CH2–CHX–CH2–CHX CH2–CHX + CH2–CHX
End-chain scission : CH2–CHX–CH2–CHX CH2–CHX + CH2–CH2X
Depropagation
CH2–CHX–CH2–CHX CH2–CHX + CH2=CHX
Hydrogen chain transfer
Intermolecular : CH2–CHX + CH2–CHX–CH2–CHX–CH2
CH2–CH2X + CH2–CHX–CH=CHX+CH2
CH2–CHX + CH2–CHX–CH2 CH2–CH2X + CH2–CX–CH2
Intramolecular : CH2–CHX–CH2–CHX–CH2 CH2–CHX=CH–CHX–CH3
b-cleavage: CHX–CH2–CX–CH2 CHX+CH2=CX–CH2
Formation of branches
CHX–CH2
CH2–CHX + CH2–CX–CH2 CH2–CX–CH2
CH2–CX–CH2 + CH2–CX–CH2 CH2–CX–CH2

CH2–CX–CH2
Termination
Bimolecular coupling: CHX–CH2 + CHX–CH2 CHX–CH2–CHX–CH2
Disproportionation
CH2–CHX–CH2 + CHX–CH2–CH2 CH2–CHX–CH3 + CHX=CH–CH2
Figure 5.1 Reaction mechanism of polymer
• Chain-stripping; the reactive substituents or side groups on the polymer chain are
eliminated, leaving an unsaturated chain. This polyene then undergoes further reaction,
including β-scission, aromatization and coke formation. (Polyvinylchloride, polyvinyl
fluoride, polyacrylonitrile)
• Cross-linking; the formation of a chain networks occur from thermosetting polymers,
when heated at high temperature. This is pyrolytic condensation and rearrangement
of carbon networks to form high-strength materials. (Thermosetting plastics)
132 K.-H. LEE
These different mechanisms are related to the bond dissociation energies, the chain
defects of the polymers, the aromatic degree and the presence of halogen and other
hetero-atoms in the polymer chains. For the reaction mechanism of the main components
in waste thermoplastics, the pyrolysis of PVC occurs by the chain-stripping mechanism
with much less monomer recovery, whereas that of PS with cyclic structure occurs by
both end-chain and random-chain scission mechanism and the monomer recovery is very
high. Especially, PE and PP which comprise the main polymers in waste plastics pyrolyze
by random-chain scission, which yields a wide range of hydrocarbon products. The oil
products consist of higher-boiling-point hydrocarbons with low valuable products as well
as lower-boiling-point hydrocarbons. Thus, in the pyrolysis process the more cracking of
high-boiling-point hydrocarbons to obtain valuable light oil product with high yield must
be taken into consideration in a large-scale plant.
A new macroscopic degradation mechanism of polymers studied by Murata et al. [6]
was suggested with two distinct mechanism in the thermal degradation of PE, PP and PS.
One is a random scission of polymer links that causes a decomposition of macromolecules
into the intermediate reactants in liquid phase, and the other is a chain-end scission that
caused a conversion of the intermediate reactants into volatile products at the gas–liquid
interface. There are parallel reactions via two mechanisms. The random scission of poly-
mer links causes a reduction in molecular weight of macromolecules and an increase of the
number of oligomer molecules. The chain-end scission causes a dissipation of oligomer
molecules and a generation of volatile products.
The cracking reactions of heavy hydrocarbons using a catalyst such as solid acid and
bifunctional catalyst, etc. have been explained with the difference of simple thermal degra-
dation of the polymer. In the depropagation of the polymer chain using the catalyst, the
molecular weight of the main polymer chains may be rapidly reduced through successive
attacks by acid sites on the catalyst, yielding a high fraction of low-molecular product.
Also, the carbonium ion intermediates in the catalytic reaction progress can undergo rear-
rangement by hydrogen or carbon atom shifts with producing the isomers of high quality
and can undergo cyclization reactions, by means of the intramolecular attack on the double
bond of an olefinic carbonium ion.
In the case of a bifunctional catalyst playing different active site roles, this catalyst con-
sists of both acidic and metal material as reforming catalyst. The metallic sites catalyze
hydrogenation/dehydrogenation reactions, while the acidic sites on the support catalyze
isomerization reactions, as shown in Figure 5.2. This catalyst can promote the isomeriza-
tion of straight-chain paraffins into branched-chain molecules, the dehydrocyclization of
straight-chain paraffins into cycloparaffins and also the dehydrogenation of naphthenes into
metal site
n–C5 n–C5 (olefin) + H2
acid site
n–C5 (olefin) i–C5 (olefin)
metal site
H2 + i–C5 (olefin) i–C5 (paraffin)
Figure 5.2 Reaction mechanism of hydrocarbon on bifunctional catalyst [5]. (Repro-

duced with permission from Elsevier)
aromatics. These reactions improve the octane numbers of light hydrocarbons. However,
this catalyst is very expensive. Thus, its use in oil recovery from waste plastics containing
contaminated material must be taken into careful consideration.
Characteristics of thermal and catalytic degradation of heavy hydrocarbons can be
described with the following items, respectively.
• In the case of a thermal reaction
1. High production of C1 s and C2 s in the gas product
2. Olefins are less branched
3. Some diolefins made at high temperature
4. Gasoline selectivity is poor; that is, oil products are a wide distribution of molecular
weight
5. Gas and coke products are high
6. Reactions are slow compared with catalytic reactions
• In the case of a catalytic reaction
1. High production of C3 s and C4 s in the gas product
2. Olefins are the primary product and more branched by isomerization
3. Gasoline selectivity is high; that is, oil products are a short distribution in the
gasoline range
4. Aromatics are produced by naphthene dehydrogenation and olefin cyclization
5. Larger molecules are more reactive
6. Pure aromatics do not react
7. Paraffins are produced by H2 transfer
8. Some isomerization occurs
3 PROCESS FLOW DIAGRAM
In this section we discuss the process flow diagram for the pyrolysis of waste plastics.
This is required to be a compact process that can be controlled in a stable and continuous
way, because of movement of the high-viscosity material for each unit system in the
process. This material can block the flow line and make difficult the continuous control
of unit process.
In order to obtain an oil product in the pyrolysis of waste plastics, the major steps for
waste plastics that are derived from the household, industry, etc. are basically shown in
Figure 5.3, Waste plastics as a reactant for obtaining the valuable products are invari-
ably contaminated with materials such as soil, iron and wood etc. and also consist of
various types of plastics. This material cannot be directly used in the pyrolysis process.
Therefore, in the next step separation treatments must be applied to obtain waste plastic
with a homogeneous composition. If it contains a lot of various contaminative materials
in waste plastics, it leads to poor economics by increasing the recycling procedure cost.
Thus, the important point for the pyrolysis process is the purification of waste thermo-
plastics, especially excluding PVC and PET in the reactant. Here, PVC and PET in the
plastic feedstock can cause unfavourables emission due to the presence of Cl as well as
high char/coke yields since they are not well degraded in the general pyrolysis process,
respectively. The waste material must be separated into individual components, such as
thermoplastic, PVC, PET, thermosetting, iron, aluminum and paper, etc.
134 K.-H. LEE
Waste plastic
Separation
Feeding system
Gas neutral system
Melting system
Sludge treatment
Pyrolysis
Catalytic degradation
Distillation
Gas product Light oil product Heavy oil product
Figure 5.3 Continuous process flow diagrams for waste plastics into oil recovery
In the third step, the separated plastics are delivered by the feeding system such as the
conveyer, hopper and extruder, etc. to the melting reactor, after cutting to a small size. The
feeding system is continuously controlled with a constant reactant amount and classified as
heated or nonheated case of the extruder. By preheating the plastic feedstock the melting
time in the melting reactor can be shorted thus improving production rates. Moreover,
the film type reactant is very bulky and voluminous, which makes it difficult to ensure
continuous feeding, is easily dosed at the melting system after melting in the feeding
system. In the unheated case, a hard reactant of several millimeter size is adequately
controlled by a continuous feeding system. Thus, the feeding system will be determined
by the profile of waste plastics that are exited from industry, agriculture and household,
etc. Other important point is that if there is trouble in a continuous automatic feeding
system, it can be quickly transferred to a manual system.
The next step is the melting system, where the solid plastic is changed to a low-
viscosity melt. If there is sufficient time to melt the polymer in the melting reactor, the
pyrolysis and/or catalytic degradation process as the next step of melting system will be
well controlled without trouble in a continuous system. The residence time of plastics in
the reactor depends on the plastic type and the desired viscosity extent. Thus, in order
to reduce the melting time of reactant in the melting system, it needs be heated in the
feeding system prior to the melting system. Moreover, as the system is scaled up to a big
plant, this is a very important parameter for heating the feeding system.
In the pyrolysis and catalytic degradation of polymer at temperature 300–450◦ C the
melted reactant is degraded into a smaller molecule and also upgraded to oil product with
a high quality. Several processes of pyrolysis and catalytic degradation are available, such
as pyrolysis process only, liquid-phase catalytic degradation after the melting process and
catalytic degradation after the pyrolysis process, according to the characteristics of the oil
produced.
For the processes of different reactor types, kiln and retort pyrolysis processes are char-
acterized by a relatively low capital investment. However, they suffer from unfavorable
economics, due to the high processing costs compared with the value of the oil product
obtained. Also, the characteristics of this process are relatively long residence times of
waste in the reactor, poor temperature control due to large temperature gradients across
their internal dimensions, fouling walls of the reactor by carbon residue and low liquid
product quality due to the production of a diverse number of pyrolysis products.
Fixed-bed pyrolysis–catalytic cracking process for oil recovery of waste plastic is in
use at several commercial processes. The reactor type in the pyrolysis or/and catalytic
cracking process is generally constant stirred tank reactor (CSTR) and plug flow reactor.
The problem is the fact that carbon residues tend to foul the walls of the reactor and thus
give poor heat transfer from the external wall to the center of the reactor. Furthermore,
CSTR type can deal with a relatively high viscosity reactant, but the problem of heat
transfer by a big reactor diameter can be more important, compared with that of plug
flow reactor. Basically, waste plastics are melted to materials of low viscosity and then
the liquefied reactant is thermally decomposed to low-molecular-weight hydrocarbons in
the pyrolysis reactor. These reactants are cracked in a fixed-bed reactor using solid catalyst
to yield the oil and gas products. The characteristics of this process are the quality of the
oil product, very similar to that of conventional gasoline, kerosene and diesel oils, but the
drawback of the catalyst is high cost and short life-cycle due to poisoning/deactivation.
The fluidized-bed process yields a uniform product and a high conversion during a
short reaction time. In addition, the problem of low thermal conductivity of polymers is
overcome by a fluidized system and thus heat transfer gradients are eliminated. Some
advantages are high-quality product, low energy requirement supplied by combustion of a
portion of the gas by-product, good temperature control, the efficient removal of impurities
present in the waste plastic, application on a relatively small scale, and also a robust and
relatively inexpensive process to establish. On the contrary, this process has problems
with toleration in the chlorine produced, the removal of solid sludge from the fluidized
bed and also its long-term durability.
In the pyrolysis process, one of the most important decision items is the degradation
temperature in the reactor. The degradation temperature must be decided by the type
and composition of plastics contained in mixed thermoplastics, because of their different
degradation temperatures. For a reactor with a big diameter in a large-scale plant the
temperature gradient must also be taken into consideration in determining the degradation
temperature, because of heat transfer limitations for viscous fluids with low thermal con-
ductivity in the large reactor. Moreover, the coke accumulated on the internal surface of
reactor during a long reaction time hinders heat transfer between heat source and viscous
fluid in the reactor. Thus, the heat supply of the plant is gradually increased with the
progress of reaction time. Optimization process control for hindering the coke formation
is an important key in a large-scale plant.
Also, the impact on the environment in the pyrolysis of waste plastics must be taken
into consideration. If a PVC material is contained in the reactant, the hydrochloric acid is
evolved during decomposition of PVC which causes air pollution. Thus, a system is needed
136 K.-H. LEE
in order to remove the chlorine components in gas products. The rest of the gas products
consisting of light hydrocarbons can be used as fuel gas in the heating system. Also
the nonvolatile material generated in the melting and pyrolysis process, which includes
a small amount of volatile hydrocarbon components, is discharged to a sludge treatment
system. After being sufficiently heated in the sludge system, the product obtained is used
as a valuable oil, but the solid char/coke retained is landfilled or incinerated.
Finally, the product obtained is separated from the distillation tower, such as gas prod-
uct, light oil product and heavy oil product. Our target is light oil product and/or heavy
oil product, which is generally obtained by control of reactor temperature and distilla-
tion system such as temperature gradient, reflux ratio and reboiler temperature, etc. The
distribution of the oil product must be decided by market circumstances.
4 TOTAL MASS BALANCE

Total mass balance is based on input and output amount in a simple process flow dia-
gram, as shown in Figure 5.4. In this process, the optimization control condition is the
maximum production of the oil product and the minimum production of the gas product
and the sludge. Generally, the yields of gas and oil product are below 20% and above
70% respectively, based on 100% of feeding amount. Also, the sludge amount is much
decreased to below 10%, which should be discharged in much smaller amounts, if pos-
sible. Increased amount of sludge discharged increases treatment cost and also decreases
desired product yields, which has a great influence on economic decisions on the pyrolysis
process of waste plastic.
As an example, the experimental data using stirred semi-batch laboratory-scale reac-
tor [7] was obtained from the catalytic degradation of various plastics over spent FCC
Feeding material (100%)
Water (<5%)
Melting zone
Light oil product
Sludge
Reactor
(<10%)
Distillation
tower
Gas product Light oil product Heavy oil product

(<20%) (A) (B)
(A + B > 70%)
Figure 5.4 Total mass balance of a simple process flow diagram in the pyrolysis of
waste plastics
100
Liquid
Solid
Gas
80
60
Yield (%)
40
20
0
HDPE LDPE PP PS
Plastic type
Figure 5.5 Yield of liquid, solid and gas products in catalytic degradation of various
plastics using spent FCC catalyst. (Reproduced with permission from Elsevier)
catalyst at 400◦ C, as shown in Figure 5.5. In general thermoplastics, the yield of liquid
products is 80% or over, which is the following order; PS > PP > PE. Plastics with a
polycyclic structure have higher liquid yield than that of polyolefinic structures. On the
contrary, the gas yields in these types of plastics are in reverse order compared with
those of liquid, which is below 20% yield. Also, the solid is much more produced from
polycyclic polymer than polyolefinic polymer. Accordingly, the product distribution is
very influenced by the type of plastic.
The pyrolysis of mixed waste thermoplastics in a pilot plant of 360 ton/year at the
Korea Institute of Energy Research (KIER), as shown in Figure 5.6, has an oil yield of
about 82% for continuous process control over two days. The distribution of oil product
is 27% gasoline product and 73% heavy oil product. Also the yield, of gas product is
10–15% and consists of about 18.1% C1 , 15.2% C2 , 30.3% C3 , 21.9% C4 and 14.3% C5
components. Similar results were obtained by other researchers, as shown in Table 5.1.
5 EFFECT OF TEMPERATURE
In the thermal and catalytic degradation of waste thermoplastics, the product yields
such as liquid, gas and solid products change depending on the degradation tempera-
ture. Walendziewski and Steininger [8] reported the thermal and catalytic degradation of
polyethylene in the temperature range 370–450◦ C. In the case of thermal degradation of
polyethylene, an increase in degradation temperature led to an increase of gas and liquid
products, but a decrease of residue (bp >360◦ C). However, according to the increase of
degradation temperature, the yield of gas products resulted in not too large increase and
that of residue decreased sharply. Similar results were obtained in the catalytic degradation
and hydrocracking process.
138 K.-H. LEE
(3rd and 4th floor)
(1st and 2nd floor)
Figure 5.6 Overall view of pyrolysis plant of waste plastics in KIER process
Table 5.1 Composition of gas products obtained from cracking of polyethylene at 400◦ C
Component Thermal (KIER)a Thermalb Catalyticb Hydrocrackingb

Methane 18.1 22.7 12.4 21.1
Ethane 12.3 27.4 20.4 21.2
Ethylene 2.9 1.4 2.3 0.1
C3 30.3 26.6 30.4 23.7
C4 21.9 11.0 20.3 20.7
C5 14.3 6.9 5.6 7.3
C6 0.2 2.1 3.3 3.8
a
Reactant: mixed plastics
b
Based on [8]
100
80
Gas and distillate yield (%)
60
40
20
Catalyst : Silica-alumina
0
100 200 300 400 500 600 700
Temperature (°C)
Figure 5.7 Influence of temperature on the catalytic degradation of polyethylene.

Beltrame et al. [9] have also studied polyethylene degradation over silica, alumina,
silica–alumina and zeolites in a small pyrex vessel reactor without a stirring, in the
reaction range 200–600◦ C. Thermal degradation and degradation catalyzed by alumina
or silica leave the residue amount, even at 600◦ C. However, at this temperature the gas +
distillate yield obtained in the presence of these two catalysts is much higher than that in
the thermal degradation. For the silica–alumina with higher activity, the degradation gave
much more gas and distillate fraction at 400◦ C, but at temperatures lower than 400◦ C it
did not reach completion. In conclusion, the gas + distillate yield over silica–alumina,
as a function of temperature, increased linearly up to 400◦ C, as shown in Figure 5.7.
Production occurs even at 200◦ C and reaches 100% yield of gas + distillate at 400◦ C.
140 K.-H. LEE
The catalytic upgrading of the pyrolysis gases derived from the pyrolysis of polyethy-
lene at 500◦ C has been investigated by Bagri and Williams [10]. The catalytic upgrading
was done over zeolite in the temperature range 400–600◦ C. As the zeolite bed tem-
perature was increased, the gas yield increased with a decrease in oil yield. However,
coke formation showed a small decrease with increase of catalyst temperature. Venuto
and Habib [11] also showed that as the catalyst temperature was increased from 480 to
590◦ C, coke formation in the zeolite catalytic cracking of petroleum was reduced and
also alkene gases in gas product increased. Sharratt et al. [12] carried out the catalytic
degradation of high-density polyethylene using ZSM-5 zeolite. As the reaction tempera-
ture was increased from 290 to 430◦ C, the gas yield was increased, whereas the oil yields
was decreased. The oil obtained in the pyrolysis of polyethylene contained a low concen-
tration of aromatic compounds. After it was catalyzed, there was a marked increase in
the concentration of aromatic compounds in the oil, which further increased in aromatic
concentration as the temperature in catalyst bed reactor was raised.
Lee et al. [13] have described the cumulative amount distributions of liquid product by
catalytic degradation of waste HDPE at different reaction temperatures and at a reactant
amount of 200 g, as shown in Figure 5.8. These distributions were clearly dependent on
reaction temperature. Thus the slope from the cumulative amount of liquid product versus
the initial reaction time was defined as the initial rate of degradation, which is shown as
a function of reaction temperature in Figure 5.9. The initial rate of degradation of waste
HDPE was exponentially increased with increase of reaction temperature and moreover at
160
430°C
400°C
370°C
120 350°C
Cumulative product weight (g)
80
40
0
0 100 200 300 400
Lapse time (min)
Figure 5.8 Cumulative amount of distillation as a function of reaction time for catalytic
degradation of waste HDPE using spent FCC catalyst (catalyst content = 9.1 wt%)
8
6
Initial rate of degradation (g/min)
0
320 360 400 440
Reaction temperature (°C)
Figure 5.9 Initial rate of degradation as a function of reaction temperature for catalytic
degradation of waste HDPE using spent FCC catalyst (catalyst content = 9.1 wt%)
a higher temperature was sharply increased from about 1 g/min (400◦ C) to about 6 g/min
(430◦ C), a great influence of reaction temperature.
6 EFFECT OF CATALYST
Because the addition of catalyst in the pyrolysis process has many advantages, many
researchers have looked for ways of improving light oil yield and oil quality from waste
plastics. According to the catalyst addition in plastic pyrolysis, the degradation tempera-
ture for achieving a certain conversion is reduced drastically. Also, the increase of catalyst
content in waste plastic further lowers the degradation temperature. In the liquid prod-
uct from catalytic degradation, more products in the gasoline range and moreover more
isoalkanes and aromatics in the C5 –C10 range can be produced. Also, the reaction rate
is increased significantly. The product distribution over the catalytic degradation can be
controlled by the selection of a suitable catalyst and its modification.
A simplified example [14] is illustrated by the difference in the product yields between
thermal and catalytic degradation using spent FCC catalyst of waste HDPE in a stirred
semi-batch reactor with on a laboratory scale, as shown in Table 5.2. Spent FCC catalyst
can be supplied from commercial FCC process, which is very cheap and retained with
adequate activity. Thus, it can be used as an alternative catalyst in liquid-phase catalytic
degradation of polyolefin. Compared with thermal degradation, the catalytic degradation
142 K.-H. LEE
Table 5.2 Yields of gas, liquid and residue obtained from thermal and
catalytic degradation of waste HDPE at 430◦ C
Gas (%) Liquid (%) Residue (%)

Thermal degradation 20.0 75.5 4.5
Catalytic degradation 19.4 79.7 0.9
showed an increase of liquid yield whereas that of residue was reduced, due to the
decomposition of heavier residues into lighter oil product.
Furthermore, the difference of cumulative yield distribution in liquid product between
thermal and catalytic degradation of waste HDPE was clearly apparent, as shown in
Figure 5.10. The catalytic degradation produced initial liquid product with more rapid,
higher degradation rate into liquid product and also much more liquid yield in comparison
with thermal degradation. It is supposed that if waste plastic in the thermal degradation
process is subject to short residence time in a continuous stirred tank reactor, partial
degradation of plastic can occur, while the rest of the feed can produce high-viscosity
product, such as wax.
The paraffins, olefins, naphthenes and aromatics (PONA) distribution of liquid product
with time on stream for thermal and catalytic degradation of waste HDPE at 430◦ C is
shown in Figure 5.11. In the case of thermal degradation, paraffin and olefin components
are the main products and aromatic compounds hardly appear, without change by increase
100
80
Yield of liquid product (wt%)
60
40
20
0
0 100 200 300 400
Lapse time (min)
Figure 5.10 Cumulative yield of liquid products obtained from thermal and catalytic
degradation of waste HDPE using spent FCC catalyst (solid line: catalytic degradation;
dotted line: thermal degradation, for reaction temperature; circles: 430◦ C; squares: 400◦ C)
100
Paraffin
Olefin
Naphthene
80
Aromatic
60
Fraction (%)
40
20
0
0 50 100 150 200 250 300 350
Lapse time (min)
(a)
100
80
60
Fraction (%)
Paraffin
Olefin
40 Naphthene
Aromatic
20
0
0 50 100 150 200
Lapse time (min)
(b)
Figure 5.11 Fractions of paraffin, olefin, naphthene and aromatic products for ther-
mal (a) and catalytic (b) degradation of waste HDPE at 430◦ C
144 K.-H. LEE
of reaction time. On the other hand, the catalytic degradation using spent FCC catalyst
showed about 80% olefin products as the main product. Also, the paraffin products were
decreased, whereas aromatic compounds were increased, compared with those of thermal
degradation. Spent FCC catalyst improved the fraction of liquid olefin and aromatic com-
ponents with comparatively high octane number. Molecular weight distribution of liquid
product obtained at a similar reaction time is compared over thermal and catalytic degra-
dation of waste HDPE in Figure 5.12. In the case of thermal degradation, both paraffin
and olefin as a main liquid product were distributed in a wide molecular weight range,
between 80 and 400, whereas naphthene products with cyclic structure showed a nar-
row molecular weight distribution. On the other hand, the catalytic degradation produced
mainly light olefin products in the range of gasoline with molecular weight below 200.
Walendziewski and Steininger [8] have described thermal and catalytic conversion of
waste polyethylene and polystyrene into oil recovery, in a small autoclave reactor. The
optimum thermal cracking temperature of waste polyolefins is 410–430◦ C, while that
of catalytic degradation is 390◦ C. Also, the yield of gas and liquid fraction with b.p.
<360◦ C was attained more than 90%. In the range of 0.3–1 wt% catalyst content, the
catalyst amount is small influenced on polyolefin conversion and product composition.
The thermal and catalytic degradation of PE, PP, PS and their mixture using alkaline
catalyst was investigated by Walendziewski [1]. In two cases, the yield of liquid and gas
fuel was over 95%. The application of cracking catalyst results in lowering of degradation
temperature, boiling temperature range in liquid product and density of liquid products,
and also the increase of gas product yield. Moreover, the products obtained in the cracking
of polymers are highly unsaturated components, containing olefins and diolefins that can
be hydrogenated over a bifunctional catalyst.
Aguado et al. [15] reported the thermal and catalytic degradation of low-density
polyethylene using a continuous two-screw kiln reactor. Compared with thermal
degradation, catalytic degradation is considerably faster and shows a completely different
product distribution. It was stated that thermal degradation gives rise to a broad product
distribution in liquid product, whereas the catalytic degradation over Al-MCM-41 leads
mainly to the gasoline range hydrocarbons (C5 –C12 ) with selectivities up to 80%, in
spite of low degradation temperature, as shown in Figure 5.13. n-paraffins, iso-paraffins,
olefins, naphthenes and aromatics (PIONA) analyses of gasoline fractions obtained in
the LDPE catalytic degradation indicate that the main components are olefins (50%) and
isoparaffins (20%), whereas the aromatic content is below 6%.
7 VARIOUS CATALYSTS
The thermal degradation of waste HDPE can be improved by using suitable catalysts in
order to obtain valuable products. However, this method suffers from several drawbacks.
The catalysts are deactivated by the deposition of carbonaceous residues and Cl, N com-
pounds present in the raw waste stream. Furthermore, the inorganic material contained
in the waste plastics tends to remain with the catalysts, which hinders their reuse. These
reasons necessitate a relatively high purity of waste plastics, containing very low con-
centrations of a contaminant. Thus, various pretreatments are required to remove all the
components that may negatively affect the catalyst.
25
Paraffin
Olefin
Naphthene
20
Aromatic
15
Fraction (%)
10
0
50 100 150 200 250 300 350 400
Molecular weight
(a)
25
Paraffin
Olefin
Naphthene
20 Aromatic
15
Fraction (%)
10
0
50 100 150 200 250 300 350 400
Molecular weight
(b)
Figure 5.12 PONA distributions of liquid products for thermal (a) and catalytic
(b) degradation of waste HDPE at 430◦ C
146 K.-H. LEE
20
Thermal(3 rpm, T1/T2 = 450/550°C)
Catalytic(15 rpm, T1/T2 = 400/450°C)
16
12
Selectivity (%wt)
0
0 10 20 30 40 50
Atom carbon number
Figure 5.13 The selectivity of carbon atom number obtained in the thermal and catalytic
degradation of LDPE in two-screw kiln reactor. (Reproduced with permission from
Elsevier)
The pyrolysis process of waste plastics is classified into either liquid-phase contact
or vapor-phase contact of catalyst in the continuous flow reactor. In the liquid phase
reaction, the catalyst is a fine powder type with high external surface area which is
contacted with melted plastics, which are degraded into light products from polymer
chain on the active sites of catalyst. This process uses a large amount of catalyst, which
becomes a high portion in total cost. Thus, the catalyst must be of low price and reused
after regeneration, if possible. In the vapor-phase reaction, the polymer is first degraded
into the hydrocarbon vapor in the thermal degradation process, aimed at reducing the
viscosity of melted plastics and enabling the separation of undesired components. The
cracked products are then contacted with the catalyst packed in the flow reactor, which
plays a reforming role over the products formed by thermal degradation of polymers.
Various catalysts used in the two processes have been described as follows; zeolite,
alumina, silica–alumina, FCC catalyst, reforming catalyst, and others. The most common
catalysts used in the cracking of heavy hydrocarbons are acidic catalysts; alumina and
silica–alumina with mesopores, and also zeolite with micropores, etc. They are typically
used in the commercial petroleum process. For the chemical properties of catalyst, the
catalysts consist of Lewis and Brönsted acid sites, which is an important factor in deter-
mining the catalytic activity and product selectivity. This is because Brönsted acid sites
play a proton addition role and Lewis acid sites involve hydride abstraction, which leads
to different reaction pathways in the cracking of hydrocarbons. Also, these acid sites are
generated by Al species in the catalyst consisting of silica and alumina. Thus, Al content
per unit cell or Si/Al ratio of catalyst is very related to the acid site density, which also
has a masked influence on the cracking reaction. High acid site density favors the crack-
ing reaction of hydrocarbons, but promotes undesired reactions such as coke formation.
Thus, in order to design the catalysts with a high activity and also high selectivity of
desired product, the acid site density of the catalyst is controlled by preparation methods
and various pretreatment methods such as steam or acid/base solution treatment, etc.
In addition to the chemical properties of the catalyst, the physical properties are also
very important in determining the catalytic activity and product selectivity. These param-
eters are the surface area, pore size, pore volume, pore size distribution, pore structure,
etc. As an example, the zeolite has a micropore crystalline structure with pore size below
1.0 nm, whereas alumina and amorphous silica–alumina are mesoporous materials with
a wide distribution of large pore size. Various natural or synthetic zeolites have relatively
high surface area, but small pore size and also small pore volume. The narrow distribu-
tion of zeolite having a pore size below 1.0 nm allows different molecules to control a
limited diffusion inside the pores, known as shape selectivity, which is selectively reacted
on active sites within pores. Also, other advantages of zeolites are high acid strength,
high stability and low coke formation, etc. Accordingly, zeolites such as zeolite Y and
ZSM-5 have been extensively used for catalytic cracking of heavy hydrocarbons in many
commercial processes. However, the catalytic degradation of waste plastics using zeolite
may be a difficult problem due to a limited diffusion of big molecules into zeolite pores,
which can be overcome with small crystal size and also high external surface area due to
the use of a fine powder. Also, activated carbon impregnated with transition metals is a
micropore material with a high surface area, which promotes hydrogen transfer reactions
during decomposition of hydrocarbons like the reforming catalyst.
On the contrary, alumina and amorphous silica–alumina have relatively low surface
area, but big pore size and large pore volume, due to their mesopore structure. They have
low acid strength compared with zeolites. However, they have a sufficient diffusion of
heavy hydrocarbon having large kinetic diameter through the pores, without control of
different molecules. A similar catalyst is MCM-41, although it has high surface area, has
a uniform mesopore structure. The utility of its high surface area and uniform mesopore
in catalytic degradation of polyolefin has recently studied by several researchers [16–19].
Also, sulfated zirconia known as a superacid solid can be used as a catalyst in catalytic
reaction of hydrocarbons [20, 21]. FCC catalyst has been developed for the cracking of
heavy hydrocarbon molecules into gasoline range hydrocarbons. The catalyst consists of
silica–alumina with a mesopore structure and zeolite with a micropore structure, which
can be well cracked by step-by-step diffusion of heavy molecules in the catalyst of
different pore structure. FCC catalyst has been found to have a significant effect in the
pyrolysis of thermoplastics [22. 23].
Seo et al. [24] have described the catalytic degradation of polyethylene using various
acidic catalysts at 450◦ C. The yields of gas, liquid and residue are illustrated in Table 5.3
and the PONA distribution in liquid products is shown in Table 5.4. Catalytic degradation
148 K.-H. LEE
Table 5.3 Yields of liquid, gas and coke produced from thermal and catalytic degradation of
HDPE with various catalysts at 450◦ C
Yields of products Liquid Gas Coke Liquida (wt%)

(wt%) (wt%) (wt%)
C6 –C12 C13 –C23 ≥C24
Thermal cracking only 84.00 13.00 3.00 56.55 37.79 5.66
ZSM-5 (powder) 35.00 63.50 1.50 99.92 0.08 0
Zeolite Y (powder) 71.50 27.00 1.50 96.99 3.01 0
Zeolite Y (pellet) 81.00 17.50 1.50 86.07 11.59 2.34
Mordenite (pellet) 78.50 18.50 3.00 71.06 28.67 0.27
Silica-alumina(powder) 78.00 21.00 1.00 91.31 8.69 0
Alumina(powder) 82.00 15.90 2.10 53.02 43.27 3.71
a
Determined by GC/MS
Table 5.4 PONA distribution in oil products from thermal and catalytic degradation of HDPE
with various catalysts at 450◦ C
Catalyst Total (Total paraffin) Total Naphthene Aromatics Othersa

paraffin olefin
n-paraffin i-paraffin
Thermal cracking 40.75 40.47 0.28 39.93 18.50 0.68 0.14
ZSM-5 (powder) 1.63 1.51 0.12 16.08 23.55 58.75 0.01
Zeolite Y(powder) 5.39 0.00 5.39 79.92 7.68 7.01 0.00
Zeolite Y (pellet) 25.10 20.68 4.42 49.28 12.05 8.43 5.14
Mordenite (pellet) 31.07 30.89 0.18 57.07 11.51 0.13 0.22
Silica–alumina (powder) 0.20 0.20 0.00 91.62 5.62 0.39 2.17
Alumina (powder) 32.57 32.57 0.00 50.19 14.99 1.14 1.11
a
Others = hydrocarbons containing oxygen or unidentified organic compounds
of HDPE with zeolite Y, mordenite and silica–alumina gave 71–81 wt% oil yields,
which mostly consist of C6 –C12 hydrocarbons in the gasoline range, whereas thermal
degradation of HDPE produced 84 wt% oil yield with a much longer hydrocarbons like
wax. In catalytic degradation, pellet zeolite Y that possesses less external surface area
showed more oil yield and less gas yield than powder zeolite Y. Both all zeolites and
silica-alumina increased olefin content in oil product. Particularly ZSM-5 and zeolite
Y enhanced the formation of both aromatics and branched hydrocarbons having a high
octane number. ZSM-5 among zeolites showed the greatest catalytic activity in cracking
of heavy hydrocarbons to small gaseous hydrocarbons and formation of aromatics, which
was related to the restricted channel of this zeolite that favors oligomerization reactions
of olefins to form small alkyl aromatics, whereas mordenite produced the greatest amount
of coke, due to its unidimensional straight-channel structure. Amorphous silica–alumina
showed high yield of lighter olefins due to its strong acidity, but no activity in the
formation of aromatics and branched hydrocarbons because of its amorphous structure.
Audiso et al. [25] has studied the catalytic degradation of polypropylene using silica,
alumina and silica–alumina and zeolite catalysts in the range 200–600◦ C. The main
products in oil production using more efficient catalyst were C5 –C12 olefins. Also the
highest oil yields were obtained around 400◦ C. In catalysts, silica–alumina catalyst in
comparison with alumina and silica only was much more reactive.
The liquid-phase catalytic degradation of HDPE over BEA, FAU, MWW, MOR and
MFI zeolites with different pores in a batch reactor at 380 or 410◦ C has recently been
studied by Park et al. [26]. Among zeolites, high activity was obtained with BEA and MFI
zeolites, because of their bent pore structure suppressing carbon deposit, whereas MOR
zeolite showed low activity, due to the rapid blocking of the linear pore structure even by
a small amount of carbon deposit. Large three-dimensional pores of FAU enhanced mass
transfer, resulting in a high yield of liquid product and also the slow diffusion of cracked
product in MWW zeolite brought about much more cracking into small hydrocarbons.
Accordingly, the pore shape of the zeolites was very important in determining the activity
and product distribution in the degradation of polymers.
The catalytic degradation of HDPE and LDPE with MCM-41, ZSM-5 and
silica–alumina in a batch reactor at 400◦ C was investigated by Aguado et al. [27]. The
activity order in the catalytic degradation of HDPE and LDPE was ZSM-5>MCM-
41>silica–alumina. The higher activity obtained over ZSM-5 was related to its stronger
acid properties, whereas the high activity of MCM-41 compared with silica–alumina was
influenced by the large surface area of MCM-41 with above 1000 m2 /g. The cracking of
polyolefin over zeolite leads to a high proportion of gaseous hydrocarbons consisting of
high olefin content and a liquid product in the range of gasoline with a high aromatic
content. On the other hand, MCM-41 generated less olefinic gas products and, in addition
to the gasoline fraction, the middle distillates in the range C13 –C22 are produced. These
activities and product distributions are highly related to the acidic and pore properties of
the catalysts.
The activated carbon impregnated with different transition metals (Pt, Fe, Mo, Zn, Co,
Ni and Cu) as a catalyst for PE conversion in a fixed-bed reactor has been studied by
Uemichi et al. [28]. This catalyst plays a bifunctional role, with cracking and dehydro-
genation/hydrogenation activity. The major effect of the metal impregnated on activated
carbon was to increase the selectivity of aromatics with high octane number and to
decrease the formation of n-alkanes. The aromatic yield was the most effective in Pt, Fe,
Mo among various metals and also depended strongly on the support, which was much
more efficient on activated carbon than on silica–alumina and alumina. It is proposed
that two active sites with different function are to take part in the dehydrocyclization step
involved in the degradation reaction. The abstraction of hydrogen atoms from polymer
occurred predominantly on the acitivated carbon sites and the resulting hydrogen atoms
migrate to the metal sites, while the metal sites catalyzed the desorption of hydrogen
atoms.
8 EFFECT OF ADDITION OF OTHER THERMOPLASTICS
Lee et al. [29] reported the effect of PS addition in the catalytic degradation of waste
HDPE and PS mixture using spent FCC catalyst at 400◦ C. Figure 5.14 shows the cumu-
lative amount distributions of liquid products as a function of reaction time for the catalytic
degradation of waste HDPE and PS mixture in different proportions. The increase of PS
content in HDPE and PS mixture showed much high initial degradation rate and high
150 K.-H. LEE
HDPE: PS = 100:0
HDPE: PS = 80:20
HDPE: PS = 60:40
HDPE: PS = 40:60
HDPE: PS = 20:80
HDPE: PS = 0:100
HDPE: PS = 100:0 (no-cat.)
Reaction temperature
200 500
B
A
160 400
Cumulative amount (g)
Temperature (°C)
120 300
80 200
40 100
0 0
0 100 200 300 400
Lapse time (min)
Figure 5.14 Cumulative amount distributions of liquid products for catalytic degra-
dation of waste HDPE and PS mixture using spent FCC catalyst at 400◦ C. (A initial
degradation region; B final degradation region). (Reproduced with permission from
Elsevier)
liquid product yield, whereas that of HDPE showed high final degradation rate after a
sufficient lapse in the reaction time.
According to the increase of PS content in HDPE and PS mixture, in Figure 5.15 the
fraction of gasoline components in the liquid products was increased from about 85 wt%
(pure HDPE) to about 98 wt% (pure PS) and the rest was kerosene + disel (C13 –C24 ).
No heavy oil (>C24 ) was detected. In the catalytic degradation of pure HDPE without
PS, the major product was olefin components whereas the paraffin products as well as the
aromatic and naphthene products with a cyclic structure were minor products. Accord-
ing as PS content in the reactant increased from 0 to 20 wt%, the fraction of paraffin
Paraffin
Olefin
Naphthene
Aromatic
< C13 (gasoline)
C13 − C24 (kerosene + diesel)
> C24 (heavy)
100
80
Fraction of liquid product (wt%)
60
40
20
0
0 20 40 60 80 100
PS content (wt%)
Figure 5.15 PONA and carbon number distributions of liquid products as a function of
PS content for catalytic degradation of waste HDPE and PS mixture using spent FCC
catalyst at 400◦ C. (Reproduced with permission from Elsevier)
products was sharply increased whereas that of olefin products were decreased, because
of the increase of paraffin products by the availability of hydrogen in the carbenium ion
from PS degradation to olefinic intermediates [30, 31]. However, in the range of PS con-
tent 20 wt% or above, the fraction of aromatic products as a function of PS content was
sharply increased whereas that of paraffin products was sharply decreased. The PONA
distribution of liquid products was influenced by the interaction of the degraded interme-
diates from HDPE and PS degradation. Furthermore, the aromatic product was accelerated
with the cyclization of paraffinic and olefinic intermediates from HDPE degradation as
well as the aromatic fragments from PS degradation. In aromatic products, as shown in
Figure 5.16, the increase of PS content in the mixture was linearly increased the styrene
product fraction, but decreased the ethylbenzene product fraction. Styrene product was
152 K.-H. LEE
Benzene
Toluene
Ethylbenzene (EB)
C3+ benzene
Styrene
C1+ styrene
EB+Styrene
80
70
60
Selectivity in aromatic products (wt%)
50
40
30
20
10
0
0 20 40 60 80 100
PS content (wt%)
Figure 5.16 Selectivity in aromatic products as a function of PS content for catalytic

degradation of waste HDPE and PS mixture using spent FCC catalyst at 400◦ C. (Repro-
mainly produced from the degradation of PS while ethylbenzene product was influenced
by HDPE content, due to the cyclization of the olefinic and paraffinic intermediates
obtained by the first catalytic degradation of HDPE. Also their fraction with two car-
bon numbers in the side group showed the highest selectivity of 60 wt% or above. The
addition of PS in the catalytic degradation of HDPE using spent FCC catalyst acceler-
ated the production of ethylbenzene and styrene in pores of spent FCC catalyst as shape
selectivity.
60
370°C
370°C
50
Yield of liquid product (%)
40
350°C
30 350°C
20
10
0
0 100 200 300 400 500 600 700
Lapse time (min)
Figure 5.17 Yield of liquid product as a function of lapse time for catalytic degradation
of waste HDPE and mixed plastics (HDPE:LDPE:PP:PS = 33%:22%:33%:11%) using spent
FCC catalyst at 350◦ C and 370◦ C (solid line: mixed plastic; dotted line: HDPE)
Walendziewski [1] was reported the thermal and catalytic degradation of PE, PP, PS
and their mixture using alkaline catalyst. The catalytic degradation of PE + PS, compared
with that of PE, showed high aromatic content and low boiling temperature, and also high
density, high RON and MON values in the gasoline fraction.
According to the type of plastics, the characteristics of oil product in thermoplastics
was clearly differed. Figure 5.17 shows the cumulative yield distributions of liquid prod-
uct as a function of reaction time for catalytic degradation of pure waste HDPE and
mixed plastic (HDPE:LDPE:PP:PS = 33%:22%:33%:11%) at 350 and 370◦ C, respec-
tively. Here the ratio in the mixed plastic was the average weight ratio of general
thermoplastics generated in Korea. The mixed plastic showed much higher initial rate
of liquid product yield than that of pure HDPE. Also, the catalytic degradation of mixed
plastic occurred at lower reaction temperature (by about 20◦ C) than that of pure HDPE
plastic, because it was included the plastics with low degradation temperature in the mixed
plastic.
9 FRACTIONAL DISTILLATION OF PRODUCTS
Reactor effluent that is composed of oils with various boiling temperatures is fed
into the base of the fractional distillation tower where it is fractionated into selected
product streams. Various product streams in the distillation tower are fractionated from
154 K.-H. LEE
Condenser
Gas products
Light oil (LO)
Heavy oil (HO)

Condenser
Feeding of
product
Reboiler
Heavy oil settler
Recycled oil
Figure 5.18 Flow diagram of distillation tower
reactor effluent due to their different boiling temperatures. The control variables are the
temperature gradient in distillation tower, temperature of reboiler located at the main
column, reflux ratio of product oil and pressure (vacuum or atmospheric pressure).
Figure 5.18 shows two streams produced from the main column, including light product
and heavy oil (HO). However, these product streams can be changed by regulation of the
tower structure. Light products are taken overhead to the accumulator of light product
after it is cooled in condenser, and are separated into both gas products and light oil
(LO). The condensation of the product streams in the condenser may be cooled by a
water stream. Gas products consisting of C5 and below, with mainly alkane components
may be used as fuel gas in the pyrolysis process or sent to a gas plant, the quality of
which can be continuously monitored by an on-line analyzer.
Light oil is mainly obtained in the gasoline range and has a partial reflux stream by
control of the reflux ratio that controls the temperature gradient in the distillation tower
and also the product quality. HO consists mainly of kerosene and diesel range compounds,
which is the desired product as fuel oil with high calorific value. The boiling range of
LO and HO depend on the current desired product specifications, which are obtained
by control of experimental variables in the distillation tower. A portion of the main
column bottom passes to the heavy oil settler, which receives the overflowing heavy oil
with high viscosity generated from the main column bottom. They are returned to the
melting reactor or cracking reactor, in order to crack the heavy oil again into the light
oil. In many cases, the oils produced by this method are marketed without any additional
processing.
10 PROPERTIES OF LIQUID PRODUCT [32]
The need for various grades of the product oils separated in the distillation tower is
evident. In order to keep the various grades on a uniform basis, the authorities in each
country have standardized on a few grades by the properties of the oil produced.
It is necessary to compare reliable properties of the oil produced, as a comparison with
those of commercial gasoline, kerosene and diesel. It is essential to determine the physical
measurements such as those listed for a variety of the oils, as shown in Table 5.5. Based
on these values, the oil produced in the process plant is tested, to determine whether it
can be put on the market.
As the density of the oil produced is decreased, the heat value per volume decreases, but
the heat value per mass will increase. If the oil is usually purchased and sold on a volume
basis, heavy oil is more efficient. Also, if it is necessary to choose the most important
specific of the oil produced, viscosity will be selected. Viscosity can aid combustion and
can also be the cause of the greatest trouble. For proper and efficient combustion an oil
should have a reasonable viscosity at the burner. In the case of too high viscosity, difficulty
in pumping in the process and trouble at the burner are encountered and also carbon residue
is high due to poor combustion. However, in case of too light oil, incomplete combustion
occurs and there will be a loss of economy.
Further sources of trouble with the oil produced is water and sediment present in the
oil, when it is used as a fuel oil. Water causes sparking, spitting and flashback of the
flame, which result in loss of heat as a result of improper combustion. Sediments such as
sand and carbon, etc. cause the erosion of burner tips, pump parts and sensitive control
valves, etc. Also, some chemical compounds present in an oil will absorb oxygen from
air or water, to form new compounds. Unfortunately, some of these chemical compounds
are insoluble in the oil, with the result that they will either remain suspended in the
oil or will drop to the bottom of the tank. They must not reach the suction lines in a
storage tank.
When discussing the oil produced, the subject of carbon becomes an issue. Carbon is
formed during cracking of hydrocarbons at high temperature and pressure. This carbon
is present in heavy oil and will be suspended within the oil. However, oil containing a
small amount of carbon is easily combustible without any trouble. The carbon content is
Table 5.5 Properties of the oil product
Items LO (in KIER)a Gasoline HO (in KIER)b Kerosene Diesel

◦
Ignition point ( C) 74 >40 >40
Pour point (◦ C) <−50 −12.5 <−15 <−15
Copper corrosion (100◦ C, 3 h) <1 <1 1 <1 <1
10%carbon residue (wt%) 0.01 0.21 <0.15
Ash (wt%) 0.001 0.003 <0.02 <0.02
Kinematic viscosity (40◦ C) <1.0 6.5 1.4–3.0 1.9–5.5
Density (kg/m3 ,15◦ C) 757 831 815–855
Distillation (T90) 232 <175 430 285–325 <360
Heat of combustion (kcal/kg) 11,180 10,983 11,020 10,800
Water & sediment (vol%) <0.01 <0.005 <0.02
a
Light oil produced in KIER process
b
Heavy oil produced in KIER process
156 K.-H. LEE
measured by the Conradson carbon test, as a relative value of coke formation. This is the
amount of carbon remaining after evaporating all the volatile materials in a certain type
of apparatus. It is representative of the tendency of the oil to form coke, in many practical
uses such as household and industry, etc. But the light oil is very thin and does not have
much carbon residue. This oil is distilled until 90% of the sample has been vaporized.
The remaining 10%, the heaviest of the entire sample, is used to run the carbon test as
10% carbon residue value measured. For an example, the values for commercial kerosene
and diesel would be below about 0.2.
There are certain impurities present in most fuel oils. These organic and inorganic
substances are noncombustible and after combustion of the fuel oil they will form a
residue called ash. The greatest percentage of ash found in various oils is directly related
with the crude oils from which they are refined. The crude oil is usually mixed with water,
mud and sand, etc. Most of these contaminants are removed from the crude oil, but very
small amounts will still remain suspended in the crude oil. Moreover, the ash-producing
materials found in crude oil are concentrated in the heaviest oils such as the residuals. In
order to determine the ash amount, the oil in the presence of air is burned. The remaining
materials are noncombustible ash, which is computed as the total percentage of ash in the
sample. The ash amount measured for kerosene and diesel is below 0.2 wt%, but the oil
of two types produced in KIER process is very low.
As the oil is heated, the oil vapors and air will ignite without the application of an
external flame or spark at a certain temperature, which is called the ignition point of
the oil. Generally the spontaneous ignition temperature reduces with increase in carbon
number and is high for the aromatic hydrocarbons, due to the inherent structural stability
of the benzene ring [33]. The ignition point of kerosene and diesel is required to be above
40◦ C. Thus, the oil produced in the pyrolysis process must be blended with a component
of high ignition point, which should be watched with great care.
The temperature at which an oil will just flow under standardized conditions is known
as the pour point. This test has particular significance in connection with oils that may
require heating to liquefy them and also to enable them to be pumped. If an oil of low
pour point begins to solidify in the storage tank in cold weather, some other means will
be needed to prevent the mass from solidifying completely. For example, when the plant
is shut down in cold weather, the oil in the line and tank, etc. will solidify and thus the
oil is too viscous to be pumped. So the pour point of the oil produced must be checked
during cold weather.
Sulfur is one of most important elements present in an oil, although the sulfur content
may be very low. It is usually in combination with carbon, hydrogen, oxygen and nitro-
gen, forming many different compounds. They have mainly a high boiling point and are
therefore concentrated in the residual oils. In the petroleum refinery industry, they break
down during the refining processes such as the hydrodesulfurization process, which can
lead to low-sulfur residuals. This process brings the residual oil into contact with hydro-
gen gas and a catalyst. The residual oil is split into low-sulfur oil and hydrogen sulfide
gas. The most important trouble for oil containing sulfur is corrosion by its combustion
products such as sulfur dioxide and sulfur trioxide. Moreover, the corrosiveness of these
sulfur compounds is increased by moisture. But the sulfur has little effect on the handling
and storage of the oil and also industrial instruments such as pump and mechanical parts.
Chemical compounds will boil at a certain temperatures. Thus, oil consisting of various
compounds is made up of a series of fractions, defining the distillation range of the oil.
Distillation range is the difference in degrees between the initial boiling point (IBP) and
the end point (EP). Thus distillation range will vary according to the type of oil. The
initial boiling point is the temperature at which the first drop of condensed vapor appears
in a distillation test. The next temperature point is the 10% boiling point, which is the
temperature that 10% of total volume of oil will distill off. The spread between the IBP
and the 10% point should be small so that the oil will continue to burn in case of ignition.
If the spread is too large, ignition and starting will be difficult. Also, the 90% point and
the end point must be watched. If the spread between the 90% point and end point is very
great, the oil has been blended or contaminated. This can cause poor combustion. If the
end point is high, the 90% point will also be high, these high values may be difficult to
burn and can cause carbon trouble. For efficient combustion, the distillation curve should
be smooth. A fluctuating distillation curve implies an oil that may give irregular operation
due to unstable conditions. Therefore, the distillation test is one of the best methods for
detecting the quality of the oil produced such as light or heavy oil fractions.
As an example, the distillation curves of LO and HO obtained in KIER process
was compared with those of commercial gasoline, kerosene and diesel are shown in
Figure 5.19. The distillation curve of LO product was distributed between commercial
550
500 Gasoline
Kerosene
Diesel
450
LO
HO
400
350
Boiling Point(°C)
300
250
200
150
100
50
0
0 10 20 30 40 50 60 70 80 90 100
Mass(%)
Figure 5.19 Boiling point distribution of commercial gasoline, kerosene and diesel, and
LO and HO products obtained in the KIER process
158 K.-H. LEE
gasoline and kerosene. For LO product, the spread between the 90% point and end point
is big, because of the mixing of heavy oil. On the other hand, HO product has a higher
boiling point distribution than commercial diesel. Their distillation curves can be changed
by experimental variables in the distillation tower, such as temperature gradient, pressure,
reflux ratio and reboiler temperature, etc.
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160 K.-H. LEE
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6
Development of a Process for the

Continuous Conversion of Waste
Plastics Mixtures to Fuel
TAKAO MASUDA AND TERUOKI TAGO
Division of Chemical Process Engineering, Graduate School of Engineering, Hokkaido
University, N13 W8 Kita-ku, Sapporo 060–8628, Japan
1 INTRODUCTION
The amount of waste plastics discarded each year is constantly increasing and is causing
serious pollution-related problems worldwide. Chemically recycling such waste might
provide cheap and abundant sources of useful chemicals and energy. Among a number
of potential approaches to recycling, chemical approaches, which convert waste plastics
to useful hydrocarbons, have been recognized as being of particular promise.
Presently, about half of the waste generated in Japan is derived from factories as
specific plastics, such as polyolefins, polystyrene (PS) [1–4], poly(ethylene terephthalate)
(PET) [5–6], and polyvinylchloride (PVC) [2, 3, 7–11]. To date, several studies have
focused on the individual degradation of these waste plastics. The remaining half of the
waste plastics in Japan is generated from households in the form of plastic mixtures and
waste-containing kitchen refuse. PVCs can be removed from such waste mixtures by
utilizing PVCs with a higher density than that of other plastics. However, there remain
certain unresolved issues, such as the lack of an efficient continuous chemical recycling
process for application to a mixture of remaining waste plastics. Specifically, it remains
problematic that each type of plastics has different pyrolytic properties, as is the fact
that large amount of sublimate materials, such as terephthalic acid (sublimation point
∼300◦ C), are produced from the degradation of some plastics, such as PET. Terephthalic
acid is precipitated as a hard, solid body around valves and pipelines, i.e. at locations
where the temperature is below 300◦ C.
Waste plastics are primarily generated by small-to-medium-size enterprises and house-
holds. Therefore, it is preferable to build chemical plants for the recycling of waste
162 T. MASUDA AND T. TAGO
plastics locally, i.e. in each self-governing region or prefecture. However, in this respect,
it should be noted that it is costly to use nitrogen or hydrogen as the carrier gas.
Because steam is cheaper and easy to handle, it is a potential candidate carrier gas in
such plants.
The chemical recycling of waste plastics consists of two processes: the first is the
degradation of waste plastics for the production of heavy oils, and the second is a catalytic
cracking process that converts the heavy oils into useful hydrocarbons. To achieve these
recycling goals, it remains necessary to develop efficient chemical recycling processes
that can operate in a steam atmosphere.
In this chapter, a chemical recycling method for the mixtures of waste plastics is
described. First, a number of possibilities are examined that would realize the formation
of pyrolytic properties with a uniform reaction rate among oxygen-containing plastics;
furthermore, it would be advantageous to achieve the degradation of such plastics with
the production of a minimal carbonaceous residue [5–6]. To this end, a new pyrolytic
reactor [12] has been proposed that has been shown to achieve high hold-up, a high level
of heat transfer, and good contact between melted plastics and steam, thus accelerating
hydrolysis. Using this reactor, a mixture of waste plastics can be degraded and further
decomposed over an FeOOH catalyst in a steam atmosphere. Second, chemical processes
are described here that can achieve a catalytic cracking of the heavy oil, achieved by
the pyrolysis and hydrolysis of the waste plastics, and producing useful fuels [13–15].
The catalyst used in the recycling process must exhibit high and stable activity during
the catalytic cracking of the heavy oil in a steam atmosphere [16]. Finally, the rationale
for and usefulness of the proposed chemical recycling method are both validated by the
experimental results obtained in a pilot-scale plant.
2 RECOVERY OF HEAVY OIL FROM WASTE PLASTIC
The waste plastics generated from households are in the form of plastic mixtures; among
such mixtures, the amount of PET generated as a household waste has rapidly increased
as the production of PET bottles has increased. PET is formed by the ester bonding
of terephthalic acid and ethylene glycol. When PET is heated above 380◦ C, pyrolysis
suddenly starts, yielding oxygen-containing hydrocarbons and a significant amount of
carbonaceous residue [17–19]. Accordingly, in order to develop a recycling process for
the conversion of waste plastics into useful liquid hydrocarbons, a method for the degrada-
tion of a mixture of waste plastics without the production of such a carbonaceous residue
is required.
2.1 DEGRADATION OF VARIOUS PLASTICS
The relationship between the rate of PET degradation and the molar fraction of steam
in the carrier gas was investigated using a thermogravimetric apparatus equipped with
a thermobalance. Figure 6.1 shows the remarkable change in the fraction of unreacted
PET as the molar fraction of steam in the carrier gas was varied. When a pure nitro-
gen stream (steam molar fraction = 0%) was used, the degradation of PET was initiated
CONTINUOUS PROCESS FOR FUEL PRODUCTION 163
1.0
Heating rate:
5°C min−1
0.8 Molar fraction
Unreacted fraction, 1−x

of steam = 0.7
0.6 0.5
0
0.3
0.4
0.15
0.2
0
200 300 400 500 600
Reaction temperature T / °C
Figure 6.1 Change in the fraction of unreacted PET in a steam atmosphere. Heating
rate: 5◦ C min−1 . (Reproduced with permission from Elsevier)
at about 380◦ C and was terminated at about 530◦ C, leaving about 16% carbonaceous
residue. When the carrier gas contained steam, the fraction of carbonaceous residue was
drastically reduced from 16% (100% nitrogen) to below 2% (70 mol% steam). Further-
more, the initiation temperature for pyrolysis decreased by about 30◦ C. Figure 6.2 shows
the relationship between the molar fraction of steam in the carrier gas and the amount
of carbonaceous residue remaining at 520◦ C. The circles, triangles, and squares represent
the results obtained at heating rates of 2.5, 5.0, and 10◦ C min−1 , respectively. All data lie
on a single curve, suggesting that the amount of carbonaceous residue depends only on
the partial pressure of steam, and not on the rate of increasing temperature. The amount
of residue thus decreases with increases in the partial pressure of steam. Less than 1%
residue was found to remain under 100% steam carrier gas conditions.
20
Plastic: PET Heating rate
2.5°C min−1
15 5.0°C min−1
Yield of residue / wt%
10°C min−1
10
0
0 20 40 60 80 100
Fraction of steam in the carrier gas
/ mol%
Figure 6.2 Relationship between the molar fraction of steam in the carrier gas and the
yield of residue at 520◦ C. (Reproduced with permission from Elsevier)
C=O C=C C−O −(CH2)n−

(ester) (aromatics) (ester) (s −bond)
Unreacted PET
A.U.
PET at 60%
conversion in nitrogen
PET at 70%
conversion in steam
2000 1600 1200 800 400
Wave number /cm−1
Figure 6.3 FTIR spectra of unreacted PET and of residues obtained from PET at 60%
conversion in both nitrogen and steam (70 mol%) atmospheres. (Reproduced with
permission from Elsevier)
Figure 6.3 shows the FT-IR spectra of residues obtained in nitrogen at a PET conversion
of 60%, and in a steam atmosphere at a conversion of 70%. This figure also shows the
spectrum for unreacted PET. PET is formed by the ester bonding of terephthalic acid
and ethylene glycol. In the case of thermal pyrolysis in nitrogen, the dehydration of the
chemical bonds and the random scission of the main chain of PET occurred, resulting
in a reduction in the peak strengths corresponding to bonds involving the oxygen atom
(C–O, C=O) and σ-bonds, leaving a hydrogen-poor residue. On the other hand, when
the degradation of PET was conducted in the presence of steam, the C–O bond and σ-
bond were preferentially weakened, and a peak corresponding to free aromatics (C=C)
appeared. These aromatics were considered to be terephthalic acids at the ends of the main
chain of PET. Hence, steam was found to accelerate the hydrolysis of PET, producing
monomers of PET such as terephthalic acid.
Figure 6.4(a, b) shows the thermogravimetric curves (TG-curves) for plastics at a heat-
ing rate of 5◦ C min−1 in nitrogen and in steam, respectively. Seven types of plastics were
used in this series: polyethylene (PE), polypropylene (PP), polycarbonate (PC), poly-
butyleneterephthalate (PBT), polystyrene (PS), nylon-6 (N6) and nylon-6,6 (N6,6). The
curves for the degradation of PET are also shown in the figure for comparison. The TG
curves were remarkably different among the plastics in a nitrogen stream, due to differ-
ences in the main chains of the plastics. Furthermore, polyester resins, such as PC, PBT,
and PET, yielded large amounts of carbonaceous residue at 527◦ C, due to dehydration
during the degradation in nitrogen. In contrast, in a steam atmosphere, the TG curves of
PC, PBT, and PET were remarkably altered by shifts to lower temperature regions and
by reducing the amount of carbonaceous residue, as compared with those in a nitrogen
atmosphere. Accordingly, it was concluded that the dominant mechanism of degradation
of polyester resins changed from thermal pyrolysis to hydrolysis by introducing steam as
the carrier gas.
Under the nitrogen steam conditions, PC showed the lowest degradation rate. On the
other hand, the plastic resin with the lowest degradation rate was PE in a steam atmo-
sphere. Therefore, the size of a degradation reactor could be designed by considering the
degradation rate of PE alone.
1.0
Fraction of unreacted resin /-

0.8 PS
N6,6 N6
0.6 PBT
PE
0.4
PC
Carrier gas: N2 PP
0.2 PET
Heating rate: 5 °C•min−1
0
200 300 400 500 600
Temperature / °C
(a)
1.0
Fraction of unreacted resin /-
PS PE
0.8
N6
0.6 PET
PP
0.4 PBT PC
Carrier gas: steam N6,6
0.2
Heating rate: 5 °C•min−1
0
200 300 400 500 600
Temperature / °C
(b)
Figure 6.4 Change in the fraction of unreacted plastics used in this study at a heating
rate of 5◦ C min−1 : (a) in nitrogen; (b) in steam. (Reproduced with permission from
Elsevier)
2.2 CATALYTIC CRACKING OF WASTE PLASTICS WITHOUT RESIDUE
The degradation of PET in a steam atmosphere is effective at reducing carbonaceous

residue, and this type of degradation produces terephthalic acid and oxygen-containing
compounds. However, terephthalic acid is precipitated as a hard solid body around valves
and pipelines, because this compound is a sublimate material (sublimation point ∼300◦ C).
Therefore, in this case, sublimate materials such as terephthalic acid should be converted
into liquid hydrocarbons. In order to convert this produced terephthalic acid, a catalyst
for cracking carbonyl groups of terephthalic acid is required. For this reason, transition
metal oxides, which easily form carbonyl complexes, were considered to be suitable
catalyst materials. Moreover, the transition metal oxides such as iron oxide and nickel
oxide are inexpensive. In this section, a method for the decomposition of terephthalic
acid into useful liquid hydrocarbons is described. The screening of potential catalysts was
conducted using transition metal oxide catalysts.
The catalytic cracking of PET was carried out using a fixed-bed type of reactor in
a steam atmosphere. The reactor was heated to the desired temperature in a mixture of
steam and nitrogen as the carrier gas. After feeding PET particles into the reactor, the
particles were heated to the reaction temperature, and then underwent the hydrolysis in a
steam atmosphere to be decomposed to terephthalic acid and lighter hydrocarbons. These
molecules were cracked through the catalyst bed. The liquid products were condensed in
two condensers cooled with ice and water. Lighter hydrocarbons were collected in a gas
pack. The amount of carbonaceous residue was calculated from the difference between
the mass of the catalyst before and after the experiment. The reaction was conducted at
the temperatures ranging from 450 to 530 K.
Figure 6.5 shows the yields ([wt%]) of the reaction of PET using several transition
metal oxide catalysts under the following conditions: a temperature of 500◦ C, a time
factor (the ratio of the mass of the catalyst W , to the PET feed rate F ) of 0.317 h, and a
particle size of 0.21–0.25 mm. Fe2 O3 did not show activity, hence these results have been
omitted. With respect to the reduction of terephthalic acid, FeOOH, nickel hydroxide and
nickel oxide showed the decomposition activity of terephthalic acid. However, a large
amount of benzoic acid, which is also a sublimate material (sublimation point ∼100◦ C),
was produced over nickel hydroxide and nickel oxide. Because these nickel compounds
are more expensive than FeOOH, FeOOH was considered to be a suitable catalyst for the
decomposition of terephthalic acid.
Figure 6.6 shows the change in product yield with increase in the time factor W /F . The
amount of sublimate materials (terephthalic acid and benzoic acid) decreased remarkably
with increase in the time factor, and no sublimate materials were observed after approxi-
mately 0.5 h. Moreover, carbon dioxide was produced, and the yield of the carbon dioxide
Gaseous
Benzoic acid Other oil compounds
5.5% Acetoaldehyde Rresidue
Phenol
Acetophenone Benzene Carbon dioxide
4.8 FeOOH
24.1 12.9 7.7 5.9 37.2
Terephthalic acid Benzoic acid

Ni(OH)2
31.9 36.1 3.1 8.2 13.5 3.1
29.6 36.6 3.3 8.8 10.3 4.1 5.5 NiO
Benzophenone Acetic acid
Liquid products Gas products
0 20 40 60 80 100
Product yield / wt%
Figure 6.5 Production yields of the reaction of PET over transition metal
catalysts. T = 500◦ C, W /F = 0.32 h−1 , particle size = 0.21–0.25 mm, molar fraction of
steam = 0.94%. (Reproduced with permission from Elsevier)
Other gaseous
Residue compounds
100
80 Carbon dioxide
Product yield / wt%
60 Other liquid
compounds
40 Phenol
Benzene
20 Benzoic acid
Acetophene
Terephthalic acid
0
0 0.081 0.159 0.317 0.634
W /F/ (kg-cat)· (kg-PET)−1·h
Figure 6.6 (a) Change in product yield with an increase in the time factor, W /F .
T = 500◦ C, particle size = 0.21–0.25 mm, molar fraction of steam = 0.94%. (Reproduced
with permission from Elsevier); (b) Change in product yield with an increase in the time
factor. The solid curves represent the calculated results
Terephthalic acid
Carbon dioxide Benzoic acid

Lighter hydrocarbons
Acetophenone
Other liquid compounds
Figure 6.7 Reaction pathway proposed for the reaction of terephthalic acid produced
by the hydrolysis of PET. (Reproduced with permission from Elsevier)
increased with decrease in the yield of the sublimate materials. Figure 6.7 shows the puta-
tive reaction mechanisms [5], i.e. the carbonyl groups of terephthalic acid are decomposed
to yield carbon dioxide and benzoic acid, and benzoic acid undergoes further reactions to
produce acetophenone and carbon dioxide. Some of the acetophenone was converted to
benzene and phenol, which are components classified under other liquid compounds. Two
reaction pathways, from acetophenone and other liquid compounds to carbon dioxide, are
negligibly small. In the reaction path from terephthalic acid to benzoic acid, benzene and
phenol were also produced. As a result, since sublimate materials such as terephthalic
acid and benzoic acid were successfully decomposed using an FeOOH catalyst, serious
pipe blocking at source plants could be avoided.
The structure and morphology of FeOOH treated at 500◦ C in a steam atmosphere
was analyzed by X-ray diffraction and transmission electron microscopy, respectively.
The X-ray diffraction analysis showed that FeOOH was transformed to Fe2 O3 during the
treatment in the steam atmosphere. In contrast, the TEM observation revealed micropores
of 1 nm diameter in the untreated FeOOH, which was not observed with commercial
Fe2 O3 . Moreover, the pores increased in diameter to approximately 5–100 nm after the
steam treatment. This morphology was thought to be the result of the dehydration of
FeOOH. It is possible that many active sites were generated on the surface of the pores,
resulting in the observation that treated FeOOH showed high activity, even though its
crystal structure is the same as that of Fe2 O3 [6, 20].
Terephthalic acid is a useful source material of PET, as well as benzoic acid and
benzoates. However, in order to recycle the terephthalic acid, produced further purification
is required, because other organic compounds are also produced as impurities in the
degradation process of waste plastic mixtures, e.g. PE and PET mixtures described in
Section 2.3.
2.3 CONTINUOUS DEGRADATION OF WASTE PLASTICS MIXTURES FOR

THE RECOVERY OF HEAVY OIL
The dominant mechanisms of polyester resin degradation (such as polycarbonate, poly-

butyleneterephthalate and polyethyleneterephthalate) changes from thermal pyrolysis to
hydrolysis by the introduction of steam as the carrier gas. PET was successfully degraded
by hydrolysis in a steam atmosphere, yielding an amount of pure terephthalic acid that
could be predicted from the chemical formula of PET, and leaving carbonaceous residue
of less than 1%. From economic and energetic viewpoints, it is both inexpensive and
easy to employ steam as the carrier gas in chemical recycling plants. Furthermore, the
temperature required to initiate was found to decrease approximately 70◦ C when polyester
resins were degraded by hydrolysis in a steam atmosphere [12].
When the mixture of waste plastics was degraded by accelerating the hydrolysis of the
plastics with steam and by decomposing the generated sublimate materials over FeOOH
catalyst, the following reaction conditions are needed:
1. A good contact of melted plastics with steam to accelerate the hydrolysis of plastics.
2. Large rate of the heat transfer to heat plastics up to a desired temperature.
3. High hold-up of plastics in a reactor to achieve an enough reaction time for degrading
plastics.
4. Contact of vapor of sublimate materials with FeOOH catalyst to decompose the mate-
rials.
Bockhorn et al. [2, 3] proposed circulated-spheres reactor for the pyrolysis of waste
plastics. This reactor enabled one to remove gaseous products from the reaction zone and
to achieve high heat transfer rates, namely condition (2) described above. The concept
of this circulated-spheres reactor has the possibility to attain conditions (1) and (3) by
improving the reactor.
Based the discussions above, a new pyrolytic reactor can be proposed that would be
capable of achieving a high hold-up, high heat transfer, and good contact between melted
plastics and steam for the acceleration of hydrolysis. Using this novel reactor system,
a mixture of waste plastics was degraded, and further decomposition over an FeOOH
catalyst was also achieved.
This novel reactor is a pyrolytic reactor system using stirred heat-medium-particles
(Figure 6.8). This pyrolytic reactor system is composed of a series of three types of
reactor. The first reactor uses stirred heat-medium-particles (reactor 1), the second is
a tank reactor (reactor 2), and the remaining reactor is a fixed-bed reactor (reactor 3).
Reactor 2 is located under reactor 1, and is separated from reactor 1 by a stainless steel
net. The seizes of these reactors are described in the figure. The expected reaction behavior
is described below.
In reactor 1, plastic particles are fed into the top of a bed of glass beads as the heat-
medium-particles, and the particles are then melted and adhered to the beads. The glass
beads are stirred slowly by two equipped impellers, one of which is the propeller-type of
impeller, and the other is an anchor-type of impeller located at the bottom of the bed of
glass beads. The propeller-type of impeller is turned to lift the particles. In this manner,
the glass beads at the top layer of the bed of glass beads are replaced continuously by
For pyrolysis For upgrading
Particles of
plastics Oil
N2
Motor N2
Pre-heating zone of steam
Glass beads N2
Impeller Water
Reactor 1
f: 55 mm
H: 100 mm
Catalyst Sampling zone

Reactor 2
f: 55 mm
Gas pack
H: 70 mm
Condenser
Stainless steel net
Reactor 3
T=400~500ºC
f: 35 mm
Muffle furnace H: 80 mm
(a)
Figure 6.8 (a) Schematic view of the proposed reactor system for the chemical recycling
of plastics; (b) photograph of the proposed reactor system. (Reproduced with permission
from Elsevier)
Reactor 1
Inlet of plastic
particles
Muffle furnace Reactor 2
Reactor 3
(b)
Figure 6.8 (continued )
other beads lying beneath the top layer. These stirred beads increase the rate of heat
transfer. Following the string of the glass beads, the melted plastics are transported over
the bed of glass beads, resulting in a high hold-up of plastics in the reactor and good
contact with the steam, which functions as the carrier gas. The melted plastics on the
glass beads are decomposed by hydrolysis with steam and the random scission of C–C
bonds. Some of the melted plastics on the glass beads are carried to the bottom of the bed
of glass beads, and are dripped onto reactor 2 (tank reactor). In reactor 2, the unreacted
plastics undergo further decomposition, yielding various gaseous compounds. Reactor 3
is filled with an FeOOH catalyst. Gaseous compounds, including the vapors of sublimate
materials, are passed through the FeOOH catalyst bed, where they undergo the catalytic
degradation.
A mixture of PE and PET was used as a model waste plastic mixture. The ratio of
PE/PET was 15:2, which is the ratio of the amounts of the two plastics discarded in
Kyoto, Japan. After continuous degradation with and without stirring of the glass beads,
the glass beads were collected from reactor 1 (Figure 6.8). When the glass beads were
not stirred, which corresponded to a trickle-bed type of reactor, a massive carbonaceous
residue remained with the glass beads on the top of the bed of glass beads. For this reason,
the heat transfer rate was low and the melted plastics did not make good contact with
the steam. On the other hand, there was not a massive amount of residue and glass beads
slightly colored yellow, when the glass beads were stirred by rotating the impellers at
rates exceeding 8 rpm. Furthermore, no residue nor oil was in reactor 2, the tank reactor,
(Figure 6.8). These results indicate that the proposed reactor system is useful for the
continuous degradation of plastics.
Figure 6.9 shows the dependency of the product yields, based on data collected at the
outlet of reactor 3 (see Figure 6.8), on the ratio of the catalyst mass W to the feed rate
of the plastics F and the time factor W /F increased from 0 to 1.5 h. Reactions were
conducted under temperature conditions ranging from 500◦ C, at a catalyst weight W of
about 2.0 × 10−2 kg. When the FeOOH catalyst was not loaded into reactor 3, a large
amount of yellow wax was obtained. When the FeOOH catalyst was loaded into reactor 3,
oil and carbon dioxide were produced. The amount of carbon dioxide and that of gaseous
hydrocarbons increased, and the yield of oil decreased, as the amount of FeOOH catalyst
loaded increased. This suggests that the FeOOH catalyst is capable of catalysis, leading
to the decomposition of a wax via oxidation by oxygen atoms from the lattice of FeOOH
and/or from H2 O.
When a wax is decomposed via oxidation by the oxygen atoms from the lattice of
FeOOH catalyst, the catalytic activity of an FeOOH catalyst will decrease. Therefore, the
gaseous product yields of the reaction were measured by sampling at different intervals
at a temperature of 500◦ C and the time factor of 1 h. The main gaseous products were
carbon dioxide (∼3 wt% for 140 min), n-C4 H10 (2 wt%), n-C3 H8 (2 wt%), C2 H6 (0.5
wt%), C2 H4 (1.5 wt%), and CH4 (0.5 wt%). Except for at the beginning of the reaction,
there were only negligible changes in the product yields. The amount of oxygen required
for producing carbon dioxide during a reaction time of 140 min was evaluated, and was
found to be larger than that generated through the phase change of iron from Fe2 O3 to
Fe3 O4 . These results suggest that the wax was decomposed by reaction with H2 O over
the FeOOH catalyst, and the catalytic activity of the FeOOH catalyst remained stable in
the steam atmosphere.
100
CO2 Coke
80
Product yields / wt%
Wax
60
Oil
40
20
Gaseous hydrocarbons
0
0 0.32 1.0 1.5
Time factor, W/F/ h
Figure 6.9 Effect of an FeOOH catalyst loaded in reactor 3 (see Figure 6.8) on prod-
uct yield; temperature = 500◦ C, carrier gas: steam. (Reproduced with permission from
Elsevier)
50
C20+
Feedstock: PE/PET = 15/2
40 Catalyst: FeOOH
W/F = 1 h
T= 500
Yield / wt%
30
20
10
0
51 0 15 20
Carbon number / -
Figure 6.10 Carbon number distribution of heavy oil produced by degradation of a

mixture of polyethylene (PE) and poly(ethylene terephthalate) (PET), at a weight ratio of
PE/PET = 15/2, temperature = 500◦ C, time factor W /F = 1 h, carrier gas: steam. (Repro-
Figure 6.10 shows the carbon number distribution of the products obtained when the
temperature was 500◦ C and the time factor was 1 h. The oil produced was considered to
correspond to heavy oil, as based on the carbon number distribution. Therefore, it would
be necessary to upgrade this oil for practical applications.
3 UPGRADING OF WASTE-PLASTICS-DERIVED HEAVY OIL OVER

CATALYSTS
In the series described thus far, it was found that the degradation of waste plastics proceeds
efficiently by both thermal pyrolysis and hydrolysis in a steam atmosphere. A wax and
carbonaceous residue produced by the hydrolysis of PET are decomposed by reaction
with steam over an FeOOH catalyst, the activity of which remains stable in a steam
atmosphere. However, the liquid product from generated from the process mentioned
above contains a large amount of heavy oil, as shown in Figure 6.10. Both catalysts and
chemical processes are required for efficiently upgrading the quality of the heavy oil.
3.1 CATALYTIC CRACKING OF HEAVY OIL OVER SOLID-ACID CATALYSTS
The most widely used conventional chemical methods are pyrolysis [21–25] and cat-
alytic cracking [13, 26–30]. The latter yields products with a smaller range of carbon
numbers and of a higher quality than products generated by the former method. Several
types of solid acid catalysts, which are known to be effective for catalytic cracking (e.g.
HZSM-5, HY and rare earth metal-exchanged Y-type (REY) zeolite and silica–alumina
(SA)) were evaluated by catalyst screening tests and are listed in Table 6.1. The acidic
Table 6.1 Properties of the catalysts. (Reproduced with permission from Elsevier)
Properties Catalyst
REY HY Silica–alumina HZSM-5 HZSM-5
(SA) (65) (1000)
Si/Al 4.8 4.8 13% 65 1000
alumina
Pore size (A) 7.4 7.4 60–100 5.3×5.6 5.3×5.6
Amount of total
acid sitesb 1.048 1.207 0.560 0.235 0.067
[mol · kg-cat−1 ]
Amount of strong
acid sitesc 0.375 0.441 0.187 0.122 0.031
[mol · kg-cat−1 ]
Supercage Yes (11.8A) Yes (11.8A) No No No
a
Measured by conventional TPD experiment
b
Based on the total amount of ammonia desorbed in the TPD experiment
c
Based on the amount of ammonia desorbed above 300◦ C in the TPD experiment
properties of the catalysts were measured from the temperature-programmed desorption

spectra of ammonia (NH3 -TPD) method. The feed oil was obtained by the pyrolysis of
solid polyethylene plastics at 450◦ C. To ensure homogeneity and to remove the lighter
hydrocarbons, the oil was distilled at 473 K. Table 6.2 shows the results of the elementary
analysis of the oil, which was used as a feed oil in the catalytic reforming reaction. A
continuous-flow, fixed-bed reactor was utilized for the catalytic reforming of the oil. The
reaction was carried out at 400◦ C under a nitrogen stream. The oil was fed at a constant
weight hourly space velocity (WHSV) of 1.0 kg-oil·kg-cat−1 ·h−1 for all catalysts.
Figure 6.11 shows the product yields for each catalyst. The products are classified into
four lumps, i.e. gas (carbon number 1–4), gasoline (5–11), heavy oil (above 12), and
a carbonaceous residue referred to as coke. In the figure, PE oil represents the feed oil
and contains a 34% gasoline fraction. The feed oil was effectively cracked by solid acid
catalysts. The gasoline yield was highest with REY zeolite. HZSM-5(65) yielded the
Table 6.2 Analysis of the feed oil. (Repro-

duced by permission of the American Chem-
ical Society)
wt% mol%
Heavy oil (≥C12 ) 95
Gasoline (C5 –C11 ) 5
Elemental analysis
H 13.7 66.0
C 82.0 32.9
N 0.0 0.0
O 4.3 1.1
H/C 2.00
RON of liquid [−] 4.5.

Gasoline Gas Coke C12+oil
HY
REY
SILICA ALUMINA
HZSM-5(1000)
HZSM-5(65)
PR OIL
0 20 40 60 80 100
Yield [wt%]
Figure 6.11 Distribution of product yields under nitrogen. WHSV = 1, T = 400◦ C and
t = 3 h. (Reproduced with permission from Elsevier)
largest quantity of gaseous compounds and the lowest amount of gasoline, which was
even lower than the gasoline fraction in the feed oil. While coke loading was highest
with HY zeolite, both HZSM-5 zeolites generated a negligibly small amount of coke
deposition. As the amount of coke deposition increased, the catalytic activity decreased.
Table 6.3 summarizes the yield of gaseous products according to the carbon number. In
this table, C2 = to C5 = indicate olefins corresponding to their respective carbon numbers.
Table 6.3 Yield of each gaseous product according to carbon number. The values in brackets
refer to the corresponding olefins. (Reproduced with permission from Elsevier)
Catalyst
Carbon REY HY Silica–alumina HZSM-5 HZSM-5
Number (SA) (65) (1000)
C1 0.09 0.20 0.07 0.12 0.01
C2 0.76 1.39 0.23 6.32 0.43
(C2=) (0.69) (1.39) (0.17) (6.01) (0.40)
C3 7.71 9.85 7.99 30.92 11.00
(C3=) (5.85) (3.25) (6.91) (29.90) (11.00)
C4 16.28 20.50 17.35 23.80 14.21
(C4=) (12.22) (15.51) (11.24) (13.78) (8.27)
C5 6.60 9.23 3.51 3.84 5.62
(C5=) (0.0) (0.0) (2.30) (1.80) (1.52)
C6 2.81 1.55 0.06 1.48 1.09
C7 1.23 1.02 0.0 0.62 0.41
C8 0.40 0.46 0.0 0.14 0.75
Total yield, (wt%) 35.88 44.20 29.20 69.04 33.52
A significant amount of C3 –C5 gaseous compounds were produced. With the exception
of ZSM-5(65) zeolite which favored the production of the C3 fraction, the other catalysts
yielded C4 as the main component.
HZSM-5 zeolite has channels within its crystals. The size of the channel is nearly equal
to that of benzene and is too small for easy penetration by oil molecules. Hence, the ends
of only certain molecules can penetrate the channels and undergo cracking. This leads to
a higher yield of gaseous products and a lower gasoline yield, indicating that HZSM-5
zeolite is not suitable for the cracking reaction of heavy oil. In contrast, the HY and REY
zeolites have larger pores. Therefore, the oil molecules can penetrate into the pores and
undergo cracking. Moreover, the existence of rare earth metals in REY zeolite results in
a decrease in the amount of stronger acid sites (see Table 6.1). This in turn leads to a
reduction in the deactivation rate and the amount of coke loading in comparison with that
obtained with HY zeolite. Accordingly, REY zeolite has the proper acidic properties and
pore size, and is suitable for the reaction with heavy oil.
3.2 PRODUCTION OF HIGH-QUALITY GASOLINE OVER REY ZEOLITES
The effects of the reaction conditions and the catalytic properties of REY zeolites on
reaction product yields and on the quality of the gasoline can now be examined.
Four types of REY zeolite (Si/Al = 4.8) with different crystal sizes and acidic prop-
erties were used. The physical and chemical properties of the fresh zeolites are given in
Table 6.4. Polyethylene plastics-derived heavy oil, shown in Table 6.2, was used as the
feed oil. The cracking reaction was conducted in a tubular reactor filled with catalyst par-
ticles under the following conditions: time factor W /F = 0.2–3.0 kg-cat kg oil−1 h−1 and
reaction temperature = 300–450◦ C. The lumping of reaction products were gas (carbon
number 1–4), gasoline (5–11), heavy oil (above 12), and a carbonaceous residue referred
to as coke. The index of the gasoline quality used was the research octane number (RON),
which was calculated from Equation 6.1 [31].
RON = −1.0729YNP2 + 0.7875YIP1 + 0.0978YIP2 + 0.3395YCP + 0.4049YAR + 69.0306

(6.1)
Table 6.4 Physical and chemical properties of the fresh REY zeolites. (Reproduced by permission
Catalyst
Property REY-1 REY-2 REY-3 REY-4
Si/Al 4.8 4.8 4.8 4.8
Crystal size (µm) 0.1 1.0 0.1 0.1
Amount of total acid sitesa 2.91 2.44 2.99 2.78
(mol kg cat−1 )
Amount of strong acid sitesb 0.79 0.57 0.66 0.70
(mol kg cat−1 )
a
Based on the total amount of ammonia desorbed in the TPD experiment
b
Based on the amount of ammonia desorbed above 300◦ C in the TPD experiment
100
450°C
Conversion of heavy oil [%]

80
350°C
60
300°C
40 300°C
400°C 350°C
20 400°C
450°C
0
0 1 2 3 4
Time factor, W/F [kg-cat kg-oil−1 h]
Figure 6.12 Dependence associated with the reaction temperature and the time factor,
W /F , on the conversion of heavy oil: zeolite crystal size = 0.1 µm. (Reproduced by
permission of the American Chemical Society)
where Yi is the weight fraction of the ith component in the gasoline fraction. The subscript
NP2 denotes the n-paraffins without C5 , IP1 the total isoparaffins from C5 to C7 , IP2 the
total isoparaffins without C5 –C7 , CP the total cycloparaffins, and AR the total aromatics.
The relationship between the conversion of heavy oil and the time factor, W /F , at
different reaction temperatures is shown in Figure 6.12. Conversion was defined as the
mass fraction of heavy oil (components above C12 ) converted to gasoline, gas, and coke.
This value was calculated from the following equation:
mass of heavy oil at the outlet

conversion = 1 − (6.2)
mass of heavy oil at the inlet
As the reaction temperature increased, the reaction proceeded. Although conversion

was greater as the temperature increased, there was no significant difference between the
conversions at 400 and 450◦ C. The effects of temperature on the respective yields of the
reaction products are shown in Table 6.5. As the temperature increased, the amount of
unreacted heavy oil decreased, and the yields of both gas and coke increased. The gasoline
yield reached a maximum value at 400◦ C, and then decreased with further increases in
temperature.
Table 6.5 Effect of temperature on product yield at W/F = 0.75 kg-cat kg oil−1 h. (Reproduced
Temperature Heavy oil Gasoline Gas Coke

(◦ C) (wt%) (wt%) (wt%) (wt%)
300 55.45 37.22 6.96 0.37
350 30.77 48.04 20.76 0.43
400 15.84 51.93 31.71 0.52
450 11.43 39.61 48.42 0.54
Figure 6.13(a) shows the effect of the reaction temperature on the relationship between
gasoline yield and the conversion of heavy oil. The gasoline yield increased with increas-
ing conversion to the maximum value, and then decreased significantly. This suggests that
the gasoline formed by the cracking of heavy oil subsequently undergoes further cracking,
which in turn yields gaseous products and coke. Thus, gasoline is an intermediate prod-
uct. The maximum gasoline yield, which is related to the rates of gasoline formation and
cracking, was observed at about 400◦ C. The same optimum temperature has been found
for the catalytic cracking of gas oil [32]. Figure 6.13(b) shows the relationship between
the gas yield and the conversion of heavy oil at various reaction temperatures. Because
almost all of the data lie on a single curve, the reaction temperature had no significant
effect on the gas yield at a constant conversion level. The yield of gas products increased
60
300°C 350°C
400°C
50
350°C
Gasoline yield [wt%]
40 400°C
450°C
30 300°C
20 450°C
10
0
0 20 40 60 80 100
(a)
100
300°C
80 350°C
Gas yield [wt%]
400°C
60
450°C
40
20
0
0 20 40 60 80 100
(b)
Figure 6.13 Effect of the reaction temperature on the relationship between product yield
and the conversion of heavy oil (zeolite crystal size = 0.1 µm): (a) gasoline yield; (b) gas
yield; (c) coke yield. (Reproduced by permission of the American Chemical Society)
1.2
300°C
300°C
0.9 350°C
Coke yield [wt%]

400°C
450°C 350°C
0.6
0.3
450°C
400°C
0
0 20 40 60 80 100
(c)
as the reaction progressed. Figure 6.13(c) shows the effect of different reaction tempera-
tures and conversion levels of heavy oil on the coke yield. At the same conversion level,
high temperatures reduced coke formation. The difference between the coke yields at 400
and 450◦ C was small. Similar findings have been reported for the catalytic cracking reac-
tion of gas oil, in which coke formation proceeded well at reaction temperatures below
400◦ C [32].
The effect of reaction temperature on gasoline quality and its main components are
shown in Figure 6.14. Below 400◦ C, the RON value increased with temperature due to
an acceleration of the formation rate of the IP1 fraction and the cracking rate of the NP2
fraction. Above 400◦ C, however, the cracking of IP1 proceeded (i.e. a reduction in the
yield of IP1), leading to a decrease in the RON value. On the basis of the gasoline, coke,
120
Composition [wt%], RON [-]
90
RON
60
AR
30
NP2
IP1
0
250 300 350 400 450 500
Temperature [°C]
Figure 6.14 Effect of the reaction temperature on the RON value of the gasoline
and main components (zeolite crystal size = 0.1 µm, W /F = 0.75 kg-cat kg-oil−1 h):
NP2 = n-paraffins without C5 , IP1 = C5 –C7 isoparaffins, AR = aromatics. (Reproduced
120
RON
Composition [wt%], RON [-]

90
AR
60 IP1
30
NP2
0
0 1 2 3
−1
Time factor, W/F [kg-cat•kg-oil •h]
Figure 6.15 Effect of the time factor, W /F , on the RON value of the gasoline and
the main components (zeolite crystal size = 0.1 µm, reaction temperature = 400◦ C):
NP2 = n-paraffins without C5 , IP1 = C5 –C7 isoparaffins, AR = aromatics. (Reproduced
Table 6.6 Comparison of commercial gasoline and the gasoline obtained from heavy oil derived
from waste plastics. (Reproduced by permission of the American Chemical Society)
Gasoline obtained Regular High-octane

Component (optimized) gasoline gasoline
IP1 (wt%) 40.44 29.47 36.78
AR (wt%) 29.03 33.23 50.53
NP2 (wt%) 12.36 15.41 9.96
RON (−) 100.92 90.44 108.01
and gas yields, as well as the RON value, the most favorable reaction temperature was
determined to be approximately 400◦ C.
The effect of the time factor, W /F , on gasoline quality and its main components
obtained at 673 K is shown in Figure 6.15. Below a W /F value of 0.75 kg-cat kg-oil−1
h, the increase in the RON value was due to the significant increase in the IP1 fraction
and the large reduction in the NP2 fraction. Above a W /F value of 1 kg-cat kg-oil−1 h,
only the reaction of IP1 to AR took place, producing a slight decrease in the RON value.
These results suggest that the optimum W /F value for the production of gasoline of the
highest quality is in the range 0.75–1 kg-cat kg-oil−1 h.
Table 6.6 compares the contents of the main components of regular and high-octane
gasoline with those of gasoline obtained under the optimal conditions, namely, tempera-
ture = 673 K, time factor = 0.75 − 1 kg cat kg oil−1 h, crystal size of the REY zeolite
catalyst = 0.1 µm, and the number of strong acid sites on the used catalyst = 0.28 mol
kg−1 . The gasoline obtained under the optimum contained a larger amount of IP1 and
a smaller amount of AR than the corresponding amounts in commercial gasoline. The
amount of NP2 in the gasoline obtained in this study was between that of regular and
high-octane gasoline.
3.3 KINETICS OF THE CATALYTIC CRACKING OF HEAVY OIL OVER REY

ZEOLITES
A rare earth metal-exchanged Y-type (REY) zeolite catalyst was found to be an effective
catalyst for the catalytic cracking of heavy oil. The influence of the reaction conditions
and the catalytic properties of REY zeolite on the product yield and on gasoline quality
have been described above. In this section, a reaction pathway is proposed for the catalytic
cracking reaction of heavy oil, and a kinetic model for the cracking reaction is developed
[14,33].
Figure 6.16 shows the typical relationship between product distribution and the time
factor, W /F , at different temperatures [13]. The experimental conditions are described in
Section 3.2. As the W /F value increased, heavy oil was cracked to produce gasoline and
gaseous products. Moreover, the gasoline product subsequently underwent further cracking
to yield gaseous products. Hence, the gasoline yield was shown to have a maximum value
100
300°C
80 Heavy oil
Composition [wt%]
60
Gasoline
40
20 Gas
Coke
0
0 1 2 3 4
Time factor, W/F [kg-cat•kg-oil−1•h]
(a)
100
350°C
80
Composition [wt%]
Heavy oil
60
Gasoline
40 Gas
20
Coke
0
0 1 2 3 4
(b)
Figure 6.16 Kinetic runs performed using a catalyst with a crystal size of 0.1 µm:
(a) 300◦ C; (b) 350◦ C; (c) 400◦ C; (d) 450◦ C. (Reproduced by permission of the American
Chemical Society)
100
400°C
Heavy oil
80
Composition [wt%]
Gas
60 Gasoline
40
20
Coke
0
0 1 2 3 4
(c)
100
450°C Gas
80
Composition [wt%]
Heavy oil
60
40
Gasoline
20
Coke
0
0 1 2 3 4
(d)
that appeared at a low W /F value and a high reaction temperature. The yield of coke
gradually increased and was considered to be the product of gasoline and heavy oil.
Figure 6.17 illustrates a possible reaction pathway that could account for the product
distributions shown in Figure 6.16. The proposed reaction pathway separately takes into
account the heavy oil, gasoline, gas, and coke lumps and is considered to represent the
product distribution.
The experimental conditions were set up to ensure that both the heat and mass transport
limitations across the film would be negligible. Moreover, limitations due to intraparti-
cle diffusion were assumed to be insignificant. The mass balance equation of the ith
component can be written as follows:
dFi
= ri (i = A, B, C, D) (6.3)
dW
where Fi is the mass flow rate of the ith lump (kg h−1 ); W is the mass of catalyst (kg);
ri is the production rate of the ith lump per unit mass of catalyst (kg (kg cat)−1 h−1 ); and
suffixes A, B, C and D refer to heavy oil, gasoline, gas, and coke lumps, respectively.
HEAVY OIL
k2 k3
GAS k1 COKE
k4 k5
GASOLINE
Figure 6.17 Reaction pathway proposed in this study. (Reproduced by permission of

Figure 6.18 shows the Arrhenius plots using the evaluated kinetic parameters. The data
were found to lie on a straight line for each parameter. The slopes of these straight lines
gave the activation energies, which are listed in Table 6.7. The activation energy for the
reaction of gas formation from heavy oil k2 is 75.5 kJ mol−1 and is comparable with
other data for gasification reactions: 58.6 kJ mol−1 in the case of a CaX catalyst (Ca
ion-exchanged X-type zeolite catalyst) [34], and 61.5 kJ mol−1 in the case of the silica
alumina [35] for the gasification of a polymer waste, and 75 kJ mol−1 for the reaction
of gas oil [36]. The difference in the activation energies between gaseous formation k2
104
103 k1
102 k2
k1, k2, k3[m6(kg kg-cat h)−1]
k4, k5, k3[m3(kg-cat h)−1]
k4
101
100
k3
10−1
k5
10−2
10−3
1.2 1.4 1.6 1.8 2.0
T −1× 103 [K−1]
Figure 6.18 Arrhenius plots of the kinetic parameters. (Reproduced by permission of

Table 6.7 Activation energies using a catalyst with a crystal
size of 0.1 µm. (Reproduced by permission of the American
Chemical Society)
Rate Rate
constants Ea (kJ mol) constants Ea (kJ mol)
k1 50.7 k4 35.1
k2 75.5 k5 42.1
k3 18.5
and gasoline formation k1 accounts for the fact that the selectivity of gaseous products
increases, while that of gasoline decreases with increases in temperature, especially at
temperatures above 400◦ C.
3.4 USAGE OF STEAM AS A CARRIER GAS
As it is both inexpensive and easy to handle, steam is a potential candidate carrier gas for
waste plastic recycling in chemical plants. Furthermore, as mentioned in Section 2.1, the
degradation temperatures for polyester resins are remarkably shifted to low-temperature
regions, and the amount of carbonaceous residue produced in the degradation process is
reduced in a steam atmosphere, as compared with that in a nitrogen atmosphere. Accord-
ingly, the preparation of a catalyst that could demonstrate both stable activity for the
catalytic cracking of PE-derived heavy oil, but that would also remain stable in a steam
atmosphere, was examined [16].
Nickel is a well-known catalyst component and is thought to play an important role
in the transformation of the hydrogen of steam to hydrocarbons. Hence, a part of the
rare earth metal in REY is exchanged with Ni to become prepared Ni and the rare earth
metal-exchanged Y-type zeolite catalyst (Ni–REY) [14, 15]. The physical and chemical
properties of the catalysts are listed in Table 6.8. The polyethylene plastics-derived heavy
oil shown in Table 6.2 was used as the feed oil.
A continuous-flow, fixed-bed reactor was utilized for the catalytic cracking of the heavy
oil. Reactions were conducted under temperature conditions ranging from 300 to 600◦ C,
at a catalyst weight W of about 1.0 × 10−3 kg and a feed oil mass flow rate F of about
1.0 × 10−3 kg h−1 . In order to examine the catalysis of Ni in Ni–REY for hydrogenation,
experiments using hydrogen as the carrier gas were also conducted.
Table 6.8 Physical and chemical properties of the catalyst samples. (Reproduced with permission
from Elsevier)
Ni–REY
REY Ni content 1.0 wt% 3.0 wt% HY MFI
0.5 wt%
SiO2 /Al2 O3 4.8 4.8 4.8 4.8 4.8 65
Crystal size (mm) 0.1 0.1 0.1 0.1 0.1 1.1
Number of strong acid sites (mol kg−1 ) 0.375 0.441 0.122
The selectivity of the products of the reaction in nitrogen and hydrogen stream at 400◦ C
was compared among the catalysts used at a feed oil conversion of about 80%. Hydrocar-
bons with carbon numbers ranging from 1 to 4 were regarded as gaseous compounds, and
those with carbon numbers from 5 to 11 were regarded as gasoline fractions. MFI-type
zeolite (ZSM-5) yielded the largest quantity of gaseous compounds (selectivity: 64%) and
the lowest amount of gasoline (35%) because its pores are too small for the penetration
of heavy oil, and reactions such as dewaxing are likely to proceed inside. As HY-type
zeolite had a large umber of strong acid sites, and excessive cracking occurred, a low
yield of gasoline was obtained (46%). The usage of REY, on which the number of strong
acid sites is lower than that on the HY-type zeolite, gave a higher yield of gasoline (57%)
as compared with that of HY. On the other hand, when the reaction was conducted using
the Ni–REY catalyst in hydrogen stream, the selectivity towards gasoline was found to
be the highest at 64%, at the same temperature and conversion of the feed oil.
The reactions over HY, MFI, and REY zeolite catalysts in nitrogen proceed over their
acid sites. During the reactions, paraffins are first decomposed to yield lighter olefins
and paraffins. The produced olefins are preferentially adsorbed on acid sites and undergo
further reaction, yielding gaseous compounds and aromatics. When a Ni–REY catalyst is
employed in a hydrogen atmosphere, the decomposition of hydrogen to hydrogen atoms
also proceeds over Ni in the catalyst. These hydrogen atoms diffuse on the pore surface
(e.g. the spillover phenomenon) and when they make contact with the olefins adsorbed on
the acid sites, the hydrogenation of the olefins occurs. The paraffins formed in this manner
easily desorb from the acid sites without undergoing any further reactions. Therefore, the
reactions using Ni–REY in this series showed the highest selectivity towards gasoline.
In order to optimize the Ni content of Ni–REY, the compositions of the obtained
gasoline fraction were measured and were divided into lumps as shown in Figure 6.19.
Figure 6.20 shows the RON value calculated from the data in Fig. 6.19 using
Equation (6.1). The results obtained with commercial regular-grade and high-RON-grade
gasoline are also shown in these figures for comparison. Commercial gasoline with
a high RON value contains large amounts of isoparaffins (IP1), aromatics (AR), and
cycloparaffins (CP), as well as a small amount of n-paraffins (NP2). For the complete
combustion of gasoline, the AR content must be low. Therefore, high-quality gasoline
must contain large amounts of IP1 and CP and small amounts of NP2 and AR. Using
Ni–REY with a 0.5 wt% Ni content, gasoline with larger amounts of CP and IP1 and
smaller amounts of AR and NP2 was obtained, as compared with a commercial high-RON-
grade gasoline. Furthermore, the RON value of the gasoline produced over Ni–REY (0.5
wt%) was larger than that of commercial gasoline. As the content of Ni increased, the
number of strong acid sites decreased, resulting in a reduction in cracking. This explains
why the amount of IP1 decreased and that of NP2 increased with the increase in the Ni
content (from 0.5 to 3.0 wt%), leading to the reduction of the RON value of the gasoline
produced in this manner. Based on the above information, it was concluded that Ni–REY
with a Ni content of 0.5 wt% could be used for the following experiments.
The effects of reaction temperature on the conversion of the heavy oil and the gaso-
line yield are shown in Figure 6.21 for reactions using Ni–REY in steam and hydro-
gen streams. At temperatures below 400◦ C, both the conversion and the gasoline yield
increased as temperature increased. However, at temperatures above 400◦ C, excessive
100
Cycloparaffin Aromatics (AR)

(CP)
80
n-paraffin (NP)
Composition/ wt%
60
40
iso-paraffin
20 (IP2)
iso-paraffin (IP1)
0
HY MFI REY 0.5 1.0 3.0 Regular High RON
(Ni content / wt%) grade grade
in N2 Ni – REY in H2 Commercial
gasoline
Figure 6.19 Comparison of gasoline fractions produced by catalytic cracking over

the various catalysts used (T = 400◦ C, W /F = 1 h). (Reproduced by permission from
Elsevier)
120
High RON grade
110 gasoline
RON value / -
100
90
Regular
80
grade
gasoline
70
HY MFI REY 0.5 1.0 3.0
(=Ni content / %)
in N2
Ni – REY in H2
Figure 6.20 Research octane umber (RON value) of the gasoline fraction produced with
the catalysts used. (Reproduced by permission from Elsevier)
cracking proceeded, followed by coke formation, leading to a decrease in both conver-

sion and gasoline yield. This tendency was clearly observed in the case of hydrogen
stream. Strong acid sites, on which coke formation proceeds and is accelerated at higher
temperatures, are partially covered by water molecules in a steam atmosphere. Therefore,
the catalyst is able to maintain activity above 400◦ C in a steam atmosphere.
100 100
80 80
Yield of gasoline fraction/%

Conversion of feed oil / %
In steam
60 60
In H2
40 40
In steam
In H2
20 20
Catalyst : Ni–REY
0 0
200 300 400 500 600 700
Reaction temperature/ºC
Figure 6.21 Dependence of both conversion and gasoline yield on reaction temperature
(W /F = 1 h)
Figure 6.22 shows the typical carbon number distribution of products obtained using
Ni–REY in steam at 400◦ C and with a time factor W /F of 1 h. The results obtained with
MFI-type (ZSM-5) and REY zeolites in N2 are also shown for comparison. Although
steam was used as a carrier gas, Ni–REY gave the largest amount of fuel, e.g. gasoline,
kerosene, and gas oil, thus suggesting the potential use of steam as a carrier gas.
30
Gas Gasoline Reaction conditions:
Kerosene T = 400 °C
W/F = 1 h
Gas oil
20
MFI in N2
Yield/%
REY in N2
Feed oil
Ni-REY in steam
10
0
5 10 15 20 25
Carbon number/-
Figure 6.22 Carbon number distribution of products of the catalytic cracking of oil
obtained by the pyrolysis of PE. (Reproduced with permission from Elsevier)
From the results discussed above, the combination of Ni–REY as the catalyst and
steam as the carrier gas was considered preferable for achieving a realistic recycling
process. In order to confirm the long-term stability of Ni–REY, repeated sequences of
reaction and regeneration were conducted. Reaction and regeneration were conducted at
400◦ C for 3 h in a steam atmosphere, and at 500◦ C for 3 h in an air stream, respectively.
This experiment was also conducted using an MFI-type zeolite catalyst for comparison
by exchanging the carrier gas in the reaction from steam to nitrogen. Figure 6.23 shows
changes in the conversion of the feed oil and the selectivity towards gasoline for REY
and Ni–REY catalysts during the sequences of reaction and regeneration. The carrier
gas in the reaction was steam for the REY and Ni–REY catalysts. Both the activity
and the selectivity remained almost constant for REY and Ni–REY, indicating that both
catalysts are stable in a steam atmosphere. The stable activity observed with REY and
Ni–REY could be ascribed to the stability of the acid sites on the REY and Ni–REY
catalysts [37]. Furthermore, Ni–REY showed higher selectivity towards gasoline (78%).
A small amount of hydrogen was detected in the exit gas of the reactor. This finding
suggested that Ni plays an important role in the hydrogen transportation from steam to
hydrocarbons, resulting in a high selectivity towards gasoline. The above findings thus
confirmed that PE-derived heavy oil can be efficiently upgraded to useful fuels when it
is reacted over Ni–REY in a steam atmosphere.
In order to verify the high efficiency of Ni–REY in an actual system, the catalytic
cracking of the oil derived from a mixture of PE and PET was conducted in a bench-
scale reactor (see Figure 6.8). The Ni–REY catalyst was placed in reactor 3, shown in
Figure 6.7. Figure 6.24 represents the carbon number distribution of the feed oil and the
product of the reaction over Ni–REY in a steam atmosphere. The fraction of aliphatic
heavy oil was completely converted to gasoline and kerosene, indicating that the Ni–REY
catalyst can be used for the upgrading of oil derived from a mixture of PE and PET. The
100
MFI
Selectivity towards gasoline/%
Conversion of heavy oil/%
80
100
Ni-REY REY
60
Ni-REY 80
40
REY 60
20 MFI
40
0
0 1 2 3 4 5
Number of sequences of reaction
and regeneration/-
Figure 6.23 Changes in the catalytic activity of the MFI-type zeolite, Ni–REY, and REY
catalysts during the repetition of a sequence of reaction and regeneration (T = 400◦ C,
W /F = 1 h), carrier gas in the reaction: nitrogen for MFI, steam for REY and Ni–REY.
50
Catalyst : Ni-REY
100% Steam atmosphere
40 T = 400 ºC, W/F = 1.0 h
Gasoline
Yield/wt% 30
Kerosene Feed oil
20 Aromatics
Paraffins + Olefins
10
0
5 10 15 20+
Carbon number/-
Figure 6.24 Carbon number distribution of products obtained by the catalytic cracking
of oil derived from a mixture of PE and PET (reaction conditions: T = 400◦ C, W /F = 1 h).
products with carbon numbers from C5 to C11 (i.e. the gasoline fraction) contained about
30% aromatics, almost the same result observed in the case of the products obtained from
the reaction over Ni–REY in H2 (see Figure 6.19). This finding suggests that cracking,
followed by hydrogenation, proceeds in a steam atmosphere due to the existence of Ni in
the catalyst.
4 CONTINUOUS PRODUCTION OF FUELS FROM WASTE PLASTICS
4.1 CONTINUOUS PRODUCTION OF FUELS
First, by decomposing waste plastics in a steam stream, it was shown that waste plastics
could be degraded without producing a carbonaceous residue. Furthermore, it was found
that the decomposition of oxygen-containing plastics can proceed at a uniform reaction
rate. Second, a new reactor was proposed to achieve high hold-up, high heat transfer, and
good contact between melted plastics with steam in order to accelerate hydrolysis. Using
this reactor, a mixture of waste plastics can be degraded, and further decomposition over
an FeOOH catalyst can also be achieved. Finally, the oil obtained was upgraded to a
variety of fuels, indicating gasoline and kerosene, over a Ni–REY catalyst in a steam
atmosphere. On the basis of these laboratory-scale experimental results, a pilot-scale plant
was built and the validity of the proposed chemical recycling process was examined.
Figure 6.25(a) shows a novel process for the continuous production of fuels from waste
plastics. The proposed process consists primarily of three reactors. A mixture of waste
plastics is fed into a pyrolytic reactor with heat-medium-particles stirred by a helical
impeller (Figure 6.25(b)), where melted plastics are hydrothermally decomposed with
steam and the random scission of C–C bonds. The produced mixture of a heavy oil
containing wax and sublimate material is carried by steam stream to the next reactor,
which is filled with an FeOOH catalyst (i.e. a catalytic hydrolysis reactor). The gaseous
compounds, including the vapors of the wax and sublimate materials, are passed through
an FeOOH catalyst bed, and the oxidative decomposition over the FeOOH catalyst with
steam proceeds. The quality of the oil thus obtained is further upgraded over Ni–REY
zeolite catalysts in the catalytic cracking reactor, and fuels, such as gasoline, kerosene,
and gas oil are produced. The weights of the FeOOH catalyst and the Ni–REY zeolite
catalyst were 45 and 20 kg, respectively. The feed rate of the waste plastics, F , was
45 kg/h (the time factor in the pyrolytic reactor, W/F = 1.0 h).
Cooling water
400°C
Catalytic hydrolysis Catalytic cracking
reactor reactor
(FeOOH catalyst) (zeolite catalyst)
500 ºC
Waste plastics Cooling
Products water
+ steam 200 °C Cooling water
Superheater
Pyrolytic
reactor
Wax
Superheated
steam Gas to Incinerator
Oil
Boiler
Residue
Water
Water
Plastics, steam
Ceramic balls
Impeller of
spiral in shape
Gaseous products
Figure 6.25 (a) Flow scheme of the continuous production of fuels from waste plastics;
(b) schematic diagram of the pyrolytic reactor used in the pilot plant. (Reproduced with
Table 6.9 Product yield at the outlet of the catalytic hydrolysis reactor and the catalytic cracking
reactor in the pilot-scale plant
Gas (C1 –C4 ) Fuel (C5 –C19 ) Heavy oil (C20+ ) Others
(wt%) (wt%) (wt%) (wt%)
Outlet of reactor with FeOOH 2.1 46.7 50.3 0.9
Outlet of reactor with zeolite 13.5 52.4 33.9 0.2
The product yields at the outlet of the catalytic hydrolysis reactor and at the catalytic
cracking reactor are listed in Table 6.9. The product yields of liquid fuel (gasoline-
kerosene) and heavy oil reached to 46.7 and 50.3 wt%, respectively, even at the outlet of
the catalytic hydrolysis reactor. The catalytic cracking reactor yielded 13.5 wt% gaseous
fuel, 52.4 wt% liquid fuels, and 33.9 wt% heavy oil, indicating that the heavy oil obtained
at the outlet of the catalytic hydrolysis reactor efficiently upgraded the quality of the fuel
oil. Using this method, the storage of carbonaceous residue and sublimate materials in
reactors, valves, and pipelines can be avoided. Moreover, recycling heavy oil at the outlet
of the catalytic cracking reactor into the pyrolytic reactor can enable an improvement in
the yield of liquid fuel to 72.4 wt%. Accordingly, the validity of the proposed process for
the continuous conversion of waste plastic mixtures to various fuels was demonstrated on
the basis of this pilot-scale plant.
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7
Catalytic Degradation of Plastic

Waste to Fuel over Microporous
Materials
GEORGE MANOS
Department of Chemical Engineering, University College London, Tornington Place,
London WC1E 7JE, UK
1 INTRODUCTION
The dramatic growth of living standards in the second half of the twentieth century was
accompanied by a drastic increase in plastic product use. This unavoidably had a huge
impact on the environment, as it caused a rapid increase in plastic waste that does not
degrade and remains in municipal refuse tips for decades. Consequently plastic waste
is a large strain on existing disposal methods, landfill and incineration. Landfill space
is becoming scarce and expensive, a problem exacerbated by the fact that plastic waste
is more voluminous than other waste type. On the other hand, incineration to recover
energy, produces toxic gaseous products, which only shifts a solid waste problem to an
air pollution one. Polymer recycling becomes an increasingly better alternative to those
methods. Polymer recycling has become a necessity.
Apart from providing a solution to a disposal problem, we can look at polymer recycling
as turning waste into valuable products, namely chemicals and fuel. We should consider
plastic waste as a cheap source of raw materials in times of accelerated depletion of
natural resources.
Ideally we would like to reuse plastic waste to form directly new plastic products, but
mechanical reprocessing of used plastics into new products has so far limited application.
It is restricted to the treatment of relatively pure and well-defined waste, mainly from poly-
mer processing factories. Mechanical reprocessing of municipal plastic waste results in
new products of quality inferior to their virgin plastic ones. Separation of waste to streams
of the same polymer type on the other hand is still very expensive. This fact restricts the
applicability of mechanical reprocessing in polymer waste that is homogeneous in type
and properties.
194 G. MANOS
Thermal and/or catalytic degradation of plastic waste to gas and liquid products, which
can be utilized as fuels or chemicals, seem to be the most promising methods to be
developed into a cost-effective commercial polymer recycling process to solve the acute
environmental problem of plastic waste disposal. These methods solve an environmental
problem, producing valuable products. Comparing pure thermal degradation in the absence
of a catalyst with a catalytic one, the first one demands relatively high temperatures and its
products require further processing for their quality to be upgraded. Hence this recycling
method is restricted to areas of existing oil refineries to whose processes the wax-type
products of the thermal degradation need to be fed for their quality to improve. Catalytic
degradation of plastic waste offers considerable advantages. It occurs at considerably lower
temperatures and forms hydrocarbons in the motor fuel range, eliminating the necessity
of further processing.
In such a recycling process, we consider the liquid fuel as the most valuable product.
Although gaseous products are useful too, as their burning can contribute to the energy
demand of an endothermic polymer cracking process, excess gas production is not desir-
able. Gaseous products are considered of low value because of their transportation costs.
Consequently, the target of a commercially viable recycling process should be an increase
of the liquid product yield.
Generally the whole polymer recycling policy has to consider the problem in a holistic
way. A combination of recycling methods has to be considered and polymer recycling
has to be viewed in conjunction with recycling of other waste type. Issues such as sorting
of waste into various waste types as well as separation issues have still to be tested.
In this chapter an overview of the characteristics of plastic catalytic degradation is
presented, focusing mainly on our own work. We will focus on polyolefins that constitute
by far the majority of municipal plastic waste [1]. Polystyrene is another polymer type
with considerable percentages in the municipal polymer waste stream and we will refer to
results of other studies trying to identify main differences from polyolefins. PVC causes
problems in recycling technologies based on degradation because of the HCl formed,
which has to be removed. In catalytic degradation formed HCl affects negatively the
catalyst stability. However we do not consider as priority to study the catalytic degradation
of PVC as it is more and more removed from food packaging and its fraction in municipal
plastic waste is decreasing steadily. PVC is now mainly used in construction, such as
PVC window frames. The life of PVC construction products is considerably higher than
packaging material, reducing the acuteness of the waste problem. On the other side PVC
products are replaced by specialized technical personnel who can ensure that PVC waste
is collected separately and is not mixed with other plastic-type waste. That gives the
opportunity for more efficient PVC-specific recycling technology to be developed.
2 OPERATION MODES
In the following a brief selective overview, rather a personal account, is presented, in order
to highlight variations in polymer catalytic pyrolysis scheme regarding modes of opera-
tions and reactor types. Prompted by the oil crises of the mid 1970s and early 1980s, the
first research projects trying to convert plastic waste to fuel go back to the second half of
the 1980s [2,3]. It was logical to extend earlier work on thermal noncatalytic conversion of
MICROPOROUS MATERIALS 195
plastic waste [4], as its products needed further upgrading in order to be utilized. The first
attempts were carried out almost exclusively in autoclaves which were opened after the
reaction was carried out and the liquid and gaseous components formed were collected and
analysed. The first catalyst systems used in those works were well-established industrial
acidic catalysts such as silica–alumina and zeolites, mainly Y-type. In the 1990s numer-
ous studies have been carried out using as catalysts silica–alumina [5–7], zeolites [6–11],
zeolite-based commercial cracking catalysts [12–14], MCM mesoporous materials [15] or
clays and pillared clays [16, 17]
Besides the direct catalytic conversion of plastic, the subsequent in situ catalytic con-
version of products of noncatalytic thermal degradation was also researched [18, 19].
These studies have confirmed the superior quality of the hydrocarbon mixtures produced
and highlighted the potential of catalytic degradation. The majority of the studies have
been carried out in batch/semi-batch systems where polymer and catalyst particles have
been both introduced into the reactor together, followed by heating up and reaction, mak-
ing this reactor operation batch wise regarding raw material and catalyst. In semi-batch
systems there is continuous flow of a carrier gas that removes formed products out of
the reactor, minimizing their further reaction. Besides batch reactor studies, a specially
designed continuous screw kiln reactor was also used for the direct catalytic conversion
of polymers [20–21] reducing overcracking compared to batch systems.
Although the more advanced version of a thermal noncatalytic process, developed
by Kaminsky’s group to pilot plant scale, is the Hamburg process [22–24] that uses
a sand fluidized-bed reactor, there are no studies involving a continuous fluidized-bed
catalytic degradation reactor, apart from tests carried out by the same group [25]. When
they replaced sand with a commercial cracking catalyst, the product spectrum shifted
drastically from waxes to gases and low-boiling aliphatic oils.
The few other catalytic studies involving a fluidized bed [10, 11, 26] operated in a
batch mode, confirming a superior heat transfer efficiency. In respect to fluidized beds
one issue that has to be researched further and solved is defluidization.
Furthermore, a study of the behaviour of a fluidized-bed reactor is very important as
one of the options for a possible commercialization of such a pyrolysis recycle process
is to co-feed plastic waste into the FCC cracker unit of an oil refinery. Studies of plastic
being a fraction of the feed of a cracking process have been carried out by Ng et al. [7]
and Arandes et al. [12, 27, 28]. They not only showed the applicability of the method,
but discovered a synergetic effect on the cracking of the oil decreasing the amount of
aromatics.
3 ZEOLITES
The decomposition of a polymer chain, being a hydrocarbon cracking reaction, is catal-

ysed by acidic catalysts. The main category of solid cracking catalysts, as well as the
more widely used in industry, are zeolites, as they constitute the main ingredient of cata-
lysts used in the FCC process in refineries. Zeolites are crystalline aluminosilicates with
a well-defined microporous structure with cages and channels of dimensions comparable
to the size of common simple organic molecules. Zeolites have SiO4 and AlO4 tetrahe-
dra as the primary structure units that link together through shared oxygen atoms in a
196 G. MANOS
three-dimensional structure. The AlO4 tetrahedra carry a negative charge that is counter-
balanced by cations inside the zeolite pore structure, usually Na+ , K+ or Ca++ . When
these cations are exchanged by protons, zeolitic acid sites are formed. Zeolite acidity can
be either of Brönsted type, proton donors, or Lewis type, electron pair acceptors. Each
acidity type leads to different reaction mechanisms, as hydrocarbon reactions are catal-
ysed by proton addition over Brönsted sites rather than by hydride abstraction over Lewis
sites. Another important characteristic of acidity is its strength that is usually measured
by temperature-programmed desorption (TPD) of base components, usually NH3 . The
catalyst sample is saturated with the base molecule first, with the physisorbed amount
removed afterwards, and then the sample temperature increases, usually with a linear
temperature programme. During the temperature programme stage the desorbed amount
is monitored using a detector, such as a TCD (thermal conductivity detector). Obviously,
the stronger the acid sites the higher is the temperature needed for the desorption of the
base molecules from these sites. Stronger acid sites favour cracking reactions.
There is a plethora of natural or synthetic zeolite structures, each one existing in a wide
range of relative compositions of Si or Al atoms, characterized by the Si/Al ratio [29]. Two
examples of widely used zeolites types are ZSM-5 and Y-zeolite. The first structure con-
sists of two sets of channels connected to each other; straight channels of 0.54 × 0.56 nm
size and zig-zag 0.51 × 0.55 nm size. Y-zeolite consists of cages of 1.18 nm connected
through 0.74 nm windows, placed in a tetrahedral arrangement, into a three-dimensional
pore structure [29, 30]. The Si/Al ratio ranges between around 10 to infinite (pure siliceous
structure named silicalite) for ZSM-5 and 1.5–3 for Y-zeolite. Ultrastable Y-zeolite
(US-Y), the active ingredient of FCC catalysts, is a special case of Y-zeolite formed
through the following process in order for the stability of the zeolitic structure to enhance.
Under the harsh high-temperature conditions of an FCC regenerator the steam present
extracts Al from the highly aluminous zeolite framework, forming holes and causing
collapse of the structure. In order to avoid this, Y-zeolite undergoes a dealumination
treatment in a similar, but controlled environment. Steam flows through a zeolite bed at
high temperature in a controlled manner. During this treatment Al is extracted from the
zeolite framework, the Si-O-Al network, but it remains inside the zeolite pore structure as
extra framework Al (EFAL) in the form of cations, e.g. Al(OH)2 + , AlO+ . It is believed
that the interaction of EFAL with the acid sites increases their strength [29]. Through
dealumination the framework Si/Al ratio decreases, while the bulk stays the same as that
of the original Y-zeolite. Dealumination of Y-zeolite to form US-Y can take place through
other processes, for example through reaction with reagents such as SiCl4 .
Chemical reactions carried over zeolites show shape selectivity, since they are able to
discriminate between reactants, products and/or transition states compared to the size of
their channels [29].
4 POLYMER-TO-CATALYST RATIO
An important aspect in a future catalytic process for degradation of plastic waste is the
amount of catalyst used in such a process. In a batch system, which is the most broadly
used so far to test the performance of various catalytic systems, the amount of catalyst
is characterized by the polymer-to catalyst mass ratio. Results from initial experiments
carried out on a TGA equipment Figure 7.1 [9] using high-density polyethylene (HDPE)
as raw material at different polymer to catalyst mass ratios showed the existence of a
limit below which the addition of more catalyst does not change the degradation pattern.
In the absence of catalyst, the polymer (HDPE) degradation pattern showed a very steep
decrease at about 773 K. The degradation set up very late at quite high temperature,
but it progressed very rapidly after initiation. In the presence of catalyst, the polymer
degradation occurred at much lower temperatures and more gradually. Even with the
smallest catalyst amount (polymer: catalyst = 9 : 1) the degradation commenced at much
lower temperature than in the absence of catalyst. As more catalyst was added the reaction
proceeded at enhanced rates. At polymer-to-catalyst mass ratios 1:2, 1:1 and 2:1 the
polymer degradation curves were very similar.
These results have been confirmed by estimating the activation energies at various
ratios by a series of experiments with different heating rates [31]. The activation energy
of pure thermal degradation of HDPE in the absence of catalyst was considerably higher
(61 kcal/mol) than even the one with only 10% of zeolite USY (HDPE: US-Y = 9:1),
47 kcal/mol. However at HDPE:US-Y ratios 2:1, 1:1, 1:2 the difference of the activation
energy was minimal, 25, 24 and 22 kcal/mol respectively.
All the above results indicated the possible existence of a limiting step over the whole
reaction process. It is reasonable to assume that large macromolecules had to react on
the external surface of the zeolite catalyst first, which could be the limiting reaction step.
140
120
m(pol + zeol. water)/m0(pol)(%)
100 6
1 2
80 3
4
60
1. HDPE:US-Y 1:2 5
40 2. HDPE:US-Y 1:1
3. HDPE:US-Y 2:1
4. HDPE:US-Y 4:1
20 5. HDPE:US-Y 8:1
6. Only HDPE
0
300 400 500 600 700 800
T[K]
Figure 7.1 TGA graphs of HDPE at various polymer-to-US-Y zeolite ratios. Heating
rate, 5 K/min; nitrogen flow, 50 mLN /min. (From [8]. Reproduced by permission of the
American Chemical Society)
198 G. MANOS
Smaller cracked fragments diffused subsequently into the zeolite pores and underwent
further reactions. It seemed that the addition of more zeolite above a specific quantity,
corresponding to a polymer-to-catalyst ratio between 1:1 and 2:1, did not increase the
overall degradation rate.
The melted polymer resided in the voids of the zeolitic bed. When the amount of
polymer was high (high polymer-to-catalyst ratio), polymer filled these voids fully with
the excessive polymer mass not being in contact with zeolite. The more zeolite was
added, the more polymer was in contact with it and more polymer participated in the
initial degradation step. This was true to a point when the added zeolite was no longer in
contact with plastic. In the last case the excessive zeolite did not contribute to the initial
degradation step of the large macromolecules.
TGA experiments however do not reveal the whole picture. They show only the overall
change of the polymer mass without any indication of product distribution. Therefore
further experiments were carried out with linear low-density polyethylene (LLDPE), this
time using a laboratory semi-batch reactor with quantities at gram levels rather than
milligrams. In these experiments various liquid fractions were collected at different stages.
Surprisingly, no difference in the liquid yield, neither conversion nor liquid selectivity,
was observed in an even wider range of USY-to-polymer ratio (Figure 7.2).
However this figure shows only part of the truth. If the results are plotted for all three
stages of the temperature programme used (Figure 7.3), the systems with the most zeolite
(US-Y), i.e. zeolite-to-polymer ratio of 1:1 and 1:2, form more liquid (indicative here of
higher conversion) than the other two systems at the first stage, i.e. lower temperature
(T = 573 K).
However this is compensated by the temperature increase. At the second stage (T =
633 K) the two systems with the lowest zeolite amounts, i.e. zeolite-to-polymer ratio of
1:3 and 1:4, form the highest liquid fraction amount. At the third stage (T = 673 K) the
degradation had been already completed for all systems. Minimal liquid amounts were
formed.
In order to confirm these results, a linear heating programme has been applied where
the relatively mild final temperature was reached only at the end of the experiment, not
leaving further time at the top temperature to react. The presence of more catalyst has
indeed formed more liquid products (Figure 7.4), confirming the above findings.
100
80
60
[%]
40
20 Conversion Selectivity
0
0 2 4
Polymer to catalyst ratio
Figure 7.2 Conversion and liquid selectivity during degradation of LLDPE over US-Y
zeolite at different ratios and a step temperature programme (0–5 min:573 K, 5–10 min:
633 K, 10–15 min:673 K)
100
Pol:Cat = 1
Fraction of total liquid [%]

80 Pol:Cat = 2
Pol:Cat = 3
60
Pol:Cat = 4
40
20
0
0 – 5 min (573 K) 5 – 10min (633 K) 10 – 15min (673 K)
Figure 7.3 Liquid formation during degradation of LLDPE over US-Y zeolite at different
ratios
100
80
60
[%]
40
20 Conversion Selectivity
0
0 2 4
Polymer to catalyst ratio
Figure 7.4 Conversion and liquid selectivity during degradation of LLDPE over US-Y
zeolite at different ratios and a linear temperature programme (16 K/min to 633 K)
5 INITIAL DEGRADATION MECHANISM

TGA is an excellent technique for a fast evaluation of the polymer degradation. However it
does not reveal anything about solid state reactions taking place during degradation. TGA
experiments showed that in the absence of catalyst, HDPE was decomposed very rapidly
at around 773 K, without any weight loss at lower temperatures, indicating that no volatile
products were formed until then. TGA experiments were not conclusive on the existence
of any solid state reaction that would have changed the polymer structure, as they would
not necessarily lead to mass change and would be undetectable by the TGA equipment.
This question of solid state reactions is an important one, as homogeneous solid state
reactions could be the initial step in the heterogeneously catalysed process. To clarify
the mechanism of the first degradation step, homogeneous or heterogeneous, a series of
experiments were carried out at relatively mild temperatures in the semi-batch reactor.
Each polymer sample was recovered at the end of these experiments and its molar mass
distribution has been determined by gel permeation chromatography (Figure 7.5) [9].
Curve number 1 shows the molar mass distribution of the original hdPE sample. Curves
number 2 and 3 show the molar mass distribution of samples heated in the absence of
catalyst over 4 h at 413–423 K (curve number 2) and 6 h at maximum temperature
200 G. MANOS
Molecular mass distribution

10.00
1. Original HDPE
2. Only HDPE 2 h 140 °C-2h 150 °C
3. Only HDPE 1K/min to 300 °C for 1 h
8.00 4. HDPE:US-Y 2:1
2h 105 °C-1/2 h 145 °C
5. HDPE:US-Y 2:1
1 K/min to 245 °C
total reaction time 3 h
Wn (log M) × 10−1
6.00
4.00
1
2
2.00
3
4
5
0.00
2.00 3.00 4.00 5.00 6.00 7.00
Log M
Figure 7.5 Molar mass distribution of fresh HDPE and heated HDPE in the absence
and presence of US-Y zeolite. (From [9]. Reproduced by permission of the American
Chemical Society)
573 K (curve number 3). The molar mass distribution curves of the samples exposed at
higher temperatures in the absence of catalyst were identical to the curve of the original
polymer sample.
This implied that the polymer structure has not been changed, indicating that no solid
state reactions took place. These experiments did not yield even trace amounts of volatile
products.
However all the samples heated in the presence of US-Y catalyst (polymer-to-catalyst
mass ratio 2:1) showed a deviation from the original polymer molar mass distribution
in the region of lower molar masses. In the first experiment, the polymer/US-Y-zeolite
sample was exposed at a temperature of 378 K, which is below its melting point, for
120 min and then for 30 min at 418 K. No volatile products were initially observed, but
traces of isobutane and isopentane were detected when the temperature was raised to
418 K. Although these conditions were much milder than in the equivalent experiment
with pure polymer (curve number 2), the molar mass distribution, curve number 5 in
Figure 7.5, was different from that of the original polymer.
In the second experiment the mixture of hdPE and US-Y was exposed at significantly
higher temperatures. From ambient temperature to 443 K with 5 K/min, then to 518 K
with 1 K/min. The experiment was stopped when the final temperature was reached and
the total experiment duration was 3 h. The sample of this experiment showed much
larger deviation in the molar mass distribution, although the conditions were again milder
than those at which the pure polymer was exposed (curve number 3). In this experiment
the first liquid drops of hydrocarbon products (∼5 mg) were collected when the reactor
temperature was 478 K.
These experiments concluded that no reaction occurred in the absence of catalyst.
The presence of catalyst was necessary to initiate solid state reactions that changed the
polymer structure, mainly by breaking of chains of low molar mass to smaller chains.
In the catalytic process the first gaseous products, even if only in traces, were formed
at about 413 K and the first liquid products slightly above 473 K. Differential thermal
analysis (DTA) runs had revealed that 413 K was the melting point of the polymer sample.
Current studies are focused on clarifying some further mechanistic aspects, namely the
question if indeed the initial decomposition step occurs on the external catalyst surface
or chain ends and/or branches intrude into the pore catalyst structure and decompose on
internal acidic sites. In order to investigate this aspect, we use selective poisoning of the
external catalytic sites using large molecules that do not enter the zeolite structure.
6 PRODUCT DISTRIBUTION
The original polymer mass in the presence of a catalyst is generally converted into volatile
products while a residue is left unconverted. This residue consists of a polymer solid
residue of genuinely unconverted plastic, although usually not of the same composition
and molar mass distribution as the original, and coke formed on the catalyst surface. From
these two residue components, the first one can be eliminated by changing the reaction
conditions; most obviously by increasing the polymer reaction temperature and time. The
second one, coke, can not be avoided. The raw polymer material, being of hydrocarbon
nature, undergoes coking reactions on acidic catalytic surfaces [29]. However, the coke
amount can be minimized depending upon process conditions and characteristics, most
importantly catalyst type.
The volatile (at reaction temperature) products can be grouped into liquids and gases,
depending upon the state they are at ambient conditions. However, for practical reasons
in all our experimental studies we used an ice bath (T = 273 K) to collect the liquid
products. This way we avoided possible condensation problems of the collected gases
as well as variations due to seasonal room temperature fluctuations. A diagrammatic
overview of the process mass balance is shown in Figure 7.6.
Gas
Polymer Liquid
Unreacted polymer
Coke
Catalyst Catalyst
Figure 7.6 Diagrammatic overview of the transformations during catalytic polymer

degradation
202 G. MANOS
In the following the characteristics of product distribution over various microporous
solid acidic catalysts are discussed. The catalysts tested were zeolites, commercial cracking
catalysts, clays and their pillared analogues.
Zeolites are widely used in acidic processes and they are an obvious catalyst choice.
The suitability of commercial cracking catalysts to degrade polymer waste is vital as one
of the options of commercializing this polymer recycling method is to co-feed polymer
waste to existing refinery crackers [13]. Furthermore, in the search for cheaper catalysts,
clays and their pillared analogues are also introduced in the polymer catalytic degrada-
tion [16, 17].
6.1 CONVERSION, LIQUID YIELD, COKE CONTENT
First, the behaviour of these catalysts on the overall conversion, liquid selectivity/yield
and coke formation is discussed. Overall conversion is the fraction of the original polymer
mass that is converted into volatile products, liquids and gases. Liquid selectivity is the
fraction of the volatile products that are in liquid form, while liquid yield is the fraction
of the original polymer mass that is converted into liquid. Coke yield is the fraction of
the original polymer mass that is converted to coke on the solid catalyst. As at most
conditions applied, no unreacted solid polymer remnants were left, the sum of coke
yield and conversion is equal to 1 (100%). Therefore overall conversion is not a good
measure of the activity of the catalyst. It rather reflects coking tendency over the specific
catalyst. Overall conversion levels over zeolites are lower than clay-based catalysts as
more coke is formed over zeolites due to their stronger acidity. The same trend is followed
by commercial FCC catalysts, where the lower amount of the active zeolitic ingredient
leads to lower density of acid sites. Compared with levels of coke yield above 10% on
USY, on commercial cracking catalysts coke yield is around 5% and well below that on
clays/pillared clays [13].
An exception is ZSM-5 which has a coke-forming resistance due to its shape selectivity
properties. The channels of ZSM-5 have a size comparable to that of many organic
molecules. This small pore size hinders the formation of bulky coke precursors and
coke molecules, decreasing the coke formation. Indeed, in polymer catalytic degradation
experiments less than 1% coke is formed over ZSM-5, most probably on the external
catalytic surface of the catalyst, compared with more than 10% over the large-pore and
strongly acidic US-Y. Another characteristic of zeolite catalysts regarding coke formation
and hence conversion is that over zeolites with cage and supercage structure, such as Y
and USY, more coke was formed than over channel structure zeolites of similar acidity,
such as β-zeolite, resulting in lower overall conversion [8].
Generally over clays and pillared clays higher liquid yield values are reached than
over zeolites [13, 16, 17]. Over US-Y zeolite values around 45% are achieved compared
with values around 70% over clay-based catalysts. The strong zeolitic acidity leads to
overcracking forming products that are collected mainly in the gaseous fraction. Over
clay based catalysts of weaker and/or lower acidity higher temperatures are needed for
the polymer degradation to occur, but much less overcracking takes place leading to
significantly higher liquid yields of above 70%.
6.2 CHARACTERIZATION OF GASEOUS/LIQUID PRODUCTS
The volatile products of catalytic degradation of polyolefins over zeolites, estimated using
gas chromatography coupled with a mass spectrometer (GC/MS), lie in the range C3 –C15
with distinctive patterns among various zeolitic structures [8]. Over large-pore zeolites,
ultrastable Y, Y and β-alkanes are the main products with less alkenes and aromatics and
only very small amounts of cycloalkanes and cycloalkenes. Over medium-pore zeolites,
ZSM-5 and mordenite, lighter hydrocarbons are formed and significantly more olefins
than over large-pore zeolites [8]. Both characteristics, length of the hydrocarbon chain
formed and chemical character of the hydrocarbons formed, seem to depend upon the
catalyst structure as well as strength/density of the catalytic acid sites. Over commercial
cracking catalysts containing only a fraction of US-Y zeolite as well as clays/pillared
clays with significantly weaker and less acid sites, significantly lower amounts of alkanes
are formed than alkenes [6, 13, 17]. Alkenes as the primary products of a cracking process
undergo secondary reactions the extent of which increases with the acidity. Furthermore
secondary reactions, being bimolecular, are sterically hindered in the constrained internal
structure of medium-pore zeolites [8].
For estimation of the relative amount of paraffins/olefins in order to avoid the laborious
GC/MS method we also used solution H NMR. GC/MS needs painstaking search as the
number of candidate molecules for a mass spectrum and their similarities increase steeply
with the molecule chain length. GC/MS provides of course a full picture of the chemical
identity of the components of a mixture. However, if specific information is looked for,
other specific methods can shorten the analysis time. In H NMR, olefinic hydrogen atoms
show separate distinctive peaks from paraffinic hydrogens. While over US-Y zeolite the
ratio of olefinic hydrogens to aliphatic (olefinic plus paraffinic) hydrogens is below 1.5%
over commercial cracking catalysts it is between 4.5 and 5.5% and over pillared clays
above 10% [13]. Due to the milder acidity of pillared clays, secondary reactions have
been limited with the result of a much higher presence of primary products alkenes in the
sample. Cracking catalysts produced intermediate figures. Due to the presence of US-Y,
secondary reactions occurred, but did not progress to the same degree as with pure US-Y.
It should be emphasized that the ratio of olefinic hydrogens to aliphatic hydrogens is much
lower than the actual molar ratio of alkenes to the sum of alkanes and alkenes, as only
hydrogens of the double bond contribute to the olefinic NMR peak, not all hydrogen atoms
of the alkene molecule, while the rest hydrogens do contribute to the paraffinic peak.
The chemical character of liquid products usually coincides with that of gaseous ones.
The gaseous products over clay catalysts are predominantly alkenes compared with alkanes
over US-Y [16, 17]. Similarly over ZSM-5 gaseous products are predominantly alkenes,
although more aromatics are formed too [8].
6.3 BOILING POINT DISTRIBUTION OF LIQUID FRACTION
Liquid hydrocarbons are considered to be the most valuable products of a potential recy-
cling process as they can be used as blends for motor engine fuels. In such a process
short-chain hydrocarbons in the gas phase are also produced and they are crucial to pro-
vide the heat needed for an endothermic reaction such as polymer cracking, but their
value is considered low due to their transportation cost.
204 G. MANOS
0.8
Commercial gasoline
0.7
US-Y
0.6
Cracking catalyst
w%/∆T [%/K]
0.5
Pillared clay
0.4
0.3
0.2
0.1
0
200 300 400 500 600 700
BP [K]
Figure 7.7 Boiling point distribution of liquid fuel formed over US-Y zeolite, a commer-
cial cracking catalyst, a pillared clay (polymer-to-catalyst ratio 2:1) and comparison with
a commercial gasoline sample
To characterize the quality of liquid fuel we use the boiling point distribution, which
we estimate chromatographically using a 100 m nonpolar column that separates the com-
ponents of a mixture according to their volatility/boiling point. Employing a calibration
mixture consisting of normal alkanes, boiling points are allocated to retention times under
the same chromatographic conditions as the ones used in the GC analysis.
Figure 7.7 compares the boiling point distribution of liquid products formed over US-
Y, a commercial cracking catalyst and a pillared clay. In the same figure is plotted the
boiling point distribution of a commercial gasoline sample.
The liquid hydrocarbon fraction formed over US-Y is similar to the commercial gasoline
sample regarding volatility. Commercial gasoline contains slightly higher amounts of
volatiles, around the boiling point range of heptane/octane. A considerable shift towards
heavier components is obvious from US-Y to cracking catalyst and even more to clay-
based catalysts. Stronger catalyst acidity enhances the extent of cracking reactions, leading
to more volatile, shorter-chain hydrocarbons. Clays and generally not strongly acidic
catalysts enhance the yield to liquid hydrocarbons. However this is accompanied by
shifting the fuel quality towards diesel rather than gasoline.
7 CONCLUDING REMARKS
The presence of acidic microporous catalysts speeds up the rate of polymer degradation,
leading to lower reaction temperatures and shorter reaction times. The energy demands
of a potential catalytic degradation process should therefore be much less than these of
a pure thermal process. Furthermore the quality of the products of catalytic degradation
are in the range of motor engine fuels, eliminating the necessity of any further upgrade.
More specifically, over microporous catalysts such as zeolites, cracking catalysts and
clays, the lower the catalyst acidity:
• the more liquid fuel is formed, and
• the more the liquid fraction distribution is shifted towards heavier hydrocarbons.
Both effects are due to the lower extent that cracking reactions take place. Over strongly
acidic catalysts overcracking leads to the formation of smaller molecules, increasing the
volatility of the liquid fraction, but also increasing the amount collected in the gaseous
fraction. Furthermore, stronger acidity leads to higher extent of secondary reactions and
the formation of more saturated products, namely paraffins rather than olefins, which
are the primary products of a hydrocarbon cracking process. Hence, mainly alkenes are
formed over clay based catalysts, while over commercial cracking catalysts the amount
of olefins is higher than their parent US-Y. On zeolites steric restriction of bimolecular
secondary reactions inside the structure of medium-pore zeolites, such as ZSM-5, leads
also to higher formation of primary cracking products, olefins.
On the way to an industrial polymer recycling process of catalytic pyrolysis of waste
plastics into fuel, a lot of research has still to be carried out. However, it is not too
early to think about the logistics of the whole operation. Although the polymer catalytic
degradation research is only in the beginning and no specific optimized reactor design has
emerged, it is important to have a holistic approach in the polymer recycling problem.
Catalytic pyrolysis is only one of a combination of recycling methods applicable. Eco-
nomic studies should assess the viability of each recycling method. Obviously the direct
recycle of plastic refuse in a plastic processing factory makes much more sense than
any other method. Only in cases where reprocessed goods do not comply with quality
specifications, other alternatives should be considered.
In particular, as far as the plastic catalytic degradation is concerned, there are various
possible scenarios. In large urban areas the best approach probably is to build a plastic
waste pyrolysis plant in an acceptable near area at not to great distance, in order to min-
imize transport cost of the plastic waste. In that case, safety and environmental concerns
of such a new plant should first be dealed with satisfactorily before the new plant can get
the go-ahead. Near refineries however, the best approach might be to co-feed plastic waste
with oil fractions into refinery crackers, or even have a unit of pure thermal pyrolysis first
with the produced wax-type fraction to be upstaged in another reactive refinery process.
In the first case of co-feeding, a lot of research has to be carried out, addressing aspects
of defluidization mainly, before an alteration of a process of the scale of FCC units can
go ahead.
In all scenarios one thing is clear already. The amount of fuel produced by a pyrolysis
process is not large enough to enable the producing company to compete in the fuel market.
Taking as basis a yearly polymer consumption of 100 kg/person [1] and assuming in the
most optimistic case (though unrealistic, as fuel density is lower than 1 kg/L) that 100 L
of motor engine fuel, gasoline or diesel, can be produced, it becomes obvious that this
amount is a small (rather tiny) fraction of the fuel consumed per person per year in the
developed world. There is no way that fuel produced from recycled polymer can dictate
terms in a very competitive market. However as mentioned in the introduction, in times
of depleted natural resources turning waste into useful products is too big an opportunity
to leave it purely on free market terms. The suggested solution is in the framework of
free market economies and has two aspects.
First, the fuel produced from recycled plastic waste needs to be exempted, at least
partially, from tax and second, agreements with fuel commercial companies need to be
reached in order for them to accept the produced fuel in their fuel pools, with the advantage
of lower tax for this fraction.
206 G. MANOS
We can not see any other way that such a process can become commercially viable.
In the end, the right degree of competition is reached only if ‘alternative competing
technologies’ are properly costed in a sustainable manner. Currently, the cost of landfill
disposal does not recover all costs to make this disposal method sustainable and in that
sense landfill disposal is heavily subsidized.
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8
Liquefaction of Municipal Waste

Plastics over Acidic and Nonacidic
Catalysts
JALE YANIK AND TAMER KARAYILDIRIM
Ege University Faculty of Science, Chemistry Department, 35100 Bornova/Izmir, Turkey
1 INTRODUCTION
Municipal waste plastics (MWP) are a significant part of municipal solid wastes which
are collected as household waste. Municipal plastic wastes usually account for about 8%
of the total municipal solid wastes (MSW) by weight and much more by volume [1].
Separation of the plastics from MSW is mainly by hand, either by the household prior
to collection or at a materials recycling facility. An average weight composition of the
separated plastic wastes is given in Table 8.1. According to an APME report, in 2003, the
amount of MWP was 13671 million tonnes in the European Union, which was 66.3% of
the total collectable plastic waste. Japan generates about 5280 million tonnes of MWP [2].
Although landfilling and incineration of solid wastes have been restricted by environmental
law since 1995, these operations are still in demand due to their ease and low cost. Thus,
large amounts of MWP are being treated by landfilling or incineration (without energy
recovery). Since mechanical recycling is the preferred recovery route for homogeneous
and relatively clean plastics waste streams, converting of MWP into liquid hydrocarbons
is being considered as a promising recycling method.
Research in producing liquid fuels and chemicals from waste plastics has been a focus
for about 20 years. Traditional thermal and catalytic–hydrocracking processes can be
applied to transform plastic wastes into liquid hydrocarbons. Thermal cracking, of plastic
waste has been investigated at the laboratory and pilot plant level, and technologies such
as the Polymer Cracking Process, BASF Conversion Process, Hamburg/ABB, Amoco,
etc. for liquefaction processing of plastic waste have been developed in Europe, Japan
and the US. However, the products of thermal cracking are distributed over a wide range
of carbon numbers and their commercial value is low. Because thermal cracking demands
210 J. YANIK
Table 8.1 Composition of MWP
A B
PE + PP + PS 81.3–86.7 79–90
PVC 4.3–9.4 3.8–1.2
PET 0.5–3.9 7.2–1.5
ABS, etc 2.1–3.6 2.0–1.3
Ash 3.7–6.8 4.0–1.9
A: collected from Nigaata city, Japan [2]

B: collected by the DSD system in Germany [3]
relatively high temperatures and its products require further processing to upgrade their
quality, catalytic cracking of plastic waste offers considerable advantages. It occurs at
considerably lower temperatures, and the composition and yield of the product can be
controlled by the catalyst.
2 CATALYTIC LIQUEFACTION OF MWP

There are different methods for carrying out the catalytic liquefaction of plastic wastes.
• catalytic cracking of plastic wastes by direct contact with the catalyst (liquid phase
contact);
• thermal cracking plus catalytic upgrading;
• hydrocracking;
• co-processing of plastic wastes in a refinery stream or with coal.
First of all, the dechlorination of waste plastics is necessary. This is because chlorine (e.g.
from PVC) in MWP causes contamination of all product streams with chlorinated organics,
as well as corrosion problems. Dechlorination of MWP can be carried out in a twin screw at
around 300◦ C, at which temperature other plastics do not start to degrade; HCl gas envolved
from degradation of PVC in MWP is recovered as a hydrochloric acid. Subsequently, the
dechlorinated MWP in the melted form is liquefied using the above methods.
2.1 LIQUID PHASE CONTACT
The catalyst makes contact with melted MWP. Good contact between plastic particles
and the catalyst is one of the key points for process development. Melted plastics can
be degraded in a fluidized-bed reactor or a fixed-bed reactor. Since the usage of fixed
beds leads to problems of blockage, scale-up to industrial size is not feasible. However
the fluidized bed has a number of special advantages for catalytic degradation of plastics,
because it is characterized by a good contact between catalyst and plastics as well as
an excellent heat and mass transfer [4]. In addition to selection of a suitable reactor, the
catalyst used is very important in the process.
Catalytic degradation involving liquid phase contact of common plastics, such as PE
and PP has already been tested extensively [5–10]. The most commonly used catalysts
LIQUEFACTION OF MUNICIPAL WASTE PLASTICS 211
in these studies were solid acids (amorphous silica–alumina, zeolites, zeolite-based FCC
catalysts, MCM mesoporous materials and super acidic zirconia, etc.). Besides acidic
catalysts, a few studies have been performed with activated carbon and nonacidic meso-
porous silica catalyst (FSM) [11–15]. Acidic cracking catalysts are very useful for direct
liquefaction of PE and PP. The catalytic effect of acidic catalysts in plastic pyrolysis has
been explained by a carbonium ion theory. The catalytic mechanism over acidic catalysts
has been reviewed by Bukens [16]. In brief, this mechanism involves: (1) an initiation
step, involving chain carbonium ion formation by proton addition; (2) a depropagation
step, chain cleavage yields an oligomer fraction by β-scission of chain-end carbonium
ions leading to gas formation on the one hand, and a liquid fraction on the other; (3) an
isomerization step, double bond isomerization of an olefin and isomerization of saturated
hydrocarbons; (4) an aromatization step; aromatic formation following cyclization via an
olefinic carbonium ion.
The problem relating to steric and/or internal diffusion hindrances in the cracking of
bulky polymeric molecules can be solved using catalysts of larger pores or zeolites with
smaller crystal size. Although suitable acidic catalysts can control the product range
in catalytic cracking of polymers, they are easily deactivated by nitrogen, sulfur and
impurities in MWP [17]. This type of catalysts can be regenerated by burning off the
coke, but this can result in a loss of activity [18].
On the other hand, activated carbon may be considered as a catalyst in the cracking
of waste plastics. This is because it is a neutral catalyst with a high surface area and,
therefore, it might be more resistant to impurities and coke formation. It has been reported
that Pt-, Fe- and Mo-supported activated carbon catalysts were effective for the pyrolysis
of PE and PP [11, 14, 15]. Use of metal-supported activated carbon catalysts has enhanced
the formation of aromatics via dehydrocyclization of straight- or branched-chain radicalic
intermediates.
Although a large variety of catalysts have been used, even if performing well, many
can be unrealistic for MWP. Thus, although the option based on cracking of plastic wastes
by direct contact with catalyst seems the simplest way, the catalyst cost can affect the
economics of the process considerably
2.2 THERMAL CRACKING PLUS CATALYTIC UPGRADING
The problems in catalytic cracking of MWP by direct contact with the catalyst can be
overcome by two-step processing. This method involves an initial thermal cracking of
waste plastics to produce low-quality hydrocarbons (vapors or liquid) that are treated
afterwards in a catalytic reactor to obtain high-quality liquid fuels.
A full-scale pyrolysis–catalytic process in which the catalytic cracking zone is directly
connected to the pyrolysis zone was developed in Japan (Fuji Process) [19]. In this
process, after separation of PVC and impurities by wet techniques, waste plastics are
thermally pretreated at 300◦ C for dechlorination and then introduced into the pyroly-
sis reactor and thermally cracked at 400◦ C. Subsequently, degradation products are fed
directly to the fixed-bed reactor using a ZSM-5 catalyst.
212 J. YANIK
Catalytic cracking yields the following products:
• oil, 80%;
• gas, 15%;
• residue, 5%.
Composition of the oil produced is:
• gasoline 60%;
• kerosene 20%;
• diesel 20%.
The main problem is the sensitivity of the zeolite catalyst towards impurities coming
from the waste.
The pyrolysis–catalytic cracking reactor scheme poses the serious engineering and
economic problems of a complicated reaction mechanism and high capital cost because
of the infrastructure needed. Another possibility is to separate the thermal cracking from
the catalytic cracking operation, in which first the waste plastics are cracked thermally
in a pyrolysis plant and the wax/oil produced is catalytically treated in a conventional
cracking or hydrocracking reactor to high yields of gasoline of improved octane rating.
A fluidized-bed pyrolysis reactor is the most suitable for thermal cracking of MWP to
obtain liquid/waxy product. Key features of the fluidized-bed pyrolysis include [3, 20]:
• conducting pyrolysis at lower temperatures, an aliphatic heavy oil and/or wax can be
obtained;
• by addition of lime into the reactor, HCl evolved from the PVC fraction in MWP is
captured. The dechlorination step is not needed for MWP containing up to 2% chlorine;
• Solid impurities in MWP either accumulate in the bed or leave the reactor with the
hot gas as fine particles which are collected in cyclones.
The liquid product obtained from thermal cracking can be either catalytically cracked/
hydrocracked or co-processed with a refinery feed. Since the catalytic cracking of oil
derived from MWP is more or less problematic, any cracking catalyst can be applied to
oil derived from pyrolysis of plastics. But the yield and the quality of gasoline obtained
from cracking step vary with the type of catalyst and the properties of the pyrolytic oil
derivated from waste plastics.
The amount of strong acid sites of the catalyst used influences the product distribution
from catalytic cracking in addition to the temperature. The reaction scheme below can be
considered for the catalytic cracking.
Wax/Heavy oil Gasoline Gas
Coke
The amount of gas product shows an increase with an increasing amount of strong
acid sites on the catalyst. Because gasoline is an intermediate product, its yield gradually
increases to a maximum value and then decreases with the increase in the amount of
strong acid sites [21].
As an example, the results from catalytic cracking of three types of waxes from thermal
cracking of PE are given in Table 8.2 [22]. The catalyst used, the equilibrium FCC catalyst,
Table 8.2 Properties of pyrolytic wax derived from PE
pyrolysis
Pyrolytic wax A B C
Fractions (vol%)
Gasoline (IBP-216◦ C) 18.0 20.2 28.2
LCO (216–343◦ C) 25 29.3 37.8
HCO (>343◦ C) 57 50.5 34
GC analysis, wt%
n-paraffins 76.8 38.6 36.2
α-olefins 18.1 34.5 42.8
Table 8.3 Some results from catalytic cracking of pyrolytic wax derived from PE pyrolysis
Feed Wax A Wax B Wax C

Temperature (◦ C) 470 510 470 470 470 470
Catalyst/oil (wt/wt) 0.43 3.99 0.47 4.15 0.48 4.20
WHSV (h−1 ) 333 20.0 300 19.3 298 19.0
Yields (wt%)
Dry gas 1.22 1.81 0.62 0.95 0.18 0.59
LPG 10.61 22.39 6.31 17.4 3.46 14.6
Gasoline 45.9 63.0 39.2 67.7 40.9 64.0
LCO 22.8 8.80 27.3 10.7 33.0 10.8
HCO 17.3 1.3 25.1 1.3 21.9 6.9
Coke 1.8 2.4 1.4 1.9 0.5 3.2
Conversion (%) 59.9 89.9 47.7 88.0 45.1 82.4
Composition of C4 –C11 in gasoline, wt%
n-paraffins 17.2 10.6 20.3 14.9 21.7 17.3
i-paraffins 12.6 31.2 12.2 47.7 10.2 46.1
Olefins 38.5 18.2 43.4 15.4 45.2 13.4
Naphthenes 14.4 15.6 12.8 11.3 14.3 12.0
Aromatics 17.3 24.5 11.3 10.6 8.6 11.2
KOB-627, is an octane-enhancing catalyst containing Y-type (US-Y) zeolite. Its matrix

(about 50 µm) cracks primarily the large and bulky molecules prior to their secondary
cracking in the small pores of the zeolite. The medium activity of this catalyst is reduced
over cracking of gasoline. This catalyst produced high yields of gasoline with improved
quality from pyrolytic waxy products, as shown in Table 8.3.
Similarly, it was observed that rare earth metal exchanged Y-type zeolite (REY) cata-
lyst, having a moderate amount of strong acid sites, has a selectivity towards gasoline in
the catalytic cracking of oils derived from plastics. HZSM-5, silica-alumina and Y-type
zeolite (REY) were tested for catalytic reforming of heavy oil derived from PE pyrolysis.
REY zeolite, which has a small crystal size and a low amount of strong acid sites, was
found to be the most suitable catalyst to obtain the highest research octane number (RON)
of 97.5 and a gasoline yield of 48 wt%. In contrast, HZSM-5 has the lowest RON value
(23) and gasoline yield (18 wt%) [21, 23].
It is however necessary to remember that products from cracking of heavy oils are
highly unsaturated and therefore they have to be further submitted to hydrofining.
214 J. YANIK
Upgrading of heavy oils derived from waste plastics by catalytic hydrocracking is also
one of the most promising processes for conversion of waste plastics. Dual-functional
catalysts, having both cracking and hydrogenation–dehydrogenation functions, are used
for this process. The cracking function is realized by an acidic support, while the hydro-
genation component is usually a metal, oxide, or sulfide of group VIII and/or VIb [17].
Commercial catalysts usually adapt Ni, Mo, W, Co and their combinations as the active
metal sulfide component, whereas silica–alumina and zeolites are used as acidic support.
Activity of these catalysts depends on the balance between the hydrogenation and acidic
functions. For example, it was found that HZSM-5 was effective for the hydrocracking of
HDPE and plastic waste [24]. But the liquid product contained much less n-paraffins and a
greater amounts of aromatics (34%) and naphthenes (21.7%) because of a lack of sufficient
hydrogenation function. The reaction mechanism over HZSM-5 can be considered as
follows;
n-Paraffins Olefins Naphthenes Aromatics
a-Olefins Naphthenes Aromatics

(C2-C4)
However, in the case of hydrocracking over a dual functional catalyst, isoparaffins are
the major compounds in the liquid product.
Although the hydrocracking process (Figure 8.1) has many advantages for the heavy
oils containing heteroatoms, there are a few studies on the hydrocracking of heavy oils
derived from plastics. The conversion of waste plastics to naphtha by thermal cracking
followed by hydrocracking over an acidic catalysts was investigated in two post-consumer
waste plastics, namely DSD and APC [25]. DSD was provided by the Duales System
Deutschland. DSD (containing 1.126 wt% of Cl and 4.4 wt% of ash) and is considered as
a real post-consumer plastic. However, APC provided by the American Plastic Council
is a relatively clean waste plastic (containing 0.03 wt% of Cl and 0.45 wt% of ash). The
catalytic effect on oil yields from hydrocracking was neglible for DSD and APC. Several
catalyst had a significant effect on the boiling point distribution for the APC plastic,
producing lighter products, but had little or no effect for the DSD plastic. Hydrocracking
of heavy oil from DSD pyrolysis yielded 55–65% gasoline fraction, whereas the gasoline
yield was more than 90% for heavy oil from APC. However, in these studies gasoline
quality was not determined.
A more detailed investigation on the quality of gasoline from hydrocracking was carried
out by Masuda et al. [26]. They examined the activity and selectivity of a Ni-REY cata-
lysts with different nickel contents in the hydrocatalytic upgrading of heavy oils obtained
from the waste PE and a mixture of PE and PET. The selectivity towards gasoline of Ni
(0.5 wt%)-REY was 78% and the RON value of the produced gasoline was 110. Besides
this, Ni-REY a showed constant activity during repetition of the sequence of reaction and
regeneration.
Based on the above results, it can be mentioned that the catalyst having both hydro-
genation and acidic functions can successfully convert heavy oil derived from plastic
wastes (relatively clean) into environmentally acceptable transport fuels. However, for
the heavy oils containing impurities, the dual functional hydrocracking catalysts still need
to be improved. In the hydrocracking process over the acidic catalyst, nitrogen content in
feed is limited because basic nitrogen compounds poison the acidic sites of the catalyst.
Hydrocracking:
Function of metals:
− 2 H+ + H+ +
Function of acidic support:
i-C4 + Cn
+
+ i-C5 + Cn
+ i-C6 + Cn
+ i-C4 + Cn
Hydrogenation:
Metal
N + H2 NH3 + H
Metal
S + H2 H2S + H
Metal
O + H2 H2O + H
Metal
Cl + H2 HCl + H
+ H2 + H2
Figure 8.1 The hydrocracking and hydrogenation mechanism of metal-supported acidic

catalyst
216 J. YANIK
In addition, in order to prevent the deactivation of the catalyst caused by the deposited
coke or coke precursor, the process needs to be operated at high hydrogen pressures and
this leads to high hydrogen consumption and high construction cost of the reactor.
Activated carbon catalysts, which are neutral, can be considered as an alternative cata-
lyst for hydrocracking of heavy oils derived from waste plastics. In recent years, carbon
has received much attention as a support for hydrodesulfurization (HDS) catalysts as high
HDS activities have been reported [27, 28], which may be due to more favorable sup-
port/catalytic species interactions. In addition, activated carbon catalysts have many other
interesting features such as high surface areas with controlled pore volume and pore size,
reduced coking activity and controllable surface functionality. The use of activated car-
bons as a catalyst support offers some advantages over the more traditional acidic oxide
supports, such as stability in acidic and basic media, ease of recovery of precious metals
supported on them, and the possibility of tailoring their properties to specific needs [29,
31]. It has been reported that metal-supported activated carbon (M-AC) catalysts have
shown excellent cracking activity in addition to hydrogenation, on petroleum-derived
heavy oils and some coal model compounds [32–38]. The catalytic effects of M-AC cat-
alysts in hydrocracking of vacuum gas oil have been explained by a radical mechanism.
Thus, activated carbons (AC) have the ability to abstract hydrogen from a hydrocarbon
and free radicals are formed on AC. These free radicals initiate the cracking reactions. In
the presence of H2 , hydrocarbon free radicals are hydrogenated by hydrogen atoms which
are generated on M-AC from gaseous hydrogen to form stable hydrocarbon molecules
and consequently to suppress overcracking. This hydrogen quenching reaction produces
the higher middle distillate yield and lower gas and naphtha yield [37]. AC catalysts have
also been found to have a better ability to restrict the coke formation and show high activ-
ity for the removal of such impurities as sulfur and heavy metals during hydrocracking
of heavy oil [32]. Even though no data are available in the literature, it can be suggested
that AC as the catalyst is well suited to upgrade the heavy oil derived from MWP:
In conclusion, it is certainly possible to develop commercial processes based on pyrol-
ysis–hydrocracking/cracking. But it must be noted that the viability of this two-stage
conversion technique depends on process economics and future regulatory considerations.
2.3 CO-PROCESSING OF MWP
Another approach in liquefaction of MWP is co-processing which has a special importance

from the viewpoint of feedstock recycling. Most co-processing studies have involved the
hydrothermal cracking of single plastics or waste plastics with coal using HZSM-5 and the
bifunctional (hydrotreating and hydrocracking) acidic catalysts. The results have shown
good conversion for autoclave liquefaction of plastic/coal mixtures. However, there were
also conflicting reports of whether co-processing led to better or worse conversions. Coal
rank and type of plastics emerges as a significant characteristic, affecting its synergy with
the various reaction parameters. Co-processing of coal and waste plastics is difficult, as
neither the reaction conditions nor the catalyst can be tailored simultaneously for both
materials. Moreover, it must be noted that, co-liquefaction of waste plastics with coal may
be a promising process to develop an economically feasible process for coal liquefaction,
since the waste plastics play the role of hydrogen donor for coal liquefaction.
A more interesting approach for co-processing is the conventional treatment of plastic
with a heavy petroleum fraction blend in a refinery unit. The main advantage of this copro-
cessing method is that it utilizes existing processes within a refinery complex, resulting
in reduced capital costs. Little research has focused on the co-processing of plastics with
a feedstock of a refinery unit. Studies have been carried out with different plastics and
refinery feeds.
Ng [39] evaluated conversion of HDPE blended with vacuum gasoil (VGO) to trans-
portation fuels by catalytic cracking over an acidic catalyst (KOB-627). It has been shown
that addition of HDPE increased the gasoline yields significantly when more than 10%
plastics were dissolved in the VGO. In cracking of light cycle oil (LCO, containing
66.9 wt% aromatics) over a neutral catalyst (mesoporous silica), the addition of poly-
olefins (PE, 10 wt% and PP, 5 wt%) to the LCO showed a synergistic effect on the
cracking of LCO and led to a remarkable decrease in the content of aromatics in the
gasoline fraction and an increase in the content of olefins, paraffins and isoparaffins. It
was stated that this result was a consequence of the high reactivity of radical intermediate
compounds from polyolefin cracking and of their global hydrogenating contribution [40].
On the other hand, studies on hydrocracking of blends containing HDPE, LDPE and
PP in HVGO over acidic catalysts showed that the effect of polymer on the crack-
ing of HVGO changed, depending on the type of catalysts [41–43]. The presence of
polyethylenes affected the cracking properties in hydrocracking over DHC-8 (a com-
mercial hydrocracking catalyst). Over DHC-8, the liquids from PE/HVGO blends were
less and waxy compounds were more than from VGO alone. However, the yields were
similar for both blend and HVGO alone over HZSM-5. Although HZSM-5 showed a
high cracking activity, it gave liquid products containing the highest amount of aromatic
species and sulfur content. The studies on liquefaction of polyolefines in HVGO showed
that the type of polymer and catalyst had a great effect on the product distribution of
cracking/hydrocracking.
The principal limitation to co-processing is the need for important refining liquid
streams which are necessary taking into account the limited amount of plastics that can be
mixed, and the restricted use of chlorine and other hetereoatoms contained in the plastics
that can negatively affect the refinery unit and catalyst.
In the case of waste polymer mixture, it is expected that impurities in the waste plastic
mixture, as well as polymer type, have an effect on the hydrocracking process. In addition,
the degradation of single polymers might be different from that of mixtures of polymers.
In conventional refinery processes utilized for the conversion of MWP into fuel, the
presence of PVC in MWP might cause some problems such as poisoning of the catalyst,
evolution of corrosive gases and products containing chlorine. For these reasons, chlorine
has to be eliminated from the feed before processing. Preheating plastic mixtures at lower
temperatures (300–350◦ C) is the conventional way of elimination of chlorine because
the thermal stability of PVC is much lower than that of other polymers. Dechlorination
of MWP in a heavy petroleum fraction is more demanding than dechlorination of MWP
alone. The heavy petroleum fraction acts a solvent during dechlorination, preventing the
blockage of gas line and decreasing energy requirement with improving heat transfer. It
might be expected that the dechlorination step is not only responsible for elimination of
chlorine, but also effects the properties of the blend which will be cracked/hydrocracked.
218 J. YANIK
Table 8.4 The composition of MWP (wt. %)
HDPE LDPE PP PVC PS PET inerts

12 21 56 2 2 1 6
Table 8.5 Product distribution of hydrocracking of MWP/HVGO blend and HVGO
Reaction products Dechlorinated MWP/HVGO HVGO

(wt%)
None DHC-8 Co-AC HZSM-5 None DHC-8 Co-AC HZSM-5
Reaction temperature at 425◦ C
Gasa 28.3 31.4 47.2 55.2 18.5 27.6
Liquid 27.1 32.4 40.5 40.4 61.2 60.1
Wax 32.9 28.3 11.2 4.4 18.6 12.3
Coke 5.4 7.2 1.1 0 1.7 0
Undegraded MWPb 31.6 3.4
Gasa 30.8 28.1 39.3 51.9 62.3 57.1 22.7 44.9
Liquid 50.2 34.2 37.3 20.1 30.1 34.1 60.8 40.5
Wax 16.5 34.0 21.2 18.9 7.0 8.5 14.3 14.2
Coke 0.9 1.0 1.5 8.6 0.5 0.3 2.2 0.4
Undegraded MWPb 8.0 13.6 0.4 2.6
Gasa 48.7 35.9 45.9 68.3 73.4 61.0 49.9 58.8
Liquid 44.2 47.3 36.0 12.9 24.4 29.4 34.1 19.1
Wax 6.6 15.9 17.5 15.5 2.2 7.1 13.0 21.4
Coke 0.5 0.9 0.5 2.9 0 2.5 3.0 0.7
Undegraded MWPb 0.4 1.9
a
Calculated from mass balance b Based on MWP charge
Liquefaction of MWP in a refinery stream has been studied at a laboratory level [44].
Thus, MWP containing mainly polyolefines (Table 8.4) has been added into the feed
of a hydrocracking plant, heavy vacuum gas oil (HVGO) and then the blend contain-
ing 20 wt% MWP has been converted to fuels by two-step processing. In the first step,
dechlorination has been carried out by preheating at 350◦ C (dechlorination step) in a semi-
batch reactor yielding a slurry of 91.2 wt% and a liquid 2.1 wt%. Then the dechlorinated
mixture containing 120 ppm chlorine has been catalytically hydrocracked at temperatures
between 425 and 450◦ C. The temperatures have been chosen on the basis of the hydro-
cracking process in the refinery. The catalysts used were HZSM-5, DHC-8 (commercial
hydrocracking catalyst consisting of non-noble hydrogenation metals on a silica–alumina
base) and a cobalt-loaded activated carbon catalyst, Co-AC. The product distribution from
hydrocracking of MWP/HVGO blend in comparison to VGO alone is given in Table 8.5.
Both the temperature and the type of catalyst effected the product distribution. Different
trends in product distribution were observed with the catalyst as the reaction tempera-
ture increased. As expected, HZSM-5 showed a high cracking activity, leading to more
gas product formation. There was a continuous increase in gas yield by increasing tem-
perature whereas liquid yield decreased dramatically. In contrast to the liquid yield, the
amount of wax did not decrease at temperatures above 435◦ C. This shows that at higher
temperature, further cracking reactions occurred, leading to gas formation and waxy com-
pounds. However, hydrocracking of blends containing individual polymer (LDPE/HVGO,
HDPE/HVGO, PP/HVGO) led to a greater amount of liquid and a smaller amount of wax
being obtained than from the MWP/HVGO blend. This may be due to two reasons. One is
that the degradation route of the individual polymer is different from that in the polymer
mixture. The other cause may be the impurities in MWP, because the activity of HZSM-5
was effected by impurities. In contrast to HZSM-5, DHC-8 has shown catalytic activity
at temperatures above 425◦ C. The increase in temperature led to the production of more
liquid and the cracking of waxy compounds. The degradation route is as follows:
Wax Liquid Gas
The studies on the hydrocracking of blends containing individual polymer showed that
the catalytic activity of DHC-8 varied with the polymer type in the blend. Although
the blends of LDPE/HVGO and PP/HVGO liquefied easily at 425◦ C over DHC-8, the
HDPE/HVGO DHC-8 showed sufficient cracking activity only at 450◦ C. These results
suggest that HDPE in blends, even at very low concentrations, such as 2.4%, plays an
important role in controlling the rate of cracking of blends in the absence of a sufficient
temperature and of catalytic activity. DHC-8 and HZSM-5 showed substantially different
activities in coprocessing of HVGO with polymers due to the differences in their acidity.
DHC-8 is an amorphous silica–alumina (ASA). It is known that the activity in ASA
is attributed to both Lewis and Brönsted acid sites. The strongest sites are not the most
favorable sites (in hydrocracking catalyst). The most favorable sites are the weak ones that
are sufficiently strong to accomplish the desired chemical reactions. However, HZSM-5
has the stronger acid sites and is more effective in the degradation of polymer. Although
acidic catalysts have good performance in conversion of pure polymers to liquid and
gaseous fuels, the impurities in wastes are poisonous for acidic catalysts and/or lead to
easy deactivation of catalyst in the case of catalytic liquefaction of waste plastics. This
is because the basic nitrogen which occurs in waste plastics poisons the active site of
acidic catalysts. A cobalt-loaded active carbon catalyst (neutral catalyst) has shown a
better cracking ability than commercial DHC-8 catalyst in co-processing of MWP. Upon
increasing the temperature, formation of gases increased. The yields of liquid and gas
products increased, depending on the increase in the cracking of waxy compounds and
waste plastics, when the temperature increased from 425 to 435◦ C. A further increase in
the temperature led to cracking of liquids to gases.
In cracking over a metal-loaded activated carbon catalyst, hydrocarbons are cracked via
a radical mechanism as in thermal cracking. However, cracking over Co-AC gave a very
different product distribution when compared with thermal cracking. At 425◦ C, the liquid
product is not generally obtained by thermal hydrocracking, whereas hydrocracking over
Co-AC produced liquid product. Over Co-AC, the free radicals on the carbon surface
initiate the cracking reaction by abstraction of hydrogen in hydrocarbons as follows.
R CH2 CH2 CH2 R + AC R CH2 CH CH2 R + H AC
On the other hand, in radical degradations the concentration of free radicals can be
controlled by H2 S [45]. In this study, H2 S is already present because the HVGO contains
220 J. YANIK
sulfur under hydrocracking conditions. In thermal hydrocracking, the hydrogen of H2 S is
abstracted by the hydrocarbon radical to form a stable hydrocarbon and HS• . Subsequently
the HS• abstracts a hydrogen from the hydrocarbon. Thus, the lifetime of hydrocarbon
radicals can not be reduced. However, in the presence of M-AC catalyst, H• and HS•
are formed from H2 S. HS• abstracts a hydrogen from the hydrocarbon or is stabilized
on the supported metal catalyst by hydrogenation. These explanations can be shown
schematically as follows.
In the thermal case:
• •
+
H2S Recombination
•
+ HS
•
+ HS
•
+ H2S
In the presence of Co-AC:
Metal • •
H2S H + HS
• Metal •
HS + H2 H2S + H
•
• + H (Hydrogen quenching)
In hydrocracking of HVGO alone the reason for decreased gas formation over Co-AC
catalyst (compared with a thermal run) may be the fact that the activated carbon leads
to the formation of more H• or HS• which terminates the radical degradation pathy-
ways. However, in the case of a blend, in the absence of catalytic activity, hydrocarbon
quenching (with radicals from derivated plastics) may be more pronounced than hydrogen
quenching (with H• ).
As in thermal runs, due to reaction between primary degradation products of HVGO
and MWP, DHC-8 showed a lower cracking activity than that of hydrocracking of HVGO
itself in the presence of DHC-8. This result is consistent with the results obtained from
hydrocracking of blends containing single plastics. In contrast, in the presence of HZSM-5,
the addition of MWP to VGO decreased the liquid yield whereas it increased the gas yield.
This shows that presence of MWP led to overcracking reactions.
Over Co-AC, the effect of MWP on cracking properties of HVGO varied with temper-
ature. At 425 and 435◦ C, similar effects were observed to those observed over HZSM-5;
production of more gas and less liquid. It is a most important point that similar prod-
uct distribution has been obtained from hydrocracking of HVGO and MWP/HVGO over
Co-AC at 450◦ C.
The catalyst type also affects the quality of liquid fuel. The changes in the composition
of liquids with temperature depend on the type of catalyst. The amount of naphtha frac-
tion in the liquid fuel increased with temperature up to 435◦ C and then decreased (over
HZSM-5 due to overcracking of naphtha) or remained constant (over Co-AC and DHC-8).
In hydrocracking of MWP/HVGO blend at 435◦ C, HZSM-5 produced liquid containing
70% naphtha (boiling point < 172◦ C), 17% middle distillate (bp 172–232◦ C), whereas in
the presence of DHC-8, the naphtha and middle distillate were 46 and 19% respectively.
At the same temperature of 435◦ C, Co-AC gave liquid containing more light compounds
than DHC-8; 55% naphtha and 18% middle distillate. As expected, the liquid derived from
thermal runs were heavier than that of catalytic runs at all temperatures.
Although in the case of hydrocracking of HVGO alone, DHC-8 commercial hydroc-
racking catalyst gave the lightest product, it did not give the best result for MWP/HVGO
blend. It may be noted that in the presence of Co-AC, the liquids from MWP/VGO blend
had lighter compounds than that from HVGO.
It is noteworthy that, although HZSM-5 is more active in hydrocracking of the
MWP/HVGO blend, it favored aromatization reactions and inhibits desulfurization, even
in the presence of H2 . The liquid fuel derived by hydrocracking over HZSM-5 at 435◦ C
had the highest amount of sulfur (2.1 wt%) and aromatic compounds (28.0 wt%). In
contrast, the aromatic content of liquids was 4.0 and 6 wt% for DHC-8 and Co-AC,
respectively. As expected the liquid from DHC-8 contained the lowest sulfur amount
(1.009 wt%) since it has been used in refinery for hydrocracking of HVGO. However,
it showed a greater desulfurization effect in the hydrocracking of blends containing
individual pure polymer. It may be concluded that impurities in wastes affected the HDS
activity of DHC-8. Co-AC catalyst also had a hydrodesulfurization effect, produced a
liquid containing 1.21 wt% sulfur. In addition, it should be noted that in the presence of
Co-AC the liquids from blends containing both waste polymer and pure polymer had a
similar sulfur amount.
3 CONCLUSIONS
As a result, MWP sorted from municipal solid wastes can be processed in a refinery, which
has a dechlorination unit installed prior to the hydrocracking unit. Even though commercial
catalysts showed satisfactory performance at high temperatures, neutral catalysts based
on activated carbon can also be utilized for this purpose.
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polyethylene with VGO using metal supported on activated carbon, Energy and
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in a refinery stream, Polymer Degradation and Stability, 75, 161–171 (2002).
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plastics treatment for high quality transportation fuel, Catalysis Today, 27, 175–179
(1996).
9
Kinetic Model of the Chemical

and Catalytic Recycling of Waste
Polyethylene into Fuels
NORBERT MISKOLCZI
University of Veszprém, Department of Hydrocarbon and Coal Processing, Egyetem u.
10, Veszprem, H-8200, Hungary
1 INTRODUCTION
There are several physical and chemical methods to investigate the degradation of poly-
mers, from methods without change of physical and chemical properties of polymers to
degradation processes for the recovery of monomers. The initiation of degradation may
be considerably different: heat (thermal degradation), heat and catalyst (thermocatalytic
degradation), oxygen (oxidative degradation), heat and oxygen (thermo-oxidative degra-
dation), radiation (photochemical degradation), radiation and oxygen (photo-oxidative
degradation), chemicals (chemical degradation), microorganisms or enzymes (biodegra-
dation or bioerosion), etc.
The common characteristic of these methods is that they cause irreversible changes in
the structure of polymers. The decomposition of the framework of polymers results in
decreasing molecular weight and significant changes of physical and chemical properties.
The widely known and thoroughly studied methods are thermal and thermocatalytic
degradation, which are referred to in the literature as chemical recycling. Chemical recy-
cling and chemical degradation are not the same, because chemical degradation means
degradations caused by chemicals (acids, solvents, alkalis, etc.)
The study of chemical recycling and degradation of waste plastics has developed since
the 1980s. During chemical recycling hydrocarbon macromolecules of polymers break
down into smaller molecules owing to thermal or thermal and catalytic effects. According
to researchers, the possibility of further utilization of cracked products is their fuel-like
use; therefore the objective of researches is the production of hydrocarbons with similar
properties to refinery streams (e.g. gasoline, kerosene, diesel oil, etc.). For this reason the
226 N. MISKOLCZI
formation of volatile products (gases, liquids) with suitable yield is a key issue during
investigations.
There are some advantages of the application of catalysts, on the other hand it may
cause difficulties (feeding of catalysts into the reactor, activity loss, etc.). Usually batch
experiments were carried out on laboratory scale (1–5 g) using one or two types of
polymers, which were virgin and not waste polymers, therefore the confrontation with
problems of greater amounts of catalysts is probable in the immediate future.
Many polymers with different structure and properties may be used as raw materials
in degradation (HDPE, LDPE, PP, PS, PVC, PET, PA, PUR, etc.) although polyolefins
(HDPE, LDPE, PP) and polystyrene (PS) have the best properties from the point of view of
their further utilization. Several reports have described the thermal and catalytic cracking
of waste polymers. Two types of polymers have been widely investigated: polyethylene
and polypropylene, because they represent 60–65% of all plastic wastes. The degradation
of plastics means heating to high temperatures where macromolecules break into smaller
fragments. Valuable mixtures of hydrocarbons (gas, liquid and residue) are obtained [1–6].
The structure of the hydrocarbons produced can be modified by the use of catalyst.
Catalytic cracking consumes less energy than the noncatalytic process and results in
formation of more branch-chain hydrocarbons. On the other hand the addition of the
catalyst can be troublesome, and the catalyst accumulates in the residue or coke. There
are two ways to contact the melted polymer and catalysts: the polymer and catalyst can
be mixed first, then melted, or the molten plastics can be fed continuously over a fluidized
catalyst bed. The usually employed catalysts are US-Y, and H-ZSM-5. Catalyst activity
and product structure have been reported [7–11]. It was found that the H-ZSM-5 and
FCC catalysts provided the best possibility to yield hydrocarbons in the boiling range of
gasoline.
2 REACTION KINETICS OF DEGRADATION
Description of decomposition reactions during degradation of plastics is quite difficult,

because they are very complex. Furthermore there are considerable differences between
thermal degradation of waste plastics in the absence and presence of catalysts, but the
type of the reactor or the amount of plastics is also important. Degradation in the pres-
ence of catalysts is called thermocatalytic degradation. Cracking experiments are done
in batch reactors in 95% of cases [1–11] and within it the thermogravimetric analysis
connected with different techniques (e.g. TG, DTG, DSC, TG-MS, DTG-MS, etc.) is
predominant [12–17]. Only a few researchers have investigated the cracking of waste
polymers under continuous or semi-continuous conditions [18–21]. One reason for this
is that considerable amounts of wastes are needed for continuous cracking and difficulties
emerge caused by the geometry of the reactor and greater amounts of materials (e.g. cir-
culation, heat transfer, coking, fouling, etc.) or the feeding of catalysts, their separation
from products and regeneration.
Some kinetic models for thermal or catalytic polymer degradation have been proposed.
The commonly used approach is first-order kinetics to investigate the characteristics
of degradation (Equation 9.1). In this approach at first the weight loss curve of poly-
mers during the decomposition is determined, and overall rate constants are calculated
KINETIC MODEL OF RECYCLING 227
[12, 14–16, 22–25]. The objectives of experiments are the determination of the apparent
activation energies and other reaction kinetic parameters (reaction rate, preexponential
constant, etc.) of degradation resulting volatile products (gases and liquids). Besides the
development of kinetic models the prediction of the yields or main properties of prod-
ucts in the knowledge of properties of the raw material are also important. The principal
problem in this case is the derivation of reaction rate constant because some factors signif-
icantly affect the conversion of degradation (physical, geometrical, steric, etc.). Usually a
constant value of reaction rate is postulated and first-order kinetic equation together with
the Arrhenius equation is used. Relations become more difficult when considering auto-
catalytic reactions. Some correlations exist to calculate reaction kinetic parameters under
dynamic circumstances [26, 27]. The activation energy and the preexponential constant
are determined from the logarithmic form of the Arrhenius equation (Equation 9.2.).
dm
− = kmn (9.1)
dt
E
k = A0 e− RT (9.2)
where m0 is the weight of sample, n is the reaction order, k is the reaction rate coefficient,
m is the weight of residue, t is the time of degradation, E is the activation energy and
A0 is the preexponential constant.
Relations might be simplified by using thermogravimetric and connected methods, but
a new parameter is to be introduced. This new parameter is the heating rate. Table 9.1
shows some of the approaches used for the determination of kinetic parameters [28–30].
When comparing the equations in Table 9.1, it is found that the equations of
Flynn–Wall, Horowitz–Metger and Friedmann gave excellent correlation in the case
of degradation of polypropylene [29, 30]. Others created a software to calculate the
reaction kinetic parameters using the first-order kinetic equation based on these equations.
Key parameters were calculated with the minimization of differences between calculated
and experimental results obtained directly by a thermogravimetric apparatus [24]. Good
correlation between data was observed in case of HDPE and PS by using this software.
Table 9.1 Summary of approaches for the determination of kinetic parameters
Method Equation

Ea 1
Flynn–Wall ln β = −1052
R T

dα Ea
Friedmann ln = ln A + n ln(1 − α) + min(α) −
dt RT

β E AR
Kissinger ln =− + ln − ln F (x)
T2 RT E

E AE
Ozarawa ln β = −0.4567 + log − log F (x) − 2.315
RT R

1 Ea
Horowitz–Metger ln ln =
1−α RTs2
228 N. MISKOLCZI
The main problem in case of thermocatalytic cracking of polymers is the activity loss
of catalysts; therefore first-order kinetics is applicable only with some simplifications in
thermocatalytic cases. On the other hand there is a relation modelling the fluid catalytic
cracking taking into consideration the catalyst deactivation in refineries [31]:
η = exp[−αC(c)] (9.3)
where η is the activation loss of catalyst, C(c) is the coking of catalyst and α is a constant
depending on the type of catalyst.
Equation (9.3) was used to model the thermocatalytic degradation of waste polyethylene
and polypropylene [22]. In this case researchers had to calculate η for each catalyst. On
the other hand it is complicated; therefore researchers disregard the change of reaction
rate and order caused by deactivation of catalysts in most experiments. The reaction rates
and other reaction kinetic parameters are given in Table 9.2 [32].
There are also some empirical equations for describing the yields of products formed
in the cracking reactions of polymers. One of them is the Atkinson and McCaffrey kinetic
model, which derives the weight loss of polymer for their initial degree of polymerization,
weight of sample and reaction rate. As a matter of fact the reaction rate constant is
calculated by using a first-order kinetic equation [33, 34].
The temperature significantly affects the conversion of thermocatalytic degradation
besides the characteristic of catalysts. The time–temperature superposition describes the
dependence of reaction rate from temperature. The conversion can be increased both
with degradation temperature and time. It means that the cracking time which is needed
to achieve the same degree of conversion decreases with increasing temperature. The
shift factor is the quotient of cracking times at different temperatures or the quotient
of temperatures at different cracking times. The value of the shift factor is affected by
the characteristics of the polymer and by the cracking conditions. There are two meth-
ods to derive the shift factors: the Arrhenius equation and the Williams–Landel–Ferry
(WLF) equation. J.H. Chan and S.T. Balke calculated the value of shift factors in case
of polypropylene degradation [35]. It was found that the product of reaction rate coeffi-
cients and cracking times at different temperatures is nearly constant. The shift factors
and constants of the WLF equations can be calculated by the use of these similarities.
2.1 REACTION MECHANISM
As a matter of fact the cracking of C–C bonds takes place as the result of competition
between reactions initiated by thermal and catalytic effects of thermocatalytic degradation.
It means that thermal and catalytic reactions do not separate from each other, therefore
in discussing thermocatalytic cracking of polymers one has to touch upon both the ther-
mal and catalytic degradation reactions. It is well known, that the thermal (noncatalytic)
cracking of plastics occurs by a radical mechanism, wherein the initiating radicals are
formed by the effect of heat. Catalytic cracking, on the other hand, generally proceeds
though carbenium ions, which are considered to be produced by the abstraction of hydride
ion (Lewis acid) from the polymer or the addition of proton (Brösted acid) to the polymer
macromolecule in the initial reaction step. Fragments formed in the first cracking reac-
tions cracked further into lower-molecular-weight hydrocarbons on the active sites of the
Table 9.2 Reaction kinetic properties of thermal cracking of different polymers
Kinetic model Equation Ea (kJ/mol) n A (min−1 ) Yield coefficient

k1 d[H DP E] −Ea1
HDPE−−−→V + R = −A1 e RT [HDPE]n1 250 0.65 1.71 × 1017
dt
k1 d[LDP E1 ] −Ea1
α1 LDPE1 −−−→V1 + R = −A1 e RT [LDPE1 ]n1 Ea1 = 120 n1 = 1.40 A1 = 1.34 × 109 α1 = 0.10
dt
k2 d[LDPE2 ] −Ea2
KINETIC MODEL OF RECYCLING
α2 LDPE2 −−−→V2 + R2 = −A2 e RT [LDPE2 ]n2 Ea2 = 220 n2 = 0.60 A2 = 1.47 × 1015 α2 = 0.90
dt
k1 d[PP] −Ea1
PP−−−→V + R = −A1 e RT [PP]n1 125 0.40 2.04 × 108
dt
k1 d[P S1 ] −Ea1
α1 PS1 −−−→V2 + R2 = −A1 e RT [PS1 ]n1 Ea1 = 120 n1 = 1.60 A1 = 1.06 × 108 α1 = 0.10
dt
k2 d[PS2 ] −Ea2
α2 PS2 −−−→V2 + R2 = −A2 e RT [PS2 ]n1 Ea2 = 185 n2 = 0.76 A2 = 2.32 × 1013 α2 = 0.90
dt
k1 d[PVC] −Ea1
PVC−−−→aHCl + bI = −A1 e RT [PVC]n1 Ea1 = 198 n1 = 1.04 A1 = 3.57 × 1018 b = 0.52
dt
k2 d[I ] −Ea1 −Ea2
bI−−−→cV1 + eR1 = b(A1 e RT [PVC]n1 − A2 e RT [I ]n2 Ea2 = 143 n2 = 1.15 A2 = 9.95 × 1010 e = 0.36
dt
k3 d[R1 ] −Ea2 −Ea3
eR1 −−−→f V2 + gR2 = e(A2 e RT [I ]n2 − A3 e RT [SR1 ]n3 Ea3 = 243 n3 = 1.58 A3 = 5.77 × 1016 g = 0.06
dt
d[R2 ] −Ea3
= g(A3 e RT [SR1 ]n3
dt
V volatile products; I intermediates; SR1 primary products; SR2 secondary products
229
230 N. MISKOLCZI
catalyst. Unstable primary fragments are cracked in further decomposition reactions. The
following elemental reactions take place both in thermal and thermo-catalytic cases:
a) initiation
b) formation of secondary radicals
• depolymerization, formation of monomers;
• favourable and unfavourable hydrogen transfer reactions;
• intermolecular hydrogen transfer (formation of paraffins and dienes);
• isomerization via vinyl groups;
c) termination by disproportionation or recombination of radicals.
In the presence of catalysts, heterogeneous catalytic cracking occurs on the surface
interface of the melted polymer and solid catalysts. The main steps of reactions are as
follows: diffusion on the surface of catalyst, adsorption on the catalyst, chemical reaction,
desorption from the catalyst, diffusion to the liquid phase. The reaction rate of catalytic
reactions is always determined by the slowest elementary reaction. The dominant rate
controller elementary reactions are the linking of the polymer to the active site of catalyst.
But the selectivity of catalysts on raw materials and products might be important. The
selectivity is affected by molecular size and shape of raw materials, intermediates and
products [36].
2.1.1 Initiation
The mechanism of initiation is partly radical in thermocatalytic degradation. The cracking
of C–C bonds occurs by homolytic cracking of C–C bonds, at regions with structural faults
or distortion of the electron cloud.
Catalytic cracking generally proceeds through a carbenium ion, which is considered to
occur by the abstraction of hydride ion from polymer or the addition of proton on the
polymer macromolecule in the initial step of the reaction (Figure 9.1).
H
O Si O Al O Si O + CH3 CH2 CH CH2 CH2 CH2 CH2 CH2 CH3
n
O
Si
H
+
O Si O Al O Si O + CH3 CH2 CH CH2 CH2 CH2 CH2 CH2 CH3
n
O
Si
Figure 9.1 Initiation in thermocatalytic cracking

The framework of waste polymers might be cracked at C–C bonds at low temperature
and both at C–C and C–H bonds at high temperature. The cracking of C–C bonds has
lower energy consumption, than that of C–H, because it has lower bond energy, by
40–60 kJ/mol, than the C–H bond. The likelihood of cracking of a carbon chain is
significantly affected by its substituents. In the case of polypropylene this means that
the lower thermal stability is the consequence of methyl groups linked to the main carbon
chain. Methyl groups have a positive inductive effect, but among others halogens and
phenyl groups have the same property; e.g. the high yield of monomer in the case of
degradation of polystyrene is attributed to this effect.
Table 9.3 shows the activation energies of elemental reactions in the case of polymer
degradation. It is noticeable the initiating reactions have the highest potential barrier.
This potential barrier can be decreased by the use of catalysts and it results a decrease of
50–100 kJ/mol in activation energy [37, 38, 39].
Tables 9.4 and 9.5 show some examples of thermal and thermocatalytic cracking on
laboratory scale.
In the presence of catalysts the beginning of cracking of C–C bonds of macromolecules
of polymer occurs at a lower temperature than in the absence of catalysts. This phe-
nomenon could be explained by the acidic sites of the catalysts, because of to the
considerably greater number of unstable molecular fragments formed at lower temperature
in the presence of catalysts. Volatile products are formed from polymers with suitable
yields only above 450◦ C without catalysts, but at 300–400◦ C using catalysts. On the
other hand some noncatalytic cracking takes place at 400–450◦ C [37, 39, 41] because
Table 9.3 Activation energies of elementary steps in polymer degradation
Elementary steps Activation energy (kJ/mol)

Initiation 284–336
Depropagation 21–77
Termination by disproportionation 4–10
or recombination
Diffusion in molten state 27
Diffusion in solid state 41
Table 9.4 Some laboratory experiments of thermal pyrolysis
Investigator Polymer Reactor Temperature Products

(◦ C)
K. Murata et al. [39] HDPE, PP, PS Continuous flow 350–450 Gas, oil
stirred reactor
R. Aguado et al. [40] PS Conical spouted bed 500–600 Gas, monomer
reactor
T. Moriya et al. [41] HDPE Bomb-type autoclave 400–425 Gas, oil
A. Karaduman et al. [42] PS Free-wall reactor 825 Aromatics
H. Bockhorn et al. [43] HDPE, PP Closed loop-type 410–480 Gas, oil
reactor
W. Kaminsky et al. [44] Mixed waste Fluidized-bed reactor 600–750 Gas, oil, aromatics
N. Miskolczi et al. [45] Mixed waste Tube reactor 500–550 Gas, oil, aromatics
F.J. Mastral et al. [46] HDPE Fluidized-bed reactor 640–850 Gas, wax, oil
232 N. MISKOLCZI
Table 9.5 Some laboratory experiment on catalytic pyrolysis
Investigator Polymer Experimental set-up Catalyst Catalyst

concentration
(%)
A. Marcilla LLDPE, LDPE Thermogravimetric 2–9 MCM-41
et al. [15] HDPE apparatus with an
initial sample mass
4–25 mg and a
heating rate of 10 and
40◦ C/min in nitrogen
atmosphere
Z.S. Seddegi HDPE The reactor containing 10–16 MCM-41
et al. [7] 3 g of polymer was
connected to a liquid
condenser and gas
collection bag. Gases
and liquid was
analyzed with GC
J. Aguado LDPE Screw kiln reactor with 2 Al-MCM-41
et al. [47] two furnaces
(2 × 52 cm) and
250 g of polymer at
300◦ C under nitrogen
atmosphere using
3.0–15.0 m3 /h
P.A. Jalil HDPE Glass batch reactor 3 and 6 MCM-41
et al. [5] under atmospheric
condition. 3 g of
HDPE pellets were
used
R. van Grieken LDPE The degradation of 50 g USY zeolite, activated
et al. [9] of plastic was carried carbon,
out in a batch reactor silica–alumina,
provided with a MCM-41, HZSM-5,
helicoidal stirrer at Pd charcoal
120 rpm under
nitrogen atmosphere
S.Y. Kim PS Batch stirred tank 1 Clinoptilolite,
et al. [3] reactor made of pyrex HZSM-5,
glass. A mixture of silica–alumina
100.0 g PS and 1 g
catalyst was loaded
inside the reactor
E.-Y. Hwang PP Semi-batch reactor with 10 Different clinoptilolites
et al. [11] nitrogen flow rate of
30 ml/min. A mixture
of 3.0 g PS and 0.3 g
catalyst was loaded
inside a Pyrex vessel
G. de la Puente LDPE Riser simulator reactor 6.5 Equilibrium Engelhard
et al. [48] FCC catalyst ASA
S. Karagöz 80% Vacuum A 100 ml stainless steel 1 DHC-8 hydrocracking
et al. [49] Gas Oil and shrank type batch catalyst HZSM-5
20% HDPE autoclave was used
S. Ali et al. [21] HDPE Fluidized-bed reactor 66.6 ZSM-5, US-Y, ASA,
under N2 Fresh commercial
FCC catalyst,
Equilibrium
Engelhard FCC
catalyst
Table 9.5 (continued )
Investigator Polymer Experimental set-up Catalyst Catalyst

concentration
(%)
Y.-H. Seo HDPE The reactor was a 1.1 L 5 ZSM-5 (powder)
et al. [5] round stainless steel Y-zeolite (powder)
bottle placed in a Y-zeolite (pellet)
furnace Mordenite (pellet)
Silica–alumina
(powder) Alumina
(powder)
P.N. Sharrat HDPE Fluidized-bed reactor 40 HZSM-5
et al. [19] using nitrogen
K. Takuma LDPE A fixed-bed tubular flow 10 H-gallosilicate
et al. [36] reactor system was HZSM-5
used in helium
atmosphere
P. Carniti PP Thermogravimetric SiO2 , silica–magnesia,
et al. [50] analysis silica–titanate,
mordenite, SALA,
SAHA
Y. Sakata HPDE, LDPE, Flow reactor under 10 Silica–alumina,
et al. [8] PP, PET, PVC semi-batch conditions. ZSM-5, KFS-16B
The degraded
products of plastics
are passed through a
fixed bed of catalyst
T. Masuda HDPE-derived A fixed-bed type reactor 10 Ni-REY
et al. [4] heavy oil
J.-S- Kim PS A batch stirred tank 1 Al2 O3 , Fe2 O3 ,
et al. [3] reactor made of pyrex Fe/Al2 O3 ,
glass was used with Fe-K/Al2 O3 ,
200 rpm stirring. 10 g Fe-Ba/Al2 O3 ,
polymer was cracked Fe-Zn/Al2 O3 ,
Fe-Mg/Al2 O3
Uemichi PE, PP Flow reactor under Silica–alumina,
et al. [21] nitrogen activated carbon,
metal-supported
silica-alumina
the preferred compounds are aliphatic ones. It is well known that above 450–460◦ C
the possibility of reactions of cyclization, aromatization and polycondensation increases
considerably and this results growing concentrations of naphthenes and aromatics [36].
If waste polyolefins (LDPE, HDPE, PP) have to be converted into aliphatic olefins and
paraffins the low temperature is a key parameter.
Another important parameter is the catalyst concentration. Thermocatalytic cracking
of HDPE and MDPE over HZSM-5 and Y-zeolite catalysts was carried out in a cycled-
spheres reactor. It was found that the required temperature of cracking could be decreased
by 2% using a low concentration of catalysts, and by 16–20% in the case of greater
catalyst concentration because the reaction rate increased with increasing catalyst concen-
tration [51]. Not only the catalyst concentration, but also the temperature is a parameter
that determines properties. Increasing temperature increases the yields of volatile prod-
ucts. At higher temperature more C–C bonds are cracked in consequence of their lower
234 N. MISKOLCZI
thermal stability. On the other hand not only the yields of volatile products are increasing
at higher temperature, but also the yield of coke.
Smaller differences were found between thermal and thermocatalytic degradations in
respect to yields and structure of products at higher temperatures (450–500◦ C), than at
lower temperatures (400–420◦ C).
The composition of feed polymers also has an important effect on the properties of
products. In the experimental work of Miskolczi et al. commercial waste plastics from the
packaging, electronic and automotive industry and the agriculture were used as raw materi-
als. The samples contained high-density polyethylene (HDPE), low-density polyethylene
(LDPE), polypropylene (PP), ethylene–propylene copolymer (EPC), polystyrene (PS),
polyamide 6.6 (PA 6.6) and polyvinyl chloride (PVC).
The decomposition of waste polymer was carried out in the tube reactor, which consisted
of three main parts: an extruder, a reactor and a separator (Figure 9.2).
Each cracking reactor had the same geometric properties (e.g. length, diameter, etc.),
and they were kept at the same cracking temperature. Inside the reactor the polymers
were melted and their carbon chain cracked into low-molecular-weight fragments. In a
separator the hydrocarbons formed were separated into volatile products and residue. The
cracking characteristics and the change of product properties were investigated depending
on temperature, residence time and composition of feed polymer. Therefore different
temperatures (500, 525, 550◦ C) and residence times (15, 18, 23, 30 min.) were used.
Municipal
plastic
waste
2
3
7 8
Gases
5 Naphtha
4
6 Diesel oil
Light
paraffinic
10 oil
Heavy residue
Figure 9.2 Cracking apparatus for cracking of municipal plastic waste: 1. motor;
2. extruder; 3. reactor; 4. separator; 5. condenser; 6. separator; 7. gas-flow meter; 8. flare;
9. atmospheric distillation; 10. vacuum distillation
The yields of valuable light products (mainly naphtha, diesel oil) increased both with
residence time and temperature, which could be caused by the differences in the thermal
stability of polymer chains. Moreover the yields of naphtha and diesel-oil-like fractions
significantly increased with increasing concentration of PS in the feed MPW [54].
The composition of gases formed in cracking reactions of polymer blends contained
mostly C2 , C3 and C4 hydrocarbons, which was the consequence of structure of
polyethylenes and polypropylene. The concentration of olefins was higher than that of
the paraffins of the same carbon number, because the possibility of β-scission reactions is
greater than hydrogen transfer reactions in thermal degradation. The cracking parameters,
apart from the composition of raw materials, did not significantly affect the composition
of gaseous products. Calculated heating value of gases were 46–47 MJ/kg, which were
quite high for gases used in energy generation (e.g. to provide the heat requirement of
cracking with gas products of degradation).
Identifying of individual compounds in liquid products, especially branched molecules
from polypropylene, is rather difficult, because of the cracking of polypropylene yields a
great number of isomer compounds. The liquid product obtained by cracking of polyethy-
lene consisted mostly of n-alkenes and n-alkanes, which were evenly distributed by carbon
number, whereas the cracking of polystyrene yielded blends of aromatic compounds,
styrene, ethylbenzene, benzene, toluene [45, 54].
By the separation of products obtained by thermal cracking of model municipal plastic
wastes different fuel like fractions were separated: naphtha-like (N), diesel-like (DO)
and light-paraffinic-oil-like fractions (LPO). The other properties of products obtained by
cracking of MPW (20% HDPE, 20% LDPE, 10% EPC, 38% PP, 10% PS, 1% PA 6.6
and 1% PVC) are shown in Table 9.6.
The naphtha-like fraction contained C5 –C18 hydrocarbons, the main components being
C7 –C9 hydrocarbons, while that of C9 –C25 and C21 –C30 hydrocarbons in case of diesel-
oil-like and light-paraffinic-oil-like fractions. The aromatic content was accumulated in
the naphtha-like fraction and its concentration in others was below 1%. This is an advan-
tageous property for further, fuel-like or petrochemical applications, because the aromatic
content in white spirit does not cause problems, on the other hand the low aromatic and
high branched hydrocarbon content in diesel gas oil is also an advantageous property.
The concentration of aromatics increased both with cracking temperature, increasing res-
idence time and PS content of the feed polymer blend. In the respect to aromatics the
dominant concentration of ethylbenzene and styrene, the building elements of polystyrene,
was found. It was significant that the concentration of aromatics in the product was sig-
nificantly higher (20–27%) than the concentration of polystyrene in raw material (10%),
because of lower activation energy of polystyrene than others. In the case of aliphatic
compounds the triple sequence could be observed, which is typical of decomposition of
polypropylene. Due to the polypropylene content of samples C6 , C9 , C12 hydrocarbons
were present in the highest concentration. Each fraction had nearly half the olefin content.
Due to aromatics in naphtha-like fraction their octane numbers were high. According to
our previous experiences the formation of notable aromatics from polyolefins did not
observe in this tube reactor system bellow 560◦ C [45, 54], because the reaction rate of
cyclization and polycondensation, which resulted in aromatics, polycyclical compounds
or coke, increased by leaps and bounds above 560◦ C.
236 N. MISKOLCZI
Table 9.6 The composition and main properties of fuel-like products
Temperature (◦ C) 500 525 550

Products
N DO LPO N DO LPO N DO LPO
Aliphatic olefin 37.9 45.3 40.6 38.8 45.5 41.9 37.1 44.2 41.7
content (%)
Paraffin content (%) 44.3 54.7 59.4 43.6 54.9 58.1 42.5 54.8 58.3
Aromatic content (%) 17.8 17.6 0.6 20.4 1.0
Benzene 0.8 0.7 0.0 0.9 0.1
Toluene 0.3 0.3 0.1 0.9 0.1
Ethylbenzene 2.7 2.2 0.2 2.1 0.3
Styrene 12.2 13.0 0.1 14.5 0.2
Xylenes 0.8 0.3 0.0 0.5 0.2
Other 1.0 1.1 0.2 1.5 0.1
Density (g/cm3 ) 0.753 0.781 0.818 0.766 0.793 0.823 0.759 0.789 0.828
Flash point (◦ C) 98 217 98 219 94 216
Pour point (◦ C) −47 −9 68 −43 −13 64 −49 −10 61
CFPP (◦ C) −3 −4 −2
RON 95 97 96
MON 84 85 85
Diesel index 69 68 69
Cetane number 64 63 64
Viscosity (mm2 /s, at 4.4 4.3 4.3
40◦ C)
M (g/mol) 118 242 117 246 121 248
C/H 6.0 6.1 6.2 6.1 6.2 6.2 6.0 6.1 6.1
Cl content (ppm) 47 239 216 45 240 217 52 253 224
S content (ppm) 14 11 15 9 11 11 10 10 14
N content (ppm) 218 458 761 224 440 759 222 462 771
The fraction of diesel-oil-like hydrocarbons had also a triple sequence and the main
aliphatic compounds may be characterized with carbon numbers 12, 15, 18, 21, 24, 27.
In contrast with the experimental results of naphtha diesel oil had considerably lower
concentration of aromatics. In the case of each MPW sample its concentration was not
more than 1%, because aromatics with lower boiling point stayed in the naphtha-like
fraction. Similarly, as mentioned above, the diesel-oil-like fraction also had favourable
properties for further fuel-like application. The olefin content was a bit smaller than in
case of naphtha-like fractions, because cracking reaction resulting olefins (e.g. β-scission)
produced hydrocarbons with a shorter length of carbon chain. Both cetane numbers and
diesel indexes of products were high enough, while the CFPP was rather low.
It was found that the light-paraffinic-oil-like fractions had olefin and paraffin content
without aromatics and naphthenes. These fractions are appeared in solid phase at room
temperature due to their hydrocarbon structure with boiling point 250–380◦ C.
In the residue fractions aromatics were present as oligomers of styrene with higher
carbon number, which could not distilled from melted polymers. These fractions were
wax-like and their melting points were about 100◦ C, and they had the highest molec-
ular weight, about 2500 g/mol, which decreases a bit with increasing concentration of
polyamide and polyvinyl chloride waste plastics. This phenomenon could be attributed to
the greater degradation of MPW, in consequence of initiating effect of radicals from, e.g.
PVC on C–C bond cracking. Mechanical impurities and water content were not detected
in theses fractions. Their calorific values were about 41.3 MJ/kg, which is quite high for
application of these fractions for energy production.
Unfortunately the favourable properties of fractions were decreased in consequence of
increasing concentration of PA 6.6 and PVC, because both the concentration of nitrogen
and chlorine increased. This is a disadvantageous property for further utilization; therefore
the removal of chlorine and nitrogen needs to be solved.
2.1.2 Formation of Secondary Unstable Compounds

Unstable molecular fragments (radicals and ions) formed in the initiating reaction take part
in further decomposition reactions with uncracked macromolecules of polymer or radicals
and ions, resulting, among others, in secondary instable compounds of lower molecular
weight. Generally the β-scission of primary radicals and ions results in oligomers and
perhaps monomer. It was found that generally intermolecular hydrogen transfer reactions
followed by β-scission take place, particularly at lower temperature. This reaction leads
to formation of stable radicals and ions. At higher temperature the polymer chain cracked
to a greater degree; therefore the primary unstable fragments react with alkanes. It is
important to note that the probability of formation of aromatics by Diels–Alder reactions
is greater. In these reactions, e.g. polyenes might be the precursors of benzene at higher
temperature. In the olefins it is found that the double bond moves toward the end of
the framework in the case of nonbranched structures, and that of tertiary carbons in of
branched structures. Terminal double bonds turn into internal ones in the case of catalytic
cracking, but this is not typical in thermal cracking.
(A) β-scission
+
−CH2 −CH2 −CH2 −CH −CH2 − CH2 −CH2 − CH2− − CH2 −CH2−CH = CH2
+
+
CH2 − CH2 −CH2 − CH2 −
(B) Isomerization of carbon framework
+
− CH2 − CH2 − CH2 − CH −CH2 − CH2 − CH2 −CH2−
CH3
+
CH2− CH− CH2− CH2− CH2− CH2− CH2−
CH3
+
CH3 − C− CH2− CH2 − CH2 − CH2 − CH2−
+
238 N. MISKOLCZI
Isomerization of double bond
+H+ + +H+
−CH2 −CH2−CH =CH2 −CH2 −CH2−CH −CH3 −CH2 −CH2=CH−CH3
(C) Hydrogen transfer reactions

Intermolecular hydrogen transfer reactions
−CH2− CH2−CH2+ + −CH2 −CH2−CH2 −CH2− −CH2−CH2−CH2−

+
−CH2 −CH2 −CH2−CH2+
Intramolecular hydrogen transfer reactions
+ +
− CH2− CH2− CH2− CH2 −CH2− CH2− CH2 − CH2 − CH2 − CH2 − CH2 −CH2 − CH2− CH2−
(D) Cyclization and aromatization
+ − H+ − H2
R1−CH = CH2 + CH3−CH2− CH2− CH− R2 R1 − R1
R2 R2
Generally the concentration of iso-paraffins and olefins increased with decreasing tem-
perature because the increase in further degradation of branched hydrocarbons is greater,
than that of non-branched with increasing temperature. A similar phenomenon could be
observed in the case of catalysts possessing a weak hydrogenation property accompa-
nied by considerable acidity, because the olefin intermediates formed are isomerized in
greater ratio on the acidic sites of catalysts. On the other hand not only the probabil-
ity of isomerzation, but catalyst activity is decreases with decreasing of the acidity of
catalysts.
2.1.3 Termination with Recombination or Disproportionation

Primary and secondary unstable molecular fragments formed in the cracking reactions
could be stabilized in several ways. Recombination or disproportionation of unstable
fragments is one simple way. As a result of recombination the molecular weight and
branching of products might be significantly increased. It is important to note that both
recombination and disproportionation are second-order reactions according to reaction
kinetics.
Cyclization, aromatization or polycondensation are other ways of termination. Basi-
cally cyclic alkenes, alkenes, mono and polynuclear arenes or coke are formed in these
reactions. Termination reactions are principally controlled by the properties of polymers
and the temperature.
3 CATALYSTS
3.1 MONOFUNCTIONAL CATALYSTS
Monofunctional catalysts are catalysts having only the cracking property. Their struc-
ture may be crystalline or amorphous. Typical crystalline cracking catalysts are zeolites.
Amorphous catalysts are alumina-silicate, magnesium-silicate, titanium-silicate, titanium-
alumina-silicate, titanium–alumina, silica–alumina dispersed in alumina, alumina-borate
and other oxides with acidic characteristic. Usually the acidity of catalysts and the C–C
cracking function is increasing in the order Al2 O3 <Al2 O3 -halogen<SiO2 -Al2 O3 <zeolite.
Zeolites are natural or artificially produced microporous crystalline silica–alumina with
ion-exchange, molecule filter or sorption properties. The production of artificial zeolites
is carried out at controlled parameters (temperature, pressure, pH, etc.) by the reaction of
stoichiometric silica-halides or tetrahydro-silicate and sodium-alumina. The other impor-
tant parameter is the reaction time because the degree of crystallinity and pore structure
of zeolites is basically affected by the reaction time. The structure of zeolite is composed
of AlO4 and SiO4 tetrahedra which are connected with others through common oxygen
atoms. In the final step of formation of catalyst cations without catalytic activity (tetrahe-
dral and alkali-earth metals) have been replaced into elements possessing catalytic activity
(lanthanum, cerium, neodinium, etc.). Nevertheless generally inactive cations are replaced
by hydrogen ions. Cations are first changed with NH4 + , which are transformed by the
heat treatment.
Compared with amorphous catalysts, zeolite-based catalysts have the following advan-
tages: better thermal stability, better selectivity in respect to volatile products and resis-
tance to catalyst poisoning, greater acidity (resulting in greater cracking activity). In
general ZSM-5, mordenite, X, Y, β, ω, mezoporous zeolites (e.g. MCM-41) were used.
The high surface area and porosity of catalysts play an important role in forming of
the structure of cracked hydrocarbons. There are several properties of catalysts that are
important to cracking (acidic sites of macropores, micropores). The catalyst selectivity is
affected by the crystalline structure of zeolites and their characteristics.
Cracking of large macromolecules of polymers gets started at the amorphous acidic sites
of the catalysts, then further cracking may proceed on the crystalline part of the catalysts
if molecules have such small size that they can get into the pores of the catalyst. Strong
acidity favours the cracking of heavier fractions. Acidity of catalysts is expressed by the
ratio of Si/Al. The acidity increases with greater Si/Al. One method of increasing the
acidity of the catalyst is to decrease of alumina content (e.g. with ammonium-hexafluoro-
silicon or silicon-tetrachloride). Furthermore the pore size and ion-exchange property
decreases while acidity and thermal stability increase with decreasing concentration of
aluminium. Table 9.7 shows the main properties of some preferred polymer cracking
catalysts.
As mentioned above the structure of zeolite and its pore size fundamentally determine
the cracking property of the catalyst. The difference in activity of mordenite and zeolite
catalysts (e.g. HZSM-5, Y-zeolite) is unambiguously due to variation in structure [1].
Mordenite contains pores of relatively large size (about 7 × 8 Å), while the pores of
240 N. MISKOLCZI
Table 9.7 Physicochemical properties of the catalysts [9, 11, 47, 48]
Catalyst HZSM-5 β-zeolite FCC MCM-41 SA HY HNZ

Commercial HZSM-5 β-zeolite Engelhard MCM-41 Silica Y zeolite Clinoptilolite
name catalyst catalyst FCC catalyst alumina catalyst catalyst
catalyst
Si/Al 31 39 12.9 45 36 3 4.0
Pore size 0.55 0.64 2.4 2–12 0.74
(nm)
BET area 361 613 151 1164 261 583 271
(m2 /g)
Surface area 7 25 73 9
(m2 /g)
Pore volume 0.18 0.35 78 0.79 0.97 0.26 0.107
(cm3 /g)
Micropore 0.17 0.24 0.23
volume
(cm3 /g)
Crystal size 3 0.20 0.2–2 0.50
(µm)
Acidity 0.52 0.32 0.22 0.24 0.37
(mequiv of
NH3 /g)
Tmax . (◦ C) 470 422 338 302 300
ZSM-5 are smaller (about 5 × 5 Å). The pore size basically determines the length of
products. Generally the greater the pore size the longer the hydrocarbons formed. Not only
the pore size of catalysts is important, but also their geometry. As is well known the acidity
of catalysts mainly determinates the cracking behaviour of C–C bonds and the probability
of β-scission. However, the amorphous part of catalysts fosters the isomerization and
aromatization reactions. The high yield of gases observed with the use of amorphous
silica–alumina without 3D structural pores is explained with its great acidity. On the
other hand the low coking is the consequence of the catalyst surface which is free from
complicated pore structure on which the coke can be deposited with difficulty.
It is important to note that the reaction rate of thermocatalytic cracking decreases with
reaction time. In general it is the consequence of the blocking of active sites of catalysts
by coking.
The ZSM-5 catalyst shows quite high selectivity in the formation of paraffins and
olefins and branched hydrocarbons, while the yield of gases is also high. Both high yields
of gases and lighter liquids are the consequence of the large microporous surface area.
Another important parameter is the catalyst grain size and its distribution. There is
less area for cracking of C–C bonds in the case of greater catalysts particle size. For
example lighter hydrocarbons are formed with considerably higher yield in cracking
reactions of waste polymer over smaller sized catalyst [1]. Furthermore, higher concen-
tration of unsaturated hydrocarbons was found due to more β-scission. On the other hand
some other catalysts show great efficiency in the formation of unsaturated hydrocarbons:
ZSM-5, silica–alumina, MCM-41.
The further utilization of products obtained by degradation of polymers (wastes and
by-products of the plastic industry) is not solved yet. One possibility of their utilization
is fuel-like application or mixing in fuels as blending components. It is important to
Table 9.8 The change of properties of products
Property Presence of catalysts Increasing temperature

Density ⇓ ⇓
Viscosity ⇓ ⇓
RON ⇑ ⇑
MON ⇑ ⇑
Cetane number ⇑ -
Pour point ⇓ -
S content - -
N content - -
⇓: decreasing in property, ⇑: increasing in property, -: no change in property
note that before blending the high olefin content is to be saturated with hydrogen, or
hydroisomerized. These steps result in a high-quality synthetic diesel fuel, with high
cetane number, and theoretically free from sulfur, nitrogen and metals. In practice these
fractions generally have very low heteroatom content, even if the raw material was pure
and not waste, because some polymers contain, e.g. sulphur containing anti-flame or
antioxidant additives etc. Therefore the determination of practical properties (density,
viscosity, pour point, RON, MON, cetane number, impurities etc.) of products obtained
by cracking of polymers is important. However, there are considerably few references in
respect to these properties. One reason of this fact is that the measurement of practical
properties needs a relatively large quantity of products, not produced in most experimental
work. The change of some main properties of products is shown in Table 9.8.
It can be stated that generally the presence of catalysts is favourable and increasing
temperature might be favourable for further fuel-like utilization in respect of products
in the same boiling point range. The decrease of density, viscosity and partly the pour
point is due to the greater cracking of C–C bonds. On the other hand the isomerization
of carbon framework may also cause a decrease in the pour point.
The octane number is a quite important property of the products. The octane number of
light liquid fractions increases in the presence of catalysts, but considerable differences
could be observed in respect to RON and MON depending on the catalyst properties.
The research octane number of light liquids changed between 60 and 115 in the case
of cracking at 415◦ C in a batch reactor using different catalysts [1, 11]. Principally the
concentration of aromatics, n-aliphatics and branched hydrocarbons determines the octane
number. Increasing concentration of branched compounds and aromatics resulted in higher
RON and MON. On the other hand too high a concentration of aromatics is unfavourable
because of their high sensibility.
3.2 BIFUNCTIONAL CATALYSTS
Bifunctional catalysts have a cracking function and an other (e.g. hydrogenation) func-
tion. Generally the bifunctional catalysts used for thermocatalytic degradation of polymers
are usually impregnated transition metals on silica–alumina or zeolite. The cracking and
isomerization function is provided by an acidic support, whereas the other is provided
by metals. The hydrogenation or aromatization activity of catalysts is determined, among
242 N. MISKOLCZI
other factors, by metal type, amount of metal used, the degree of metal dispersion, the
location of metal on support or metal–support interaction. On the other hand the concen-
tration of metal across the diameter of catalyst grains also important. There are three cases
of concentration distribution: eggshell (metals only on the inside of support), eggwhite
(the maximum concentration of metal between one-half and one-quarter of grain diame-
ter) and eggyolk (the maximum concentration of metal within one-half of grain diameter).
At the same metal content considerable differences were observed in the concentration
distribution in the catalysts.
Numerous metals have been evaluated as bifunctional catalysts. Those used are noble
metals and non-noble or transition metals. Platinum and palladium have the highest cat-
alytic activity. The noble metal content is usually 1% or less, whereas that of non-noble
metals is larger 1–30%. The concentration of dispersed metal on supports plays an impor-
tant role in the activity of the catalyst, e.g. the activity of hydrogenation/dehydrogenation
increases then decreases with the concentration of metals. There are some typical reactions
of bifunctional catalysts.
(A) Isomerization
Paraffin isomerization
Naphtene isomerization
CH3
(B) Dehydrogenation
R R
+ 3H2
(C) Dehydrocyclization
+ 3H2
(D) Hydrocracking
C10H22 + H2 C4H10 + C6H14
(E) Dealkylation
+ C3H8
It is known that not only the quality of metals, but also their location on the support is
an important parameter in respect to cracking behaviour. For example it was found during
the investigation of platinum-impregnated Al2 O3 , SiO2 -Al2 O3 and activated carbon that
using Al2 O3 support the yield of aromatics was significantly higher than in other cases
and the yields of i-alkenes was 2.26 and 5% with the use of Al2 O3 , SiO2 -Al2 O3 and
activated carbon, respectively [52].
3.3 SOLID ALKALIS
Solid alkalis might catalyse the cracking reactions of polymers as is the case with
acidic catalysts. According to experimental work solid alkalis catalyse the degradation
of polystyrene more efficiently than acidic catalysts [53]. This phenomenon could be
explained by differences in the cracking mechanism of polymers. The main components
in the oils obtained by solid acids were styrene monomer and dimer. Since cracking of
hydrocarbons on solid acids has been explained in terms of β-scission of C–C bonds [19,
20], these were probably produced by β-scission of C–C bonds in the PS main chains as
follows:
−CH2 −CH −CH2 −CH −CH2 −CH −CH2 −CH −CH2 −
+
−CH2 −CH −CH2 −CH2 −CH2 −CH −CH2 −CH −CH2−
−H*
acids
+
+
CH2 −CH −CH2− CH2= CH
On the solid bases, the fraction of styrene monomer found in the product oils increased
to about 75 wt%, and the fraction of styrene, including both monomer and dimer, increased
to about 90 wt%. Partially because there was no formation of benzene and indane deriva-
tives in the oils obtained using solid bases or by simple thermal degradation, and partially
because of the considerable proportions of styrene dimer in those oils, it can be concluded
that the degradation on solid bases probably proceeds by a route similar to that for the
simple thermal degradation reaction, i.e. by depolymerization. Thermal degradation of
PS starts with a random initiation to form polymer radicals [21, 22], but the catalytic
degradation on solid bases may start with the formation of carboanions by the elimination
244 N. MISKOLCZI
of a hydrogen atom of the PS adsorbed on base sites as follows:
− −
−CH −CH2 −CH −CH2 − −C − CH2 −CH −CH2 − − C=CH2 −CH −CH2 −CH −CH2 −
−H*
bases
+
−
−C −CH2 −CH −CH2 − CH2=CH
The difference in the fraction of residues formed by thermal degradation and by catalytic
degradation on solid bases is due to the fast degradation of the vaporized fragments of
PS on base sites. Studies on the relationship between base strengths and their catalytic
activities for HCl elimination of 1,1,2-trichloroethane revealed the important role of base
sites for hydrogen atom elimination from 1,1,2-trichloroethane [23]. Although the base
strengths of solid bases employed in this work have not yet been measured, the higher
yields of styrene from PS may be ascribed to the stronger base sites on the surface of the
solid bases. From some alkalis BaO proved to be the most efficient, and polystyrene was
converted into monomer with the yield of more than 90% at 623 K.
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(2002).
49. S. Karagöz, J. Yanik, S. Ucar, M. Saglam and C. Song. Catalytic and thermal degra-
dation of high-density polyethylene in vacuum gas oil non-acidic and acidic catalysts,
Applied Catalysis A: General, 242, 51–62 (2003).
50. G. Audisio, F. Bertini and P. L. Beltrame, Catalytic degradation of poliolefins,
Makromol Chem., Macromol. Symp. 57, 191–209 (1992).
51. J. Schirmer, J. S. Kim and E. Klemm, Catalytic degradation of polyethylene using
thermal gravimetric analysis and a cycled-spheres-reactor, Journal of Analytical and
Applied Pyrolysis, 60, 205–217 (2001).
52. Y. Uemichi, Y. Makino and T. Kanazuka, Degradation of polyethylene to aromatic
hydrocarbons over metal-supported activated carbon catalysts, Journal of Analytical
and Applied Pyrolysis 14, 331–344 (1989).
53. H. Ukei, T. Hirose, S. Horikawa, Y. Takai, M. Taka, N. Azuma and A. Ueno, Cat-
alytic degradation of polystyrene into styrene and a design of recyclable polystyrene,
with dispersed catalysts, Catalysis Today 62, 67–75 (2000).
54. N. Miskolczi, Fuel-like feed stocks from plastic wastes, World Petroleum Congress
1st Youth Forum, Beijing, China, 24–27, October 2004.
PART III
Quality of Fuels
10
Production of Gaseous and Liquid

Fuels by Pyrolysis and Gasification
of Plastics: Technological
Approach
C. GISÈLE JUNG AND ANDRÉ FONTANA
Université Libre de Bruxelles, Solvay Business School – Centre Emile Bernheim, 50,
Av.F.D.Roosevelt, 1050 Brussels, Belgium
1 INTRODUCTION
The carbonization of a product consists in heating it in a confined atmosphere, i.e. in the

absence or lack of oxygen. When heating a material above 300◦ C in the absence of air,
the organic material decomposes in three phases: gas, liquid and solid.
In the pyrolysis processes, a thermal degradation occurs between 400 and 600◦ C in the
complete absence of oxygen. These processes are characterized by the indirect heating of
the material through the furnace wall (or pipes). The pyrolitic products, the solid (mix
of char metals and mineral matter) and the hot gases (condensable and noncondensable
mixture), are collected. Their relative proportions depend on the nature of the material,
the applied technology and the pyrolysis conditions, i.e. temperature, pressure, heating
rate, etc. The reductive atmosphere of the furnace is mainly a function of the pyrolitic
gas composition.
In the gasification processes, the material is directly heated at higher temperatures
(800–1000◦ C) by partial combustion of the contained carbon into carbon monoxide. A
limited amount of air (or oxygen) is admitted to the furnace according to the stoichiometry
(formation of CO2 and H2 O) so that the reductive atmosphere in the furnace is governed
by the ratio CO/CO2 .
Wood carbonization is a very well known process, used in the past for the production
of charcoal in primitive extractive metallurgy. In this case, the volatile matter and the
water are extracted from the wood, leaving solid charcoal.
252 C.G. JUNG AND A. FONTANA
The carbonization of a sample proceeds progressively from the outside to the inside: it
will depend on the heat transfer to the material, but also on the heat transfer inside the
material. The residence time at the selected temperature is then of major importance in
order to complete the carbonization. For each kind of material, the residence time has to
be increased with its dimensions. If the residence time is too low, incompletely carbonized
material will be found at the heart of the piece.
Slow reactions at very low temperature maximize the solid yields, as in charcoal pro-
duction since antiquity. Changing the heating rate, temperature, pressure and residence
time leads to substantial modifications in the proportions of the gas, liquids and solids.
High heating rates (up to 1000 K/min) minimize the char formation and rapid quenching
favours the condensation of the liquid phase before the cracking into gaseous products.
Table 10.1 gives a general overview of the different kinds of processes (hydrogenation
and reactive processes are not included).
It is then very difficult to compare the gas, liquid and solid yields obtained for a
specific material by different authors as the operating conditions can be very different
(mass between a few milligrams to few grams, heating rate from a few K/min to tens of
K/sec, etc.).
The use of polymers has increased by a factor of about three since 1980 and life-cycle
analysis shows that energy and raw material saving could be reached by the reprocessing
of plastics recovered from waste streams. Today, PVC, PE and PET are easily sorted from
different waste streams for reprocessing, but all sorting plants evolve large quantities of
mixed plastics. The main conditions for efficient material reprocessing concern the purity
of the recycled feedstock, i.e. the quality of the sorting process. For a lot of waste streams,
as well as for sorting plant refuse, it is not economic to separate the different kinds of
polymers. This explains the large amount of plastic waste landfilling in Europe. When easy
and cheap plastic waste sorting is feasible to produce high-quality secondary products,
material reprocessing is the best solution. When wastes containing large quantities of
plastics are not suitable for sorting, the main alternative to landfilling is incineration,
but the high net calorific value of this kind of waste could be a major problem. For
mixed plastics low in PVC, energy valorization (upgrading) in cement kilns or in the
steel industry is useful. An alternative way consists in pelletizing the mix in order for it
to be gasified, but the preparation costs are relatively high.
Another cleaner alternative consists in producing solid, liquid and gaseous fuels by
pyrolysis. The solid fuel could be upgraded by mechanical separation of metals and min-
erals in order to produce a cheap feedstock to a classical gasifier. Moreover, selected addi-
tions during pyrolysis could entrap pollutants such as chlorine and heavy metals [1–3].
The main advantage of pyrolysis over direct combustion in a waste-to-energy unit is a
tremendous reduction in the volume of product gases (10- “to” 20-fold). This leads to a
significant reduction in the complexity of the exhaust gas purification system. Moreover,
pyrolysis of waste containing plastics could be performed with less charge preparation,
so that minerals and metals are easily separated during the solid fuel conditioning and
less ash are produced.
The thermal degradation of polymers has been extensively studied for different pur-
poses, performed by analytical pyrolysis for information on the kinetics and mechanisms
of degradation and has been extended during the last few decades to studies of the catalytic
effects taking place under pyrolysis of complex waste materials [4,5].
Table 10.1 Pyrolysis processes
Process Feed size Moisture Heating Residence Temperature Pressure Products

rate time (◦ C)
Slow carbonization Large Very low Days 450–600 Atmospheric Charcoal
Slow pyrolysis Medium <200 mm <15% 10–100 K/min 10–60 min 450–600 Atmospheric/vacuum Gas, oil, char
Fast pyrolysis Small <1 mm <10% Up to 1000 K/s 0.5–5 s 550–650 Atmospheric Gas, oil, (char)
PRODUCTION OF GASEOUS AND LIQUID FUELS
Flash pyrolysis Small <1 mm <10% Up to 10 000 K/s <1 s 450–900 Atmospheric Gas, oils, (char)
253
Table 10.2 Influence of operating conditions on carbonization yields
of polyethylene
Slow Fast Slow Fast

(500◦ C) (500◦ C) (700◦ C) (700◦ C)
Gas (wt%) 10 10 15 50
Liquid (wt%) 88 90 85 50
Solid (wt%) 2 0 0 0
This section is dedicated to a survey of the literature on carbonization product yields.

Very large discrepancies can be seen between the results obtained by different authors in
the carbonization yields for the same material (Table 10.2).
The following section reviews the literature data summarizing the behaviour during
carbonization of five individual polymers, i.e. polyethylene (PE), polypropylene (PP),
polystyrene (PS), polyvinyl chloride (PVC) and polyethylene terephthalate (PET). For
each polymer, results will first be presented for flash pyrolysis then for slow pyrolysis by
the isothermal and dynamic methods.
In slow pyrolysis, temperatures are generally lower than for flash pyrolysis, but res-
idence time is longer. Meanwhile, there are two different methods. One method is the
isothermal–static method where the charge is directly heated at a given temperature
and maintained during a certain time while in the dynamic method (TGA) the charge is
progressively heated.
2 LITERATURE REVIEW ON PLASTICS CARBONIZATION
The thermal decomposition of polymers which generates degradation products has been
largely studied during the last few years and a review of these results will be presented.
The literature shows the results on mass balance for the different products issued from
the polymer carbonization as well as phase composition, decomposition mechanisms
and kinetic data. Different techniques are used (dynamic or isothermal measurements)
such as thermogravimetry (TGA) or batch small-size pyrolysis reactors fixed-bed (static),
fluidized-bed (FB) and circulating extruder at atmospheric or low pressure. The prod-
ucts issued from different technologies are classified in two main categories ‘slow’ and
‘fast/flash’ pyrolysis. In summary, the review of the results from the literature performed
at laboratory scale shows the strong dependence of the carbonization products in relation
to the main process parameters such as final temperature, pressure, heating rate and resi-
dence time. A choice of several important polymers is made with regard to their common
use with the purpose of comparing the different carbonization processes able to produce
substitution fuels.
The physical characteristics of the plastic input influence the carbonization process. In
static conditions, the heating rate of small particles is higher than for large particles. In
this case, difficulties could occur for the extrapolation from small-scale carbonization data
to pilot- and industrial-scale units. The physical and chemical properties of the material
are of great importance in order to be able to evaluate the heat transfer from the reactor
inside the material.
PRODUCTION OF GASEOUS AND LIQUID FUELS 255
2.1 POLYETHYLENE (PE)
For flash pyrolysis of PE, the mass balance at different temperatures is presented in
Table 10.3. G, L and S are respectively the gas, liquid and solid phases.
An increase in temperature will favour the quantity of gas phase and will decrease the
liquid phase. The composition of the liquid fraction is presented in Table 10.4.
In the gas fraction, the main products are methane, ethylene, ethane and propene. It
is shown that by increasing the temperature, the propane and propene content decreases
while methane and ethylene increase.
The molar fraction of the monomer (ethylene) does not vary regularly with the temper-
ature. Kaminsky [11] and Conesa [12] find respectively 24 and 34% of methane between
650 and 790◦ C. Some discrepancies are observed in the results of Scott [6]; 45–55% of
methane is found in the same range of temperature; this can be explained by differences
in operating conditions (heating rate, residence time, etc.).
In the oil fraction, the main products (at 740◦ C) are benzene, toluene, naphthalene and
other aromatics [11].
Slow pyrolysis PE decomposition is presented in Table 10.5.
Table 10.3 PE flash pyrolysis: mass balance
Conditions Parameters Mass balance References

◦
Reactor type p (atm) T ( C) m (g) G (%) L (%) S (%)
FB 1 515 89.8 5.9 6
FB 1 530 7.6 92.4 0 7
FB 1 550 3 11.4 66.7 8
FB 1 550 3 21.4 53.2 8
FB 1 654 17.5 73.5 1.1 6
RCR 1 650 80 20 9
FB 1 730 51.2 37.5 2.1 6
FB 1 740 59.1 39.2 1.8 10
FB 1 740 59.9 39.8 0.9 10
FB 1 740 58.6 39.6 1.8 11
FB 1 760 55.8 42.4 1.8 11
FB 1 780 51.2 46.2 1.8 11
FB 1 790 61.5 32.8 0.2 6
FB 1 800 1 66.2 28.3 5.5 12
FB fluidized bed; RCR rotating cone Reactor
Table 10.4 PE flash pyrolysis: gas phase composition
T (◦ C) H2 CH4 C2 H6 C2 H4 C3 H8 C3 H6 C4 H10 C4 H8 Other CO2 CO References

(%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)
550 1.9 7.3 8.0 25.7 5.4 21.1 2.6 25.2 2.5 0 0 8
760 1.4 42.7 12.0 35.8 0.1 10.0 0.7 2.9 0.4 0 0 11
800 44.2 4.5 46.7 0.2 4.0 0.2 0.3 0 0 0 12
Table 10.5 PE slow pyrolysis decomposition: mass balance

◦
−8
TGA 10 405 0.1 2.5 86.1 11.4 13
TGA 10−8 450 0.1 3.1 95.5 1.4 13
Static 4–35 430 7.9 90.8 1.3 14
TGA 1 430 0.02 72∗ 15
TGA 1 440 0.02 47∗ 15
TGA 1 450 0.02 28∗ 15
TGA 1 460 0.02 10∗ 15
TGA 1 470 0.02 3∗ 15
TGA 1 480 0.02 0∗ 15
Static 700 16.8‡ 79.7‡ 16
Static 700 15.0# 84.3# 16
‡
HDPE; # LDPE; static: fixed-bed (batch static reactor)
∗
Value estimated using the TGA graph
100
Madorsky (low pressure)
80 Bockhorn (atm pressure)
Conversion x (%)
60
40
20
0
250 300 350 400 450 500 550
T (ºC)
Figure 10.1 PE slow pyrolysis conversion yield (%)
The conversion yield (x) is expressed by the ratio of the weight loss over the initial
mass. The evolution of the conversion yield versus the temperature is represented in the
Figure 10.1.
Figure 10.1 shows that the conversion is more efficient at lower temperature under
vacuum [13] than at atmospheric pressure under an inert atmosphere [14, 15]. This is
explained by the fact that volatilization is favoured at lower pressure.
In slow pyrolysis by the dynamic method, the temperature domain is generally large
and in this case, the main parameter is the heating rate. Table 10.6 indicates the tem-
perature interval for the decomposition of the PE defined between the temperatures T5
and T95 . These two temperatures are defined respectively as the temperature at which the
conversion starts (T5 at 5% conversion) and T95 (close to the end of conversion, at 95%).
The maximum rate of conversion occurs between T5 and T95 , at Tmax .
According to Wu [17], the decomposition interval lies between 390 and 490◦ C. The
lower temperature range found by Anderson [18] is related to lower pressure conditions.
Table 10.6 PE slow pyrolysis (dynamic method): characteristic parameters
Conditions Parameters Temperature References

◦ ◦ ◦
Reactor p (atm) Heating rate m (g) T5 ( C) T95 ( C) Tmax ( C)
(K/min)
TGA 1 10 0.02 420∗ 490∗ 470∗ 15
TGA 1 1 0.004 390–400∗ 450–460∗ 17
TGA 1 2 0.004 400–410∗ 465–470∗ 17
TGA 1 5.5 0.004 420–425∗ 490∗ 17
TGA 10−3 5 0.1 <340∗ 460∗ 18
∗
Values estimated using the TGA graph
The initial temperature for the decomposition of LDPE is lower than that of HDPE [17].
For the two types of PE, total degradation occurs at 490◦ C. The gas phase composition
in slow pyrolysis is presented in Table 10.7.
At 425◦ C, at a pressure of 10−4 mmHg, the main component is propylene, in larger
proportion than ethylene [20]. At higher temperature, the formation of alkanes is favoured.
In slow pyrolysis, the gas phase contains less methane and ethylene and more ethane and
propane than by flash pyrolysis (see Tables 10.4 and 10.7). The product yields obtained
in the literature by different authors for the PE for slow pyrolysis (Pinto, Madorsky,
Bockhorn, Tsuji and Williams) and fast pyrolysis (Kaminsky, Williams, Scott and Conesa)
are respectively presented in Figures 10.2 and 10.3.
Table 10.7 PE slow pyrolysis: gas phase composition

(%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)
425 0 27.2 9.1 11.6 18.3 22.4 5.3 6.0 0 19
500 6.49 7.53 13.8 13.2 17.4 28.9 7.5 5.2 0 20
500 5.69 2.93 11.2 5.6 20.7 15.5 20.8 15.7 0 20
700‡ 0.7 11.3 13.2 18.4 7.8 27.2 1.3 2.1 0 16
700# 0.3 7.6 11.1 26.6 8.9 26.6 2.1 13.3 3.4 16
‡
HDPE; # LDPE
100
80
Gas
60
Liquid
40
Solid
20
0
400 500 600 700 800 T (°C)
Figure 10.2 PE slow pyrolysis: product yields (%)

100
80
60 Gas
Liquid
40
Solid
20
0
400 500 600 700 800 T (°C)
Figure 10.3 PE flash pyrolysis: product yields (%)
100
80
60 Gas
40 Liquid
Solid
20
0
550 650 750 850
Figure 10.4 PE gasification: product yields (%)
During the slow pyrolysis of polyethylene, for a temperature increase from 400 to
700◦ C, the yield in liquid phase remains higher than 80% with a very small increase in the
yield of gas phase (less than 20%). On the other hand, in flash pyrolysis of polyethylene,
an increase of temperature from 550 to 700◦ C leads to a decrease of the yield in the liquid
phase to less than 40% with an increase in the yield of the gas phase up to 60%.
In the 1970s Sawagushi et al. [21] presented results and validated a kinetic approach
to the intensity function in the case of steam gasification of PE in a fixed-bed reactor.
These results are presented in Figure 10.4.
The maximum total gas yield reaches 75% at 700◦ C. In comparison with pyrolysis,
thermal gasification of polymers is also a suitable process because its products are of
simpler composition and have a narrower range of molecular weights.
By a two-stage pyrolitic gasification process (470 and 800◦ C), it is possible to improve
the quality of the gaseous products and the gas yield. In these conditions, the gas yield
reaches 80% [22].
2.2 POLYPROPYLENE (PP)
The flash pyrolysis of PP is realized at temperatures higher than 500◦ C. The mass balance
at different temperatures is presented in Table 10.8.
These results show that for temperatures in the range of 750◦ C, the proportions of the
three phases produced are constant. Gas and liquid fractions are close to 50% while the
solid fraction is less than 2%. The composition of the gas phase is presented in Table 10.9.
Table 10.8 PP flash pyrolysis: mass balance

◦
FB 1 510 6.3 93.7 0 7
FB 1 550 3 6.5 69.8 8
FB 1 740 49.6 48.8 1.6 11
FB 1 760 51.4 46.9 1.7 11
FB: fluidized-bed
Table 10.9 PP flash pyrolysis: gas phase composition

(%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)
550 3.7 6.8 6.9 22.8 10.3 16.6 4.0 30.0 0 8
740 1.4 56.9 8.1 28.0 0.2 7.5 0.8 0.8 11
At lower temperature, Williams [8] finds mainly ethylene, propane, propene and butene
as major components. Kaminsky [11], at higher temperature, finds mainly methane and
ethylene.
In slow pyrolysis, the experiments are conducted at constant temperature and the mass
balance is presented in Table 10.10.
In order to be able to compare the results, the conversion yields are presented in
Figure 10.5 after a residence time of 30 min in the reactor.
As for polyethylene, working at low pressure [23,24] shows that the decomposition of
polypropylene occurs at lower temperature compared with the results at atmospheric pres-
sure [25,26]. In both pressure conditions, the solid fraction is very weak for temperatures
higher than 400◦ C.
Table 10.10 PP slow pyrolysis: mass balance
Conditions Parameters Mass Balance References

◦
TGA 10−8 328 0.006 1.5 6.7 91.8 23
TGA 10−7 400 1 14.5 65.7 19.8 24
TGA 10−8 410 0.006 11.2 85.2 3.6 23
TGA 1 410 0.04 65 25
TGA 1 420 0.04 42 25
TGA 1 430 0.04 25 25
TGA 1 440 0.04 10 25
TGA 1 450 0.04 1 25
TGA 10−8 500 0.006 17.5 82.1 0.4 23
Static 700 3 13.6 84.4 0.2 16
Static: fixed-bed (batch static reactor)

100
80
Conversion x (%)
60
40
Bockhorn (atm pressure)
Madorsky (low pressure)
20
Tsuchiya (low pressure)
0
250 300 350 400 450 500 550
T (°C)
Figure 10.5 PP slow pyrolysis: conversion yield (%)
Table 10.11 PP slow pyrolysis (dynamic method): characteristic parameters
Conditions Parameters Characteristic temperatures References

◦ ◦ ◦
Reactor type p (atm) Heating rate m (g) T5 ( C) T95 ( C) Tmax ( C)
(K/min)
TGA 1 1 0.004 360∗ 440∗ 17
TGA 1 2 0.004 375∗ 455∗ 17
TGA 1 5.5 0.004 390∗ 480∗ 17
TGA 1 5 0.02 340 481 456 27
TGA 1 10 0.02 354 489 469 27
TGA 1 15 0.02 371 494 477 27
∗
By slow pyrolysis, the dynamic method is more appropriate to estimate the decomposi-
tion interval for the polypropylene decomposition. Table 10.11 indicates the temperature
interval for the decomposition of the PP defined between the temperatures T5 and T95
When the heating rate increases, the temperature interval for the decomposition is
displaced to higher temperatures. It can be seen that the decomposition of PP is totally
achieved at 490◦ C. Large quantities of the monomer are produced at low temperature
and it decreases at higher temperature. Ethylene becomes the main component in the gas
phase. Details of the gas phase composition are given in Table 10.12.
Table 10.12 PP slow pyrolysis: gas phase composition

(%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)
400 0 11.0 13.4 0 5.5 61.1 0.2 8.8 28
500 1.58 14.9 26.4 0.84 4.9 47.9 0.4 2.4 20
700 0.4 6.8 10.6 25.8 7.3 25.9 1.7 9.5 16
At higher temperature (700◦ C), in slow pyrolysis, the gas phase contains less methane
and more propane, propene and butene than by flash pyrolysis (see Tables 10.9
and 10.12).
The product yields obtained in the literature by different authors for the PP for
slow pyrolysis (Bockhorn, Pinto, Tsuji and Williams) and fast pyrolysis (Kaminsky and
Williams) are respectively presented in the Figures 10.6. and 10.7.
The carbonization of polypropylene is similar to that of polyethylene. During slow
pyrolysis of polypropylene and for a temperature increase from 400 to 700◦ C, the yield
in the liquid phase remains higher than 80% with a very small increase in the yield of
gas phase (less than 20%). On the other hand, in flash pyrolysis of polypropylene, an
increase of temperature from 550 to 700◦ C leads to a decrease of the yield in the liquid
phase down to 40% with an increase of the gas phase up to 60%. As presented for PE
(see Section 2.1), Sawagushi et al. [21] present the results of steam gasification of PP in
a fixed bed reactor (Figure 10.8).
The maximum gas yield reaches 65% at 650◦ C whereas the carbon deposit increases up
to 20–30%. These results show that the liquid yield decreases more rapidly than by flash
pyrolysis. By a two-stage pyrolitic gasification process (450 and 800◦ C), it is possible to
improve the quality of the gaseous products and the gas yield. In these conditions, the
gas yield reaches 74% [22].
100
80
60 Gas
Liquid
40
Solid
20
0
400 500 600 700 800
Figure 10.6 PP slow pyrolysis: product yields (%)
100
80
60 Gas
Liquid
40
Solid
20
0
400 500 600 700 800
Figure 10.7 PP flash pyrolysis: product yields (%)

90
80
70
60
50 Gas
40 Liquid
30
20 Solid
10
0
500 600 700
Figure 10.8 PP gasification: product yields (%)
Table 10.13 PS flash pyrolysis: mass balance including the yield of monomer, styrene

◦
Reactor type p (atm) T ( C) m (g) G (%) L (%) S (%) Styrene (%)
FB 1 520 0.1 23.0 0 76.8 29
FB 1 532 11.5 12.3 0 76.2 6
FB 1 550 3 0.7 71.4 0 8
FB 580 9.9 24.6 0.6 64.9 11
FB 1 615 15.7 10.6 0 72.3 6
FB 1 708 15.2 7.7 0 75.6 6
FB: fluidized-bed
2.3 POLYSTYRENE (PS)
For the flash pyrolysis of PS, the results in mass balance are presented in Table 10.13.
The yield of monomer is added because styrene is the major component during the
carbonization of PS.
A significant liquid phase is observed during the flash pyrolysis of polystyrene with
styrene as the main component [8]. Except for one experiment by Kaminsky [11] the
yield in styrene formed during the flash pyrolysis of PS (between 520 and 710◦ C) is near
75%. The major other products are aromatic compounds (oligomeric styrenes) [11].
The conversion yield x of polystyrene by slow pyrolysis after a residence time of
60 min is presented at different temperatures in Table 10.14.
By the dynamic method, the temperature intervals (T5 and T95 ) are determined and the
results are shown in Table 10.15 for PS.
From these results an average interval for the decomposition of PS is estimated between
330 and 425◦ C.
The main product yield (after slow or flash pyrolysis) is the liquid phase and Sawagushi31
found that this is mainly composed styrene monomers, dimers and trimers. For a residence
time of 60 min, increasing the temperature from 310 to 350◦ C increases the monomer fraction
up to 78%. Table 10.16 shows the proportions of these three components in the liquid phase
as a function of the temperature.
Table 10.14 PS slow pyrolysis: mass balance

◦
−9
TGA 10 335 0.006 95 30
TGA 10−9 345 0.006 88 30
TGA 10−9 350 0.006 82 30
TGA 10−9 360 0.006 43 30
TGA 10−9 365 0.006 59 30
Static 1 700 3 3.4 83.8 3.5 16
Table 10.15 PS slow pyrolysis (dynamic method): characteristic parameters

◦ ◦
Reactor type p (atm) Heating rate m (g) T5 ( C) T95 ( C)
(K/min)
TGA 1 1 0.004 330∗ 390∗ 17
TGA 1 2 0.004 345∗ 405∗ 17
TGA 1 5.5 0.004 336∗ 425∗ 17
TGA 10−3 5 0.1 370∗ 415∗ 18
∗
Table 10.16 PS slow pyrolysis: liquid phase composition (styrene)
T (◦ C) Styrene References
Monomer (%) Dimer (%) Trimer (%)
310 25.0 28.3 46.7 31
330 60.2 13.1 26.6 31
350 78.4 9.4 12.2 31
The styrene fraction is similar to that in flash pyrolysis at higher temperature [6,11].
McNeill32 studied the volatilization of PS under vacuum.
The survey of the literature results for the behaviour of polystyrene during slow pyrol-
ysis (Koo, Pinto, Takai, Tsuji and Williams) and for fast pyrolysis (Kaminsky, Scott and
Williams) are respectively presented in Figures 10.9 and 10.10.
It can be seen that during slow and fast pyrolysis of polystyrene, if the temperature
increases respectively from 400 to 700◦ C and 550 to 700◦ C, the yield in the liquid
phase remains higher than 80% with a relatively stable yield in the gas phase, less
than 20%.
By a two-stage pyrolitic gasification process (450 and 800◦ C) [22], the gas yield is very
low because styrene monomer, dimer and trimer hardly decompose in these conditions.
100
80
Gas
60
Liquid
40 Solid
20
0
400 500 600 700 800 T (°C)
Figure 10.9 PS slow pyrolysis: product yields (%)
100
80
Gas
60
Liquid
40
Solid
20
0
400 500 600 700 800 T (°C)
Figure 10.10 PS flash pyrolysis: product yields (%)
2.4 POLYVINYL CHLORIDE (PVC)
For the flash pyrolysis of PVC, the mass balance is presented in Table 10.17. The mass
fraction of the hydrogen chloride is included as it is one of the main products in the gas
phase.
In the same temperature range, the solid fraction found by Williams [8] is quite large,
with a low fraction of HCl compared with the results of Scott [6]. This could be explained
if carbonization is not totally complete in the first case. A higher temperature, the solid
fraction is reduced in favour of the gas and oil fractions. In the gas phase, the part of HCl
nearly reaches its theoretical yield. According to Williams [8] the oils contain principally
benzene and toluene respectively 22.1 and 9.6% by mass.
The results of the PVC decomposition in slow pyrolysis are presented in Table 10.18.
Bockhorn et al. [33,15] and Gimenez et al. [34] find a plateau between 310 and
380◦ C for about 40% (at 2 K/min) conversion which corresponds to the release of HCl.
Table 10.17 PVC flash pyrolysis: mass balance

◦
Reactor type p (atm) T ( C) m (g) G (%) L (%) S (%) HCl (%)
FB 1 520 28.3 6.3 9.1 56.0 6
FB 1 550 3 3.9 22.1 13.5 31.7 8
FB 1 740 6.8 28.1 8.8 56.3 11
Table 10.18 PVC slow pyrolysis: mass balance

◦
TGA 1 270 0.01 64∗ 15
TGA 1 290 0.01 57∗ 15
TGA 1 300 0.01 48∗ 15
TGA 1 310 0.01 45∗ 15
TGA 1 400 0.01 20∗ 15
TGA 1 410 0.01 12∗ 15
TGA 1 420 0.01 6∗ 15
TGA 1 440 0.01 3∗ 15
Static 1 700 55.4 31.7 13.8 16
∗
According to Williams [16] (at 25 K/min), after the dehydrochlorination step, a second
decomposition step starts at about 400◦ C [35–37]. This is explained by the rupture of
polyenic chains produced during the first step and the formation of benzene-derived com-
pounds [15]. The conversion yield x in slow pyrolysis of PVC is presented at different
temperatures in Figure 10.11.
By the dynamic method, Miranda [38], working between 1 and 20 K/min, finds a
plateau at 36% conversion. A weight loss of 64% is higher than the theoretical loss of
HCl. This is explained by some benzene formation during the dehydrohalogenation step.
The temperature at which the second decomposition step occurs is higher if the heating
rate increases.
According to Miranda [38], the proportion of solid depends strongly on the heating rate
(6.9–12.4% for heating rates respectively from 1 to 20 K/min). Analysis of the solid by
Williams [16] reveals a carbon content of 90.2% with only 2.9% ash.
100
80
Conversion x (%)
60 Bockhorn (1996)
Bockhorn (1999)
40
20
0
200 250 300 350 400 450 500 550
T (°C)
Figure 10.11 PVC slow pyrolysis: conversion yields (%)

2.5 POLYETHYLENE TEREPHTHALATE (PET)
Mass balance is presented in flash pyrolysis of PET at different temperatures in

Table 10.19. Results of Williams [8] and Kaminsky [11] show that the decomposition
of PET produces about the same quantities of gas and liquid with a proportion of solid
around 10%.
The composition of the gas phase is given in Table 10.20. According to Williams [8],
the gases contain carbon oxides (nearly 90%). These results are confirmed by those of
Kaminsky [11].
In the oils, benzene and toluene are the major components [11]. Bednas [39] finds alde-
hydes (formaldehyde and acetaldehyde) as major components at 700◦ C. If the temperature
rises 900◦ C, the amount of acetaldehyde decreases and carbon monoxide becomes more
important in proportion then carbon dioxide [39]. This is explained by the decomposition
of acetaldehyde in methane and carbon monoxide.
The results of the PET decomposition in slow pyrolysis are presented in Table 10.21.
As for flash pyrolysis, the proportion of solid remains important. The carbon content
is estimated at 84.9% with 5.9% ash [16].
The conversion yields x of PET [40–42] are presented at different temperatures in
Figure 10.12. It is important to take into account that the results by Dzieciol concern a
thermo-oxidative degradation in air (flow of 0.025 m3 /h for 20 min).
By the dynamic method, the results for PET are presented in Table 10.22 where the
conclusions are determined on the basis of TGA diagrams.
Table 10.19 PET flash pyrolysis: mass balance

◦
FB 1 550 49.1 39.4 12.8 8
FB 1 768 3 50.8 40.0 7.1 11
Table 10.20 PET flash pyrolysis: gas phase composition (%)

(%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)
550 2.1 1.8 0 3.1 0 2.6 0 0 0 37.8 52.6 8
768 9.2 14.6 0.4 0 0.1 0.1 0 0 0.1 37.5 38.1 11
Table 10.21 PET slow pyrolysis: mass balance

◦
FB 1 700 3 38.7 41.3 15.6 16
100
Villain
80 Arii
Conversion x (%)
Dzieciol
60
40
20
0
150 250 350 450 550 650 750
T (°C)
Figure 10.12 PET slow pyrolysis: conversion yields (%)
Table 10.22 PET slow pyrolysis (dynamic method): characteristic parameters

◦ ◦ ◦
Reactor type p (atm) Heating rate m (g) T5 ( C) T95 ( C) Tmax ( C)
(K/min)
TGA 1 10 0.02 430∗ 43
TGA 1 1–10 0.001 370∗ 450∗ 42
TGA 1 10 400 450 430 44
∗
Table 10.23 PET slow pyrolysis: gas phase composition (%)
T (◦ C) H2 CH4 C2 H6 C2 H4 C3 H8 C3 H6 C4 H10 C4 H8 C4 H8 CO2 CO References

(%) (%) (%) (%) (%) (%) (%) (%) (%) (%) (%)
700 12.4 3.6 0.1 4.0 0.2 0.2 0 0 0 41.4 38.1 16
850 0 11.6 0 2.6 0 0 0 0 0 36.5 48.7 45
The temperature interval estimated on the basis of these results lies between 370 and
430◦ C.
The gas phase composition is shown in Table 10.23. It consists mainly of carbon oxides
and consequently has a very low net calorific value.
2.6 PLASTIC MIXTURES
Two types of approach exist to study the behaviour of plastic mixtures during pyrolysis.
On one hand, some authors [46] work on plastic waste mixtures while other authors
[47] work on simulated mixed plastic waste prepared with a specific composition. The
proportions of the different polymers are based on mean values related to real waste
mixtures.
Table 10.24 Plastic mixtures composition and flash pyrolysis: products (%)
T (◦ C) PE PP PS PVC PET Other G∗ L∗∗ Wax S References

(%) (%) (%) (%) (%) (%) (%) (%) (%) (%)
500 62.5 7.29 13.5 11.46 5.21 0 11.6 37.8 17.3 2.8 48
550 62.5 7.29 13.5 11.46 5.21 0 25.9 38.5 18.6 5.9 48
600 62.5 7.29 13.5 11.46 5.21 0 44.7 34.3 8.7 7.6 48
650 62.5 7.29 13.5 11.46 5.21 0 89.6 20.5 0 48
700 62.5 7.29 13.5 11.46 5.21 0 69.3 18.4 0 48
717 67.6 1 1.7 9.3 20.4 40.4 19.0 40.6 49
730 65 25 1.2 2.8 6 35 51.3 13.2 50
738 65 25 1.2 2.8 6 38 50 12 50
787 67.6 1 1.7 9.3 20.4 39.7 23.2 37.1 50
790 57 19 14 5 5 43.7 30.9 25.4 11
∗ ∗∗
Gas with HCl; L: liquid phase or oil
Table 10.24 summarizes the product yield after flash pyrolysis of the simulated mixed
plastics in relation to pyrolysis temperature.
Williams [48,8] finds an increased production of gas formation on increasing the tem-
perature up to 650◦ C. There was no more wax formed from 650◦ C [48]. The amount
of HCl measured decreased from 1.8 to 0.5% in this temperature range. Scott et al. [6]
pyrolysed plastic waste in a fluidized-bed at 580◦ C with a HCl production of 34.6%,
suggesting that the PVC content was in higher proportion in the plastic mixture input.
The theoretical yield of pyrolysis products calculated on the basis of the additivity of
individual plastic pyrolysis at 550◦ C is in good agreement with the products yields for the
mixed plastics pyrolysis. However, with increase of the pyrolysis temperature, the char
and gas yield are higher (with a decrease of oil and wax yields), suggesting that there
are some interaction of the plastics in the mixture during pyrolysis [8]. Increasing the
pyrolysis temperature leads to an increase of the aromatics, and a decrease of alkanes,
alkenes and alkadienes in the oils.
Using slow pyrolysis, the results of Koo et al. [51] (atmospheric pressure, 20 g,
48 K/min and 70 min) of various proportions of PE/PS at 5 and 700◦ C are presented
in Figures 10.13 and 10.14.
PE/PS - 500°C (Koo)

100
80
60 Solid
% Liquid
40
Gas
20
0
% PS
0 50 100
Figure 10.13 PE/PS product yields: 500◦ C

PE/PS - 700°C (Koo)

100
80
60 Solid
% Liquid
40 Gas
20
0
% PS
0 50 100
Figure 10.14 PE/PS product yields: 700◦ C
PE/PS - 700°C (Williams)

100
80
60 Solid
% Liquid
40
Gas
20
0
0 50 100
% PS
Figure 10.15 PE/PS product yields (%): 700◦ C
PP/PS - 700°C (Williams)

100
80
Solid
60
% Liquid
40 Gas
20
0
0 50 100
% PS
Figure 10.16 PP/PS product yields (%): 700◦ C
Mechanisms of degradation of blends of PS and PP have been studied by DSC and the
kinetics of degradation of the blends matched with that of virgin PP for more than 50%
PP [52]. On the other hand, the results of Williams [53,54] (atmospheric pressure, 3 g,
25 K/min and 60 min) for 1:1 mixtures of PE/PS, PP/PS,PVC/PS and PET/PS at 700◦ C
are presented in Figures 10.15–10.18. These results show a deviation from additivity in
the case of PE/PS mixtures.
PVC/PS - 700°C (Williams)

100
80
Solid
60
% Liquid
40
Gas
20
0
0 50 100
% PS
Figure 10.17 PVC/PS product yields (%): 700◦ C
PET/PS - 700°C (Williams)

100
80
60 Solid
% Liquid
40
Gas
20
0
0 50 100
% PS
Figure 10.18 PET/PS product yields (%): 700◦ C
The results of Williams (Figure 10.15) show that for PE/PS mixtures (1:1) more gas
and less liquid are produced than by the pyrolysis of the individual polymers at 700◦ C.
This is in contradiction to Koo’s results (Figure 10.14). For pure PS, the results are quite
similar. The main differences are found for pure PE in the in proportions of gas and liquid
phases (Figures 10.14 and 10.15). The contradiction in these results could be explained by
the fact that the experimental conditions are quite different (3 g, 25 K/min for Williams
and 20 g, 48 K/min for Koo) and that PE is more sensitive to the experimental conditions
(see Figures 10.2 and 10.3). Indeed, the hot gas and oils are rapidly extracted co-currently
from the reactor with the nitrogen flow [16] in the experiments of Williams whereas they
are extracted counter-currently and remain longer in the hot zone of the reactor, being
partially cracked into smaller entities, in Koo’s experiments [51]. For the other binary
mixtures of plastics, there is less deviation from additivity.
Dodson et al. [55] using TGA found a stabilization effect of PS when mixed with PVC
heating up to 500◦ C (10 mg sample, 10 K/min). In a pilot extruder, Kuwabara et al. [56]
show higher dechlorination rates of PVC mixtures with PE, PP and PS rather than the
binary systems PE–PVC. HCl seems to inhibit the pyrolytic reaction of PE, resulting in
a lower conversion rate [57].
Differences between flash and slow pyrolysis have been pointed out, especially for PE
and PP. Products yields by slow pyrolysis at high temperature (700◦ C) are similar to
those in flash pyrolysis at low temperature (500◦ C). Flash pyrolysis at higher temperature
increases the gas yields.
The results in the literature for most of the polymers show that, at atmospheric pressure,
the pyrolysis temperature does not have to exceed 600◦ C to reach total carbonization.
Parameters such as heating rate and residence time will differ among different authors and
some discrepancies still exist for the individual polymers. On the other hand, for polymer
mixtures, interaction between polymers appears during pyrolysis between polymers with
more gas produced and a better quality of the oils. These interactions are not yet explained.
3 TECHNOLOGICAL APPROACH
Pyrolysis and gasification are thermal degradation or carbonization processes [58–60]

working at medium temperatures under controlled atmosphere. Pyrolysis processes involve
indirect heating and recovery of pure pyrolysis products. Gasification processes involve
direct heating and lead to the dilution of the pyrolitic gases by partial combustion products
and nitrogen. A predictive carbonization model is presented in order to estimate the solid
and gas yields during the pyrolysis of the waste mixture and also the net calorific value
of the char and the gases.
The scaling-up of the results from the predictive model and from laboratory-scale results
have to take into account the different types of technologies.
3.1 PREDICTIVE CARBONIZATION MODEL [61]
Let us consider that a mixed waste contains different components, each being characterized
by its water content W , volatile matter VM∗ and ash content A∗ (the last two being on a dry
basis). Assuming that each component behaves independently and using the hypothesis of
additivity, it is possible to estimate the product yields after carbonization. Moreover, this
model takes into account the different carbonization yields for each component (according
their physical and chemical properties). From the C, H, O analysis of each component
(easier than that for the rough mixture), it is possible to estimate the net calorific value
of the char and the gases from the waste pyrolysis.
Taking into account the proximate analysis of the input material (water content W ,
volatile matter VM∗ and ashes content A∗ ), it is possible to estimate the fixed carbon CF ∗ :
CF ∗ = 100 − VM∗ − A∗ and the dry matter DM = 100-W.
Assuming that, during slow carbonization, the volatile matter is oriented with the water
in the gas phase and that the fixed carbon is in the solid phase with the ashes, the mass
balance could be estimated:
Mass of gas phase:
DM
MG = VM + W with VM = VM∗
100
Mass of solid phase (char):
DM
MS = CF + A with A = A∗ and CF = 100 − VM − A
100
If the temperature and/or the residence time are too low, the carbonization will be
incomplete and some volatile matter will remain in the char. If ϕ is the proportion of
VM entrapped in the char, the carbonization yield is α = 1 − ϕ. One possible way of
estimating the carbonization yield could be a TGA analysis at low heating rate for the
same input material. Sampling is then the main problem for milligram sample analysis.
Therefore, the use of larger scale TGA devices up to 5 g is recommended [58]. This model
has been validated for used tyres, biomass, Tetrapak boxes, mix of plastic wastes, etc.
and gives rather good agreement (less than 10% difference) with experimental results for
slow pyrolysis [62].
3.2 SCALE-UP
Moving from batch experiments to continuous reactors, one major problem is to ensure
a good flow of the material inside the reactor (mechanical aspect). The efficiency of the
global process depends not only on the material transport in the reactor, but also on the
heat transfer to and inside the material. The feed preparation is then essential as well as
the characterization of the eventual side material (water, metals, minerals, pollutants, etc.).
The different pyrolysis and gasification technologies, selected in relation to the waste
input, generate different kinds of products that will have to be upgraded into sub-
stitution fuels. The solid fuel could be upgraded by mechanical separation of metals
and minerals in order to produce a cheap feedstock to a classical gasifier. Moreover,
selected additions during pyrolysis could entrap pollutants such as chlorine and heavy
metals [2,3,63,64].
Interactions during pyrolysis of waste containing plastics in the presence of wood
contaminated by chlorine and heavy metals have been studied at laboratory scale. The
chlorine capture and the inhibition the chlorination of heavy metals has been validated at
pilot scale [1].
The quality of the gases and oils has to be certified by analytical tests in order to be
accepted for valorization as substitutions fuels [5].
The results in slow pyrolysis for various waste at laboratory scale (PE, PVC, sorting
residues, wood, tyres, Tetrapak, etc.) are in very good agreement (less than 10% difference)
with those obtained at pilot scale (Cutec Institute, Clausthal, 25 kg/h; Thide, Vernouillet,
500 kg/h and Traidec, Ste Foy l’Argentière, 500 kg/h). Furthermore they also give good
agreement with industrial practice for slow pyrolysis (Noell, Salzgitter, 2-5 t/h, and others).
3.3 PYROLYSIS TECHNOLOGIES
The different technologies involve indirect heating and are characterized by the method of
heat transfer to the material and by the method used for mixing the charge in the furnace.
Slow pyrolysis can be performed in rotary kilns, or in static furnaces equipped with moving
blades or screws for mixing the material and increasing the heat transfer. Fast or flash
pyrolysis is usually performed in fluidized-bed furnaces or in vortex ablative furnaces.
As pyrolysis is a pretreatment, the gas, liquids and solids issued from this treatment will
need a post-treatment for further valorization.
3.3.1 Slow Pyrolysis

Rotary kilns are in common use all over the world for various applications. This technology
was developed since the 1980s by Karl Kiener, Noell, Mannesmann (actually Technip),
Babcock, Mitsui, VTA (Veba Öl), PKA, and Thide. For external heating, all technologies
propose fuel or natural gas burners except for Babcock (Burgau Plant, Germany) and Thide
(Nakaminato, JPN, Arras Plants; France) who adopted the furnace heating by exhaust gas
issued from pyrolitic gas combustion. PKA proposed burners fed by cracked pyrolitic
gases. Several pilot installations exist and are electrically heated. Some processes use a
water-tight system for the char recuperation. Minerals and metals could be easily discarded
from the char either by dry screening, or by wet elutriation.
All the processes developed during the 1980s included series of condensers in order to
recover the different fractions of hydrocarbons contained in the pyrolitic gases. They were
efficient, but this gas post-treatment was not economically viable according to petroleum
prices. The hot pyrolitic gases are usually burned in a post-combustion chamber, part
of the energy being used for the furnace heating, the rest for steam production. A sim-
ple gas cleaning system is present in order to fulfil the emissions regulations. One of
the main problems encountered is tar deposits in the gas extraction pipes. Therefore,
the main approach today is to keep the gases hot (heated pipes) and to burn the hot
pyrolitic gases directly. In the PKA system, the pyrolitic gases are cracked and con-
verted in noncondensable hydrocarbons. Now, according to increasing fossil fuels market
prices, the recovery of hydrocarbons from the pyrolitic gases becomes more and more
realistic.
The dimensions of these kilns are related to the nature of the material input and the
capacity. Different furnace modelling approaches are recently proposed in the litera-
ture [65–67]. The design of the kiln is calculated to obtain complete carbonization of
the product. Then, the power of the boiler is dimensioned according to the energy val-
orization choice. So, a plant is characterized either in terms of output power, or in terms
of capacity for a defined waste input. Table 10.25 gives examples of different rotary kiln
dimensions
Rotary kilns are commonly used for different waste streams such as contaminated soils,
petroleum residues, car shredder refuse, municipal solid waste (MSW) mixed with sludge
and industrial waste, used tyres, etc.
Moving-bed furnaces can be classified in three families:
• fixed vertical cylindrical furnaces equipped with rotating moving blades (Okadora,
Japan). Many installations exist in Japan for different waste streams, including tyres
and waste plastics;
• fixed horizontal cylindrical furnaces equipped with moving blades (Cosa, formerly
Alcyon, Taiwan). One installation for tyre pyrolysis;
• horizontal tubes equipped with Archimedean screws (Compact Power, UK). The
pyrolitic products are immediately transferred in a steam gasification reactor
Table 10.25 Examples of rotary kilns dimensions
Waste nature Capacity (t/h) Length (m) Diameter (m) Constructor

Various 5.3 28 2.8 Noell Salzgitter (1983)
Mixed plastics 1.5 28 2.8 Noell Salzgitter (1983)
Tyres 2 28 2.8 Noell Salzgitter (1983)
MSW 2.5 18 2.2 PKA
Composite material 13 1.3 Pyropleq-Technip (1990)
MSW 3 17 2.2 Siemens-Goldshöfe
MSW 5 20 2.9 Mitsui-Seibu R21
MSW 7.5 23 3.2 Mitsui-Siemens
MSW 4.0 Thide (2003)
Tyres 2.0–2.5 11.5 1.8 VTA (2004)
Syngas
Heating chamber
Waste feed
Gasification
chamber
Steam
ashes
Figure 10.19 Screw pyrolyser followed by gasification
(Figure 10.19). Demonstration plant 1 t/h for hospital waste and many runs on different
waste streams.
• horizontal hearth equipped with moving blades (Pyrovac, Canada). One plant is
devoted for biomass pyrolysis. A lot of experience on tyre pyrolysis.
The furnaces are generally heated by the exhaust gases issued from the combustion of
the pyrolitic gases. Cosa adopted an electrical heating system and Pyrovac a circulating
molten salt system.
3.3.2 Fast Pyrolysis

Fast pyrolysis (and flash pyrolysis) needs a very high heat transfer to and inside the
material. Fluidized-bed technology is therefore well adapted for this purpose [68–70].
New developments in this field involve vortex ablative pyrolysis technology. In both
cases, high heat transfer within the material needs strict charge preparation (fine grinding).
The entrained flow reactor is usually used for biomass, but can be used for mixed
plastics. A stoichiometric air–propane burner produces the inert hot flue gas that flows
upwards through the vertical reactor and entrains the particles while heating. The Georgia
Institute of Technology has developed an entrained flow reactor for biomass (6.4 m height,
Pyrolytic gas
Char
Waste feed
Propane
Air
Figure 10.20 Entrained flow reactor
Nitrogen and
Waste particles
400 m/s
Solid recycle loop Pyrolytic gas
Char fines
Figure 10.21 Vortex ablative reactor
0.15 m diameter) with a capacity of 500 kg/h (Figure 10.20). The thermal energy of the
flue gas is used to heat the particles and provide the heat for pyrolysis reactions. A typical
carrier-gas to input mass ratio is about 4:7. It seems that a large quantity of nitrogen is
needed.
In the vortex ablative reactor, the waste particles are entrained in a nitrogen flow (a few
m/s) and enter the preheated cylindrical reactor tangentially. As the residence time in the
reactor is rather low, incompletely converted solid particles are separated and recycled in
the system. The liquid oil film on the wall evaporates rapidly before cracking. The vortex
ablative reactor developed by SERI (Golden, CO) has a length of 0.7 m and a diameter
of 0.13 m (Figure 10.21). This technology can also be used for plastic waste [71].
As these technologies have been developed for small particles, scaling-up to a few t/h
is of major interest.
3.4 GASIFICATION TECHNOLOGIES
Gasification differs from pyrolysis in that oxygen is introduced in the reactor (air, steam,
or pure O2 ) and reacts partly at high temperature with some carbon available in the waste.
The partial combustion produces the heat necessary for the process inside the furnace and
in the gasification reactions, the waste is directly heated.
By pure oxygen gasification, the gas contains mainly carbon monoxide and tars. On the
other hand, by air gasification, a large amount of nitrogen is present, and a low-calorific
gas is produced (4–6 MJ/m3 ). By steam gasification there is a formation of a syngas rich
in CO and H2 . (10–15 MJ/m3 ). Combined steam and oxygen gasification is also used in
order to have better temperature control of the process (steam gasification is endothermic).
From 15 to 20 MJ/m3 can be reached for the gas produced by steam gasification under
pressure. Gasification also produces ash. Some gasifiers operate under high pressure.
3.4.1 Types of Reactor

The different gasifier types are listed here:
• shaft gasifiers: air or oxygen (updraft and downdraft);
• fluidized-bed gasifiers: air–oxygen or steam (bubbling and circulating);
• multiple hearth: air;
• rotary kilns: air.
The quality of the gasification products are related to the material input and will differ
according to the technologies used. Tar formation can be a major problem in some cases.
For a well-defined material input, the choice of the technology will depend on the products
(gas or liquids) valorization method.
During updraft gasification (fixed-bed reactor), the waste moves slowly towards the
bottom and the airflow counter-currently to the waste flow. Hot gases are generated at
the bottom and pass through the down-flowing waste. Gasification occurs progressively
in the fixed bed, the gases, tars and moisture are entrained towards the top and do not
reach the hot zone of the furnace. There is less thermal breakdown so that the produced
gas can be rich in heavy oils and tars.
In downdraft gasification (fixed-bed reactor), the air and the waste flow co-currently
down. The gasification occurs within the bed with the formation of gas, oils and tars
reaching progressively the high temperature zone so that thermal breakdown occurs. These
products react afterwards in the gasification zone with oxygen and/or steam, producing
hydrogen and light hydrocarbons with fewer tars (pilot plant Grüssing, Germany).
In the bubbling fluidized bed, the material stays in the bed during the gasification
process. The pyrolitic gas, oils and tars are entrained with the fluidizing gas with less
thermal breakdown of the tars. Ash contributes to the bed formation.
In the circulating fluidized bed, high fluidizing velocities are needed and the solids
are elutriated. They are separated from the gases and recycled to the reactor in order to
achieve the gasification process. Ash is discarded continuously. Mixed plastic pellets are
gasified by this process in a Lurgi CFB gasifier at SVZ (Schwarze Pumpe, Germany). In
Rüdersdorf, Germany, a CFB gasifier produces a gas fuel for firing a lime kiln.
In multiple hearth furnaces, the waste is fed into the top and moves down through the
hearths by the rotation of rabbling arm. Air is injected at the bottom and at different levels
so that the flue gas mixed with the pyrolitic gases flow counter-currently upstream, heating
the waste. Ash is extracted at the bottom of the furnace. A Nesa furnace has been installed
to produce fuel gas at the Origny cement kiln plant (Rochefort-sur Nenon, France).
The rotary kiln consists of an inclined cylinder lined with ceramics. The waste intro-
duced at the front end is mixed by the rotation of the kiln (a few rpm) and is heated
progressively when moving down and carbonizing while pyrolitic gases are released. The
fixed carbon with the minerals reach the other cylinder end where a controlled air input
(under-stoichiometry) gasifies the carbon into CO. The counter-current flow of hot car-
bon monoxide and nitrogen progressively heat the waste and are mixed with the pyrolitic
gases. Complete combustion occurs in a post-combustion chamber (Basse Sambre-ERI
furnaces in Budapest and Iceland).
3.4.2 Examples of Industrial Plants Treating Plastic waste

The gasification process is particularly effective for the treatment of plastics. The reducing
atmosphere and the presence of hydrogen leads to an instant breakdown of the molecular
structure of the plastic to form CO and H2 while any halogen compounds are released
for capture in the gas clean-up system [72].
SVZ (Sekundärrohstoff Verwertungszentrum Schwarze Pumpe) is a centre for the re-
use of secondary raw material. This plant consists of seven downdraft fixed-bed gasifiers
and two entrained flow reactors [73]
The Lurgi fixed-bed grate gasifiers (FBG) have been derived from Lurgi fixed-bed gasi-
fication technology [74]. They are designed to process solid waste. With 3.6 m diameter,
they operate with a mixture of steam and oxygen at a pressure of 24 bar. Each gasifier
has a capacity range between 8 and 14 t/h (depending on feedstock composition). Solid
waste such as plastics, rubber, fluff, are treated, as well as sewage sludge, contaminated
wood, residues of paint, household waste. Prior agglomeration of the feed by briquetting
or pelletizing is required for a good porosity of the charge inside the reactor and a good
counter-current flow of the descending fuel through the charge.
The British Gas/Lurgi slagging gasifier (BGL) has been integrated into SVZ installations
in order to increase the gasification capacity. This gasifier operates under pressure and
provides the gasification of large particles and assures the vitrification of the inorganic
matter.
The Lurgi multi-purpose gasifier (MPG) is an entrained flow gasifier used for liquid
wastes (tars, oils, solvents, emulsions and also the tars and oils generated by the fixed
bed reactors, and even slurries).
The SVZ plant produces synthetic gas or fuel gas at atmospheric or elevated pressure,
with the recovery of minerals in slag. There is a partial gas conditioning (CO shifting),
a gas purification system with flue gas desulphurization. This plant is characterized by a
high thermal efficiency and a flexible feedstock. A 120 000 t/a methanol plant is associated
with it.
In the Pernis plant, Texaco has adopted a downdraft reactor fed with oxygen and/or
steam according to the waste feed input. This technology has been developed for coal,
heavy oils, petroleum coke, orimulsion, wastes and mixed plastics. End products could
be energy (combined cycles), hydrogen, ammonia or methanol according the type of
feed [75].
Texaco has recently adapted its gasification process to plastics waste [76]. The project is
to develop a capacity of 40–50 kt/yr in Pernis (Netherlands). This process consists in two
parts; a liquefaction step and an entrained bed gasifier. The plastic waste is depolymerized
in the liquefaction step into synthetic heavy oil and some condensable and noncondensable
gases. The oil and the condensable gas are injected in the gasifier (mixed oxygen–steam
gasification between 1200 and 1500◦ C). The main components of the syngas are CO and
H2 with smaller amounts of methane, carbon dioxide and water. In this project, the aim is
to sell the syngas to the chemical industry. The process is classified as feedstock recycling
for mixed plastic waste [77].
Noell have develop different gasification technologies based on ‘Noell entrained-flow
gasification’ (with cooling screen and quench, with cooled walls or with cooling screens)
[78,79]. This company is also developing a process combining pyrolysis and gasification,
the Noell conversion process. The Noell-KRC gasification facilities are located in Freiberg,
Germany.
The different pyrolysis and gasification technologies, consisting of the production of
solid, liquid and/or gaseous fuels, have achieved a significant industrial throughput and
could be a clean alternative to the direct combustion of plastics.
3.5 FUEL VALORIZATION
3.5.1 By Pyrolysis
According to the principle of indirect heating, the pyrolitic gases are not diluted by
nitrogen or by combustion products. Tables 10.26 and 10.27 give some examples of
refuse-derived fuels obtained by pyrolysis of different waste streams [80].
Product yields from mixed plastics pyrolysis are about 2.9% char, 75.1% oils and 9.6%
noncondensable gas [16,48]. Calorific values of the oils are about 40 MJ/kg.
When PVC is present in the starting mixture, its thermal degradation occurs in two
steps [81]. Bockhorn et al. [33] showed that the first step starts at about 200◦ C with
dehydrochloration [82]. Hydrochloric acid is formed during the first stage of carbonization
and can react with hydrocarbon radicals to produce organochlorinated compounds in the
gas phase [3]. During co-pyrolysis and gasification of PVC with cellulose derived material
(wood and straw), McGhee et al. [83] showed that char yields are greater than those
produced by pyrolysis of individual components because of the reaction of HCl with
Table 10.26 Examples of RDF issued by pyrolysis at 500◦ C for different waste streams
Waste Gas + oils Char (% ashes) Metals and minerals

(kg/t) (kg/t) (kg/t)
Tyres 550 300 (15%) 150
Sorting refuse 1∗ 350 + 310 kg water 80 (31%) 260
Sorting refuse 2∗ 370 + 170 kg water 60 (31%) 400
Sorting refuse 3∗ 700 180 (42%) 120
Mixed waste with 280 720 (51%)
PCB-PCDD-PCDF
ASR 1 538 205 (64%) 257
Paper recycling 700 200 (33%) 100
refuse (dry)
MSW 390 + 200 kg water 240 (40%) 170
∗
With mixed plastics
Table 10.27 Examples of energy content of RDF
issued by pyrolysis of different waste
Waste Gas + oils Char

(MJ/kg) (MJ/kg)
Tyres 38 28
Sorting refuse 1∗ 20 20
Sorting refuse 2∗ 16 20
Sorting refuse 3∗ 28 5.5
Mixed waste with 9 3.3
PCB-PCDD-PCDF
ASR 31 10
Paper recycling 23 21
refuse (dry)
MSW 13 18
∗
With mixed plastics
cellulose below 330◦ C. The chars produced in these conditions are relatively unreactive.
When lignin is present in the waste, these compounds could be adsorbed on the char [84].
Addition of basic compounds during pyrolysis leads to the formation of calcium chloride
in the char that can be leached out by washing [1]. This approach has been tested at pilot
and industrial scale [85].
3.5.2 By Gasification
The syngas produced by air gasification has a rather low heating value, between 4 and
6 MJ/m3 according to the nature of the gasified material. With oxygen gasification, the
gas can reach 8–14 MJ/m3 . The best results are obtained by steam gasification (up to
18 MJ/m3 ).
The raw gas generally contains tars and fine char particles. The advantages in using
the produced gas fuel directly by combustion in a boiler or in a furnace are that these hot
gases do not have to be cleaned to a great extent. The installed piping and burners have
to be able to tolerate some contaminants in order to avoid fouling or clogging. When the
gas is used in gas turbines or prime movers in order to generate power or electricity, they
have to be cleaned to high specification [86].
The gasification of the char issued from the pyrolysis of different waste streams is
shown in Table 10.28. From the ash content of the char, it is possible to evaluate the
quantity of syngas produced by steam gasification of the chars issued from the pyrolysis
of the different waste streams. The combination of the syngas and the pyrolytic gases
allows evaluation of the total potential energy recovered by gasification.
It can be seen that a significant proportion of the energy content of the waste is recovered
by the gasification of the char and that the ultimate residue is decreased in comparison
with the quantity of bottom ash produced compared with direct incineration. Solid plastic
waste represents a significant stream for conversion back to energy [89].
There is a need to choose the best technology, well adapted to the local situation (waste
dispersion and end-products market). Taking into account the revenues from tipping fees
for waste elimination and the sale of the energy and/or the end-products, the operating
Table 10.28 Energy recovered in syngas and pyrogas [87,88]
Waste Syngas Energy in Energy in Total energy

production syngas pyrogas recovered
(kg/twaste ) (GJ/twaste ) (GJ/twaste ) (GJ/twaste )
tyres 525 9.2 20.9 30.1
Sorting refuse 1 28 0.5 7 7.5
Sorting refuse 2 21 0.4 5.9 6.3
Sorting refuse 3 126 2.2 19.6 21.8
Mixed waste with 990 17.3 2.5 19.8
PCB-PCDD-PCDF
ASR 282 4.9 16.7 21.6
Paper recycling 275 4.8 16.1 20.9
refuse (dry)
MSW 330 5.8 5.1 10.8
costs and the transport costs, a clean economic solution could be a pyrolysis or gasification
plant with on-site energy valorization or production of substitute fuels.
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11
Yield and Composition of Gases

and Oils/Waxes from the Feedstock
Recycling of Waste Plastic
PAUL T. WILLIAMS
Energy and Resources Research Institute, Houldsworth Building, The University of
Leeds, Leeds LS2 9JT, UK
1 INTRODUCTION
Plastic polymers make up a high proportion of waste and the volume and range used
is increasing dramatically. Thermoplastics are by far the most common type of plastic,
comprising almost 80% of the plastics used in Europe, they are also the most easily recy-
clable. The consumption of plastics in Western Europe is of the order of 38 million tonnes
per year and the majority is used in the production of plastic packaging, household and
domestic products, electrical and electronic goods. There is also significant consumption
of plastics for the building and construction industry and automotive industry. Figure 11.1
shows the distribution of plastics end-use in Western Europe by sector [1].
It is estimated that only about 50% of the plastics produced in Western Europe each year
are available for collection and recycling. Of this collectable waste plastic, about 15%,
representing about 3 million tonnes, is recycled in Western Europe. A further 23% of
the plastics available for collection is incinerated with other wastes, mainly as municipal
solid waste and the ‘recovery’ of the plastic in such cases is via energy recovery. The
remainder of the plastic waste is disposed of, mainly to landfill. Table 11.1 shows the
main industrial/commercial and municipal waste sectors which produce the waste plastic
and the routes for recycling, energy recovery and disposal [1].
The separated recycled plastic material is processed by the end user by being granulated
or pelletized, melted or partially melted and extruded to form the end product. The recy-
cled plastic may be added to virgin plastic during the process. Outlets for single types
of recycled plastics include for example, high-density polyethylene for dustbin sacks,
pipes and garden furniture, polyvinyl chloride for sewer pipes, shoes, electrical fittings
286 P.T. WILLIAMS
Other,
household,
domestic
Packaging
Agriculture
Automotive
Large
industry
Electrical &
electronic Building &
construction
Figure 11.1 Plastics end-use in Western Europe by sector [1]
Table 11.1 Consumption and waste management of plastics by sector for Western Europe [1]
Sector Consumption Waste Recycling Recovery Disposal

(1000 t) (1000 t) (1000 t) (1000 t) (1000 t)
Agriculture 953 286 161 0 125
Automotive 2669 851 61 35 755
Building and construction 6710 530 58 0 472
Industry 5969 4130 1418 441 2271
Electrical and electronic 2783 854 34 4 816
Household 19039 13324 1087 4103 8139
Total 38123 19980 2819 4583 12578
and flooring and polyethylene terephthalate for egg cartons, carpets, fibre filling material
and audio cassettes [2]. Applications for plastic mixtures have included plastic fencing,
industrial plastic pallets, traffic cones, playground equipment and garden furniture. Other
uses for recycled plastic products include their use in the construction industry for pipes,
damp-proof membranes, plastic lumber and plastic/wood composites [3].
The low-grade uses for mixed plastic recycled materials has led to research into feed-
stock recycling or pyrolysis of plastics where the plastic waste materials are processed
back to produce basic petrochemicals that can be used as feedstock to make virgin plas-
tic [4]. The process has the advantage that, in addition to the processing of single plastic
types, mixed plastics can also be used since all of the feedstock is reduced to petrochemi-
cals. Feedstock recycling can be via hydrogenation at high temperature and pressure or via
pyrolysis in an inert atmosphere at atmospheric pressure to thermally degrade the plastics.
Pyrolysis of plastics thermally degrades the plastic, breaking the bonds of the polymer to
produce lower-molecular-weight oligomers and monomers. The vapours resulting from
the process are condensed to produce an oil/wax hydrocarbon product which has a high
degree of purity and can be refined at the petroleum refinery to produce a range of
petrochemical products, including virgin plastic.
GASES AND OILS/WAXES 287
The key process parameters that control the product yield and composition include the
heating rate and temperature of pyrolysis. The heat is supplied by indirect heating such as
the combustion of the gases or oil or directly by hot gas transfer. Very slow heating rates
coupled with a low final maximum temperature maximizes the yield of char, for example,
the production of char from wood in the form of charcoal involves a very slow heating
rate to moderate temperatures. The process of carbonization of waste results in reduced
concentrations of oil/tar and gas product and are regarded as by-products of the main
charcoal forming process. Moderate heating rates in the range of about 20–100◦ C/min
and maximum temperatures of 600◦ C give an approximate equal distribution of oils, char
and gases. This is referred to as conventional pyrolysis or slow pyrolysis. Because of the
slow heating rates and generally slow removal of the products of pyrolysis from the hot
pyrolysis reactor, secondary reactions of the products can take place. Generally, a more
complex product slate is found. Very high heating rates of about 100–1000◦ C/s at tem-
peratures below 650◦ C and with rapid quenching lead to the formation of a mainly liquid
product, referred to as fast or flash pyrolysis. In addition, the carbonaceous char and gas
production are minimized. The primary liquid products of pyrolysis are rapidly quenched
and this prevents breakdown of the products to gases in the hot reactor. The high reaction
rates also cause char-forming reactions from the oil products to be minimized [5, 6].
At high heating rates and high temperatures the oil products quickly break down to
yield a mainly gas product. Typical yield of gas from the original feedstock hydrocarbon
is 70%. This process differs from gasification which are a series of reactions involving
carbon and oxygen in the form of oxygen gas, air or steam to produce a gas product
consisting mainly of CO, CO2 , H2 and CH4 . Table 11.2 shows the typical characteristics
of different types of pyrolysis [5, 6].
Plastic polymers make up a high proportion of waste and the volume and range used
is increasing dramatically. The two main types of plastic are thermoplastics which soften
when heated and harden again when cooled and thermosets which harden by curing and
cannot be remoulded. The six main plastics in municipal solid waste are, high-density
polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), polystyrene
(PS), polyvinyl chloride (PVC) and polyethylene terephthalate (PET). In addition there are
Table 11.2 Typical characteristics of different types of pyrolysis [5, 6]
Pyrolysis Residence Heating Reaction Pressure Temperature Major

time rate environment (bar) (◦ C) product
Carbonization hrs-days Very low
Combustion 1 400 Charcoal
products
Conventional 10 s–10 min Low–moderate Primary/ 1 <600 Gas, char
secondary liquid
products
Flash-liquid <1 s High Primary 1 <600 Liquid
products
Flash-gas <1 s High Primary 1 >700 Gas
products
Ultra <0.5 s Very high Primary 1 1000 Gas,
products chemicals
Vacuum 2–30 s Medium Vacuum <0.1 400 Liquid
288 P.T. WILLIAMS
Others
Low density
Polyurethane
polyethylene
Polyvinyl
chloride
Polystyrene
High density
polyethylene
Polyethylene
terephthalate
Polypropylene
Figure 11.2 The main plastic types found in municipal solid waste [1]
a range of thermoset plastics, including polyester, polyurethane, polyamide, polycarbonate,

phenolic and epoxy resins. Thermoplastics are by far the most common types of plastic
comprising almost 80% of the plastics used in Europe, they are also the most easily recy-
clable. In many countries, plastic is collected from commercial and industrial sources as
separate plastic fractions, much of which is recycled directly back into the plastic product
manufacturing process. Although plastics make up between 5 and 15wt% of municipal
solid waste it comprises 20–30% of the volume. The plastics in municipal solid waste are
mainly in the form of plastic film and rigid containers. Plastic film comprises about 3–4
wt% of the household waste stream and is almost impossible to recycle. However, plas-
tic containers are more easily collected separately or segregated from the waste stream.
Figure 11.2 shows the proportion of the main plastic types found in municipal solid
waste [1].
The detailed analysis of the derived oil/wax and gas products from the pyrolysis of
plastics in relation to process conditions and different types of plastic is essential in
providing data for the assessment of the feedstock recycling process. In addition, the
yields and composition of gases and oils from the pyrolysis of mixed plastic waste are
important in assessment of the process and to determine the possibility of any interactions
between the plastics during pyrolysis.
2 FEEDSTOCK RECYCLING OF PLASTICS
2.1 PRODUCT YIELD
2.1.1 Product Yield from the Feedstock Recycling of Single Plastics

Table 11.3 shows the yield of gas, oil/wax and char from the fixed bed pyrolysis of
the main polyalkene plastics, polyethylene and polypropylene, found in municipal solid
waste [7–15]. Table 11.4 shows the gas, oil/wax and char from the pyrolysis of other
plastics [7–9, 14–17]. All of the plastics produced an oil/wax and gas and in some
cases a char. The product yield related directly to the type of plastic, the reactor type
Table 11.3 Product yield from the pyrolysis of polyalkene plastics
Feedstock Reactor Temperature Gas Oil/wax Char Reference

type (◦ C) (wt%) (wt%) (wt%)
PE Fluidized-bed 760 55.8 42.4 1.8 [9]
PE Fluidized-bed 530 7.6 92.3 0.1 [9]
LDPE Fluidized-bed 700 71.4 28.6 0.0 [10]
LDPE Fixed-bed (batch) 7001 15.1 84.3 0.0 [7]
HDPE Fixed-bed (batch) 7001 18.0 79.7 0.0 [7]
LDPE Fixed-bed (batch) 5001 37.0 63.0 0.0 [15]
LDPE Ultra-fast pyrolysis 825 92.9 5 2 [11]
HDPE Fixed-bed (batch) 450 13.0 84 3 [12]
HDPE Fixed-bed (batch) 430 9.6 69.3 21.1 [13]
HDPE Vacuum 500 0.9 97.7 0.8 [14]
LDPE Vacuum 500 2.7 96.0 1.0 [14]
LLDPE Fluidized-bed 730 58.4 31.2 2.1 [8]
LLDPE Fluidized-bed 515 0.0 89.8 5.9 [8]
PP Fixed-bed (batch) 380 24.7 64.9 10.4 [13]
PP Fluidized-bed 740 49.6 48.8 1.6 [9]
PP Vacuum 500 3.5 95 <0.1 [14]
1
Final temperature
and the process conditions, particularly pyrolysis temperature. The product oil produced
from pyrolysis varies considerably in colour. For example, it has been reported that at
temperatures of approximately 500◦ C, the polyalkene plastics, PE, HDPE, LDPE and
PP produce a light-coloured waxy product [7]. Polyvinyl chloride produces a black oil,
polystyrene produces a red/brown oil and polyethylene terephthalate produces a dark,
almost black, viscous oil [7]. The condensable products derived from the thermoset plastic
polyester/styrene resin used in composite production, consisted of a yellow/brown, low-
viscosity oil, which accounted for approximately 80 vol% of the total condensable yield,
a pale yellow wax and some water. Thermal decomposition of a thermoset phenolic
resin used in a composite plastic generated a yellow/brown oil (50%), water (45%) and
wax, whereas epoxy resin produced a viscous, dark brown/orange oil with some water
(10 vol %) [18].
The distinction between the yield of condensed hydrocarbon wax and oil is a con-
sequence of the pyrolysis reaction system, temperature, condensation collection system
and condensation temperature. For example, fluidized-bed pyrolysis of various plastics at
550◦ C in a fluidized-bed reactor with rapid cooling of the condensate using water-cooled
condensers produced an oil/wax ratio of 1.23 for HDPE, 0.50 for LDPE, 0.82 for PP, 4.75
for PS and 1.48 for PET [19]. In addition, it was shown that PVC produced 100% oil
and no wax [19]. Kaminsky et al. [9] pyrolysed polyethylene in a fluidized-bed reactor
at 530◦ C and reported an oil yield of 50.3 wt% and a wax yield of 42 wt%. Miranda
et al. [14] for the vacuum pyrolysis of various plastics reported 88 wt% conversion of
LDPE to wax and 8 wt% to an oil. For HDPE, the conversion was 92.3 wt% to wax and
290 P.T. WILLIAMS
Table 11.4 Product yield from the pyrolysis of other plastics
Feedstock Reactor Temperature Gas Oil/wax Char Reference

type (◦ C) (wt%) (wt%) (wt%)
PS Vacuum 500 <0.1 99.3 0.4 [14]
PS Fixed-bed (batch) 7001 3.4 83.8 3.5 [7]
PS Fluidized-bed 500 0.2 99.7 <0.1 [16]
PS Fluidized-bed 580 9.9 89.5 0.6 [9]
PS Fluidized-bed 600 0.7 98.7 <0.2 [17]
PS Fluidized-bed 532 11.5 88.5 [8]
PS Fluidized-bed 708 15.2 83.3 [8]
PVC Vacuum 520 58.5a 32.4 8.5 [14]
PVC Fixed-bed (batch) 7001 55.8b 31.7 13.8 [7]
PVC Fluidized-bed 740 63.1c 28.1 8.8 [9]
PVC Fluidized-bed 520 84.6d 6.3 9.1 [8]
PET Fixed-bed (batch) 5001 73.4 9.1 18.5 [15]
PET Fixed-bed (batch) 7001 38.7 41.3 15.6 [7]
Thermoset plastics
Polyurethane Fluidized-bed 760 37.9 56.3 0.3 [9]
Polyester Fluidized-bed 768 50.8 40.0 7.1 [9]
Polyamide Fluidized-bed 760 39.2 56.8 0.6 [9]
Polycarbonate Fluidized-bed 710 26.5 46.4 24.6 [9]
1
Final temperature
a
Includes 58.2 wt% HCl
b
c
d
Includes 56.0wt% HCl
5.4 wt% to oil, for PP the conversion to wax was 70 wt% and 25 wt% oil. They also
showed that when polystyrene was pyrolysed in the vacuum reactor, 58.6 wt% light oil
was produced and 40.7 wt% heavy oil [14].
Table 11.3 shows that, in most cases, the three polyalkene plastics produced very similar
product yields, with high yields of wax, and hydrocarbon gas and negligible char yields.
Higher temperatures of pyrolysis result in thermal cracking of the oil/wax to produce
increased concentrations of gas. For example, Kaminsky et al. [9] reported an oil/wax
yield of 92.3 wt% and 7.6 wt% gas, at a pyrolysis temperature of 530◦ C in a fluidized
bed. However at the higher temperature of 760◦ C, the oil/wax was thermally degraded to
produce 42.4 wt% oil/wax and 55.8 wt% gas.
In addition to temperature, the type of pyrolysis reactor is also important in deter-
mining product yield. High heating rates with short hot-zone residence times and rapid
quenching of the products are regarded as favouring the formation of oil/wax products.
Such conditions are typically found in fluidized-bed reactors. The pyrolysis gases and
vapours are removed from the hot reactor and condensed before further reaction breaks
down the higher-molecular-weight species into gaseous products. Therefore, the removal
of pyrolysis products from the hot zone reduces the extent of secondary reactions which
are known to increase the yield of char and gas at the expense of oil formation [20,
21]. For example, Cypres and Bettens [20] increased the rate of removal of pyrolysis
vapours from a secondary hot zone by increasing the flow of nitrogen carrier gas. They
found that this increased the yield of oil by reducing the secondary reactions. Primary
vapours are first produced in the pyrolysis process, the characteristics of which are most
influenced by heating rate. These primary vapours then degrade to secondary tars and
gases, the proportion and characteristics of which are a function of temperature and
time. Higher oil/wax yield may also be produced where the volatile products are quickly
removed from the hot zone by, for example, nitrogen purge gas [7, 22] or under vac-
uum pyrolysis conditions [14]. Under fast pyrolysis conditions, at high temperature the
major product is gas due to thermal cracking of the oil/wax. For example, Table 11.3
shows that fluidized-bed ultra-fast pyrolysis at high temperatures produces mainly gas
from low-density polyethylene.
Table 11.4 shows the product yield of gas, oil/wax and char from the pyrolysis of other
single plastics, including thermoplastics and thermoset plastics. Pyrolysis of polystyrene
under moderate temperatures of between 500 and 600◦ C produces high levels of oil. Even
at higher temperatures above 700◦ C, there is a high conversion of the polymer to oil. In
fact the oil mainly consists mainly of the monomer styrene [8, 9, 23, 24].
Polyvinyl chloride produces a significantly lower yield of oil compared with the
polyalkenes and polystyrene (Table 11.4). This reduction in oil yield is attributable to
the conversion of the chlorine in the PVC molecule to hydrogen chloride gas under
pyrolysis conditions. For example, Miranda et al. [14] report a hydrogen chloride gas
yield of 58.2 wt%, Williams and Williams [7] report a hydrogen chloride yield of 52.9
wt%, Kaminsky et al. [9] a yield of 56.3 wt% hydrogen chloride and Scott et al. [8] a
hydrogen chloride yield of 56.0 wt% in the gas. In addition, a significant proportion of
char is produced during the pyrolysis of PVC.
The pyrolysis of polyethylene terephthalate produces large quantities of gas dominated
by carbon dioxide and carbon monoxide, in addition to a wax and significant yield of
char. Polyethylene terephthalate is characterized by a high proportion of oxygen in its
chemical structure, unlike the other common polyalkene plastics (HDPE, LDPE, PP),
polystyrene and polyvinyl chloride. The high oxygen content leads to the formation of
mainly carbon dioxide and carbon monoxide and also to a wax which is characterized by
high concentrations of oxygenated compounds.
Research on the pyrolysis of thermoset plastics is less common than thermoplastic
pyrolysis research. Thermosets are most often used in composite materials which contain
many different components, mainly fibre reinforcement, fillers and the thermoset or poly-
mer, which is the matrix or continuous phase. There has been interest in the application of
the technology of pyrolysis to recycle composite plastics [25, 26]. Product yields of gas,
oil/wax and char are complicated and misleading because of the wide variety of formu-
lations used in the production of the composite. For example, a high amount of filler and
fibre reinforcement results in a high solid residue and inevitably a reduced gas and oil/wax
yield. Similarly, in many cases, the polymeric resin is a mixture of different thermosets
and thermoplastics and for real-world samples, the formulation is proprietary information.
Table 11.4 shows the product yield for the pyrolysis of polyurethane, polyester, polyamide
and polycarbonate in a fluidized-bed pyrolysis reactor [9].
2.1.2 Product Yield from the Feedstock Recycling of Mixed Plastics

The pyrolysis of mixtures of single plastics and real-world plastic derived from municipal
solid waste has been investigated by several researchers and the yield of gas, oil/wax
292 P.T. WILLIAMS
Table 11.5 Product yield from the pyrolysis of mixed plastic
Feedstock Reactor Temperature Gasa Oil/wax Char Reference

type (◦ C) (wt%) (wt%) (wt%)
Plastic mixture Vacuum 520 6.3 91.8 1.3 [14]
Plastic mixture Fixed-bed 7001 9.6 75.1 2.9 [27]
Plastic mixture Fluidized-bed 600 44.7 43.2 7.6 [28]
Plastic mixture Fixed-bed 500 85.2 12.5 3.0 [15]
MSW plastic Fluidized-bed 787 43.6 26.4 25.4 [9]
MSW plastic Fixed-bed 430 25 59 16 [22]
1
Final temperature
a
Gas yield includes HCl
and char are shown in Table 11.5 [9, 14, 15, 22, 27, 28]. The plastic mixture represents
pure single plastics which are mixed to produce a mixture typically representative of the
proportions of those plastics found in municipal solid waste. Table 11.5 shows that such
mixtures of single plastics tend to produce lower char product yields compared with the
pyrolysis of plastics derived from real-world municipal solid waste. This suggests that
plastics derived from real-world municipal solid waste contains perhaps contamination and
also plastics other than the common plastics of municipal solid waste, that is, polyethylene,
polypropylene, polystyrene, polyvinyl chloride and polyethylene terephthalate. Perhaps
including a proportion of thermoset plastics. Higher temperatures of pyrolysis produce
increased concentrations of gas, as was found for the pyrolysis of single plastics. For
example, Williams and Williams [28] examined the influence of temperature between
500 and 700◦ C on the product yield and product composition from the fast pyrolysis
of mixed plastic waste in a fluidized bed. They found that the gas yield increased from
9.79 to 68.81 wt% as the temperature of pyrolysis was increased from 500 to 700◦ C. In
addition, there was a corresponding decrease in oil/wax yield from 55.07 to 18.44 wt%.
They also examined the influence of temperature on the separate yield of oil and wax,
they found that the wax yield was 17.28 wt% (31.4% of the total oil/wax yield) at 500◦ C
and decreased to 0.0 wt% at 700◦ C.
2.2 GAS COMPOSITION
2.2.1 Gas Composition from the Feedstock Recycling of Single Plastics

Table 11.6 shows the composition of gases derived from the pyrolysis of individual single
plastics from various researchers [7–9, 11, 19, 27]. The three polyalkene plastics, HDPE,
LDPE and PP, behave quite similarly in that the main gases to be formed are alkene
gases derived from the thermal degradation of their similar polyalkene chemical structure
as shown in Figure 11.3. Ethene, and propene are the most common hydrocarbon gases.
However, Kaminsky et al. [9], using higher temperatures of pyrolysis, found increased
concentrations of methane compared with fixed-bed pyrolysis [7]. The thermal degrada-
tion of polyalkenes has been described as a random scission process whereby during
degradation the rupture of bonds takes place at purely random points along the polymer
chain length [29, 30]. Thus, all the bonds which remain intact at any one stage in the
Table 11.6 Gas composition from the pyrolysis of single plastics
Reactor H2 CH4 C2 H6 C2 H4 C3 H8 C3 H6 C4 H10 C4 H8 CO2 CO HCl Reference

type (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (wt%)
HDPE Fixed-bed 0.12 1.90 2.21 6.08 1.31 4.56 0.22 0.36 [7]
PE Fluidized- 0.8 23.8 6.7 20.0 0.08 5.6 0.6 [9]
bed
GASES AND OILS/WAXES
LDPE Fixed-bed 0.05 1.14 1.67 4.00 1.33 4.00 0.32 2.00 [7]
LDPE Ultra-fast 22 28 18 [11]
LLDPE Fluidized- 4.6 2.2 19.4 0.8 12.0 13.11 [8]
bed
PP Fixed-bed 0.05 0.93 1.45 3.52 1.00 3.53 0.23 1.29 [7]
PP Fluidized- 0.7 28.2 4.0 13.9 0.09 3.7 0.4 [9]
bed
PS Fixed-bed 0.04 0.53 0.08 0.26 0.02 0.05 0.00 0.06 [7]
PS Fluidized- 0.06 0.04 [9]
bed
PVC Fixed-bed 0.12 0.77 0.47 0.15 0.24 0.19 0.11 0.15 52.93 [7]
PET Fixed-bed 0.31 0.71 0.03 1.41 0.13 0.09 0.00 0.00 22.71 13.29 0.00 [7]
Polyester Fluidized- 0.3 3.8 0.2 0.05 0.1 26.9 17.4 [9]
bed
Polyurethane Fluidized- 0.7 16.1 1.8 7.2 0.2 1.3 0.1 1.8 34.0 [9]
bed
Mixed Fixed-bed 0.08 0.97 1.01 1.67 0.70 0.83 0.14 2.20 2.06 2.31 [27]
plastic
Mixed Fluidized- 0.22 2.87 2.39 5.65 1.26 5.53 0.24 6.35 1.42 [19]
plastic bed
1
Total of C4 gases
293
294 P.T. WILLIAMS
[a] Polyethylene
CH2 CH2 (f) Polyester resin

O CH2CH2 O C C
O O
[b] Polypropylene H
(g) Phenolic resin OH OH OH
CH C
CH2 CH2 CH2 CH2
CH3
[c] Polystyrene CH2 CH2 CH2

CH2 CH OH
CH2 CH2 CH2 CH2
OH OH
[d] Polyvinyl chloride
CH2 CH (h) Epoxy resin CH
O C O CH2CHCH2 O
Cl
CH2 OH
[e] Polyethylene Terephthalate
O O
C C O CH2 CH2 O
Figure 11.3 Repeating chemical structures of some common plastics
degradation process have the same probability of being broken, leading to the formation
of polymer fragments of varying sizes. Since the bond energy of the C=C bond is much
higher than the other bonds found in the polymer structure [31], there is a tendency to
form alkenes in the derived product stream. The alkene gases, ethene, propene and to some
extent butene represent the low-molecular-weight range of the random scission process.
The alkane gases, methane, ethane, propane and butane are also present in significant
concentrations, again formed as part of the random scission process of the thermal degra-
dation of the polymer. The derived gases have a significant calorific value and it has been
suggested that the gases may provide the energy requirements for the pyrolysis process,
enhancing the economic viability. No carbon monoxide or carbon dioxide were formed
from the pyrolysis of the polyalkenes since there is no oxygen present in the polymer.
Polystyrene gives a low gas yield overall, since there is a much higher conversion
of the plastic to oil/wax. The derived gas composition consists mainly of alkene gases,
ethene, propene and butene and also methane.
Polyvinyl chloride gave hydrogen chloride as by far the main gas. The C–Cl bond in
the PVC structure has a lower bond energy than other bonds in its structure and upon
heating has a tendency to break first. As a consequence, PVC thermal degradation begins
around 150◦ C which is a much lower temperature than the other common plastics. The
intermolecular chain transfer reaction which follows leads to dehydrochlorination and
hydrogen chloride is produced [32]. Once dehydrochlorination is complete, PVC yields
hydrocarbon gases consistent with the thermal degradation of a vinyl polymer. Table 11.6
shows that the main hydrocarbon gases were hydrogen, alkanes and alkenes.
The pyrolysis of polyethylene terephthalate produces a gas consisting mainly of carbon
dioxide and carbon monoxide, due to the high oxygen content of the original plastic
polymer (Figure 11.3). In addition, much lower, but significant, concentrations of ethene
and propane are formed. Carbon dioxide is formed from the decarboxylation of the PET,
carbon monoxide may be formed via either decarboxylation or reaction between carbon
dioxide and char [33].
Pyrolysis of polyester produces a large conversion of the polymer to carbon diox-
ide and also carbon monoxide [9]. The generation of carbon monoxide and especially
carbon dioxide seen at all pyrolysis temperatures is due to the large number of ester
bonds in the resin. The pyrolysis of polyurethane in a fluidized bed at 700◦ C produced
mainly carbon monoxide and methane [9]. Thermogravimetric decomposition studies of
polyurethane where pyrolysis takes place in a fixed bed of sample have been shown to
produce mainly carbon dioxide and carbon monoxide [34]. It has been suggested that
the carbon dioxide is produced by the breaking of the urethane bond and that degrada-
tion begins at around 250◦ C [35]. Significant yields of methane and ethane have been
reported at temperatures above 600◦ C [36]. In addition, it has also been reported that
hydrogen cyanide can be formed during pyrolysis, from the isocyanates used in polymer
production [36].
2.2.2 Gas Composition from the Feedstock Recycling of Mixed Plastics

Table 11.6 also shows the gas composition from the pyrolysis of mixed plastic waste
representative of the plastics found in municipal solid waste. The major gases were
hydrocarbons with smaller amounts of carbon dioxide and hydrogen chloride. The major
hydrocarbons produced were the alkene gases, ethene, propene and butene and the alkane
gases, methane, ethane, propane and butane. The carbon dioxide is produced due to the
presence of the PET. Hydrogen chloride, is produced from the PVC present in the mixture
of plastics. The interaction of the various single plastics in a mixture has been investi-
gated [7]. The data suggest that less hydrogen, methane and ethane and more butane are
formed than would be expected from the theoretical estimates derived from the pyrolysis
of single individual plastics.
2.3 OIL/WAX COMPOSITION FROM THE FEEDSTOCK RECYCLING

OF SINGLE PLASTICS
The oil/wax from the feedstock recycling of plastics has potential uses either as direct
use as a fuel, for further upgrading to higher-quality petroleum refined substitute fuels
or as a chemical feedstock. As such, the detailed analysis of the oil/wax is important.
There are several routes and levels of analysis. For example, infrared analysis such as
Fourier transform infrared (FTIR) spectrometry provides a broad analysis of the chemical
groups found in the oils/wax. Similarly, the molecular weight range of the oils provides an
indication of the distillation potential of the oils to produce refined fuels. Analysis of the
oils for their potential as directly useable fuels requires standard fuel tests developed for
the petroleum industry. Detailed identification of individual compounds in the oil/waxes
requires analytical techniques such as liquid chromatography, gas chromatography and
mass spectrometry.
296 P.T. WILLIAMS
2.3.1 Fourier Transform Infrared Spectrometry of Oils/Waxes

Figure 11.4 shows the functional group compositional analysis by Fourier transform
infrared (FTIR) spectrometry of the oil/wax derived from the fixed bed pyrolysis of
HDPE, LDPE and PP [7]. Figure 11.5 shows the functional group compositional analysis
of oil derived from the fixed-bed PVC, PS and PET analysed by FTIR spectrometry [7].
Figure 11.6 shows the functional group compositional analysis of the six main mixed plas-
tics found in municipal solid waste, in their relative proportions [27]. Figure 11.7 shows
the functional group compositional analysis of oil/wax from the fixed-bed pyrolysis of
polyester resin, phenolic resin and epoxy resin [18].
Figure 11.4 shows that the polyalkene plastics, HDPE, LDPE and PP, gave very similar
FTIR spectra since their polymer structures are very similar and their thermal degradations
are likely to produce similar compounds in the derived oil/wax [7]. The peak at 3050 cm−1
is an indication of the presence of =C–H stretching vibrations typical of alkene functional
groups. The peaks between 3000 cm−1 and 2800 cm−1 indicate the presence of –CH3 ,
–CH2 and C–H functional groups which are indicative of aliphatic species such as alkanes
and alkenes. The C=C absorbance peak between 1625 cm−1 and 1675 cm−1 confirms
that alkene groups are present in the oil/wax. The presence of peaks in the region of
1350–1500 cm−1 due to the deformation vibrations of C–H bonds confirm the presence
HDPE Wax
Relative Intensity
LDPE Wax
PP Wax
3000 2000 1600 1200 1000 600

Wavelength (cm−1)
Figure 11.4 Fourier transform infrared spectra of the waxes derived from the pyrolysis
of high-density polyethylene, low-density polyethylene and polypropylene
PVC Oils
PS Oils
Relative intensity
PET
3000 2000 1600 1200 1000 600

Wavelength (cm−1)
Figure 11.5 Fourier transform infrared spectra of the oils/waxes derived from the
pyrolysis of polyvinyl chloride, polystyrene and polyethylene terephthalate
of aliphatic groups. The peaks located at 980 and 920 cm−1 represent CH stretching
and deformation vibrations of alkene structures. Two peaks between 720 and 730 cm−1
indicate C–H cyclic deformations which suggest either aromatic or more likely –CH2
which has split due to interaction in long molecular chains representing the presence of
long oligomer chains. The overall spectra of the polyalkene pyrolysis oil/wax is therefore
dominated by the presence of alkane and alkene compounds as has been found by other
workers [37, 38].
Figure 11.5 shows that the functional group compositional analysis of the pyrolysis
oil/waxes derived from the fixed-bed pyrolysis of PVC, PS and PET is very different
from the polyalkene plastic pyrolysis oil/waxes. The spectra of the PVC pyrolysis oil/wax
shows that the characteristic peaks of alkanes and alkenes are present as described for
the polyalkene plastics. Since the PVC plastic polymer is based on a similar backbone
structure to the polyalkene plastics, a similar degradation product oil/wax composition may
be expected. However, the spectra for PVC in Figure 11.5 show that there are additional
peaks in the region of 675–900 cm−1 and 1575–1625 cm−1 . The presence of these peaks
indicates the presence of mono-aromatic, polycyclic aromatic and substituted aromatic
groups. Benzene has been identified as a major constituent in oils derived from the
pyrolysis of PVC whilst other aromatic compounds identified included alkylated benzenes
and naphthalene and other polycyclic aromatic hydrocarbons [19, 32, 39]
The pyrolysis oil/wax derived from the fixed-bed pyrolysis of PS produced a strong
presence of both aromatic and aliphatic functional groups. The presence of CH3 and CH2
are indicated by the peaks between 3000 and 2800 cm−1 and the peak in the region of
298 P.T. WILLIAMS
1350–1500 cm−1 due to the presence of C–H bonds confirm the presence of aliphatic
groups. In addition, there are strong peaks present in the region of 675–900 cm−1 and
three strong peaks between 3000 and 3050 cm−1 showing a very significant presence
of aromatic compounds in the oil/wax. It has been shown that pyrolysis oil/wax from
PS produces a mainly aromatic oil [8, 40], consequently the aliphatic functional groups
indicated by the FTIR spectra probably indicates that these aliphatic groups are present
as alkyl groups attached to aromatic rings.
The FTIR analysis for the oil/wax derived from PET pyrolysis produced a complex
spectrum which included oxygenated functional groups in addition to aliphatic and aro-
matic groups. The oxygen atoms, aromatic ring and aliphatic groups in the original
polymer structure leading to a very complex composition of compounds in the resul-
tant pyrolysis oil/wax. The broad peak between 3300 and 2900 cm−1 may be due to
intramolecular OH or hydrogen bonded OH groups. The presence of such groups, cou-
pled with the presence of C=O stretching vibrations between 1650 and 1850 cm−1
indicates the presence of carboxylic acids and their derivatives. The presence of the
C=O peaks between 1650 and 1850 cm−1 may also indicate the presence of ketones and
aldehydes. Aromatic groups are indicated by the peaks between 675 and 900 cm−1 and
1575–1625 cm−1 .
Figure 11.6 shows the FTIR spectra for the pyrolysis oil from the pyrolysis of mixed
plastics. The plastic mixture simulating that found in municipal solid waste. Since almost
70% of the plastic mixture was composed of the polyalkene plastics, HDPE, LDPE and
PP, it would be expected that the thermal degradation products of these plastics will dom-
inate the mixed plastic oil/wax composition. However, since polystyrene and polyvinyl
chloride produce an aromatic oil/wax product on pyrolysis, then a significant aromatic
content in the oils and waxes derived from the pyrolysis of the mixed plastic waste
might also be expected. Figure 11.6 shows that the chemical groups found in the indi-
vidual plastics pyrolysis oils are also found in the mixed plastic pyrolysis oil. However,
it has been suggested that there is some interaction between the reaction products of
the individual polymers to produce a significantly different chemical composition com-
pared with what might be expected be mere addition of the individual polymer product
compositions [7, 27].
Figure 11.7 shows the FTIR traces from oils/waxes derived from the fixed-bed pyroly-
sis of some thermoset plastics, polyester resin, phenolic resin and epoxy resin. The spectra
produced from the polyester oil/wax featured a strong, broad peak at 3432–3437 cm−1 ,
derived from O–H stretching. The breadth of the peak suggests carboxylic acid groups,
while the relatively clear definition and high peak centre wavenumber suggests the pres-
ence of alcoholic compounds. Very prominent absorption peaks at 1720 and 1285 cm−1
were assigned to C=O and C–O stretching respectively and were consistent with the pres-
ence of carboxylic acid, carbonyl and/or ester groups [41]. Other studies have identified all
of these types of oxygenated compounds in the decomposition products of polyester [26,
42]. Groups of sharp peaks at 1500–1630 cm−1 and 700–910 cm−1 were due to skeletal
vibrations and out-of-phase C–H bending of aromatic rings respectively [41]. This evi-
dence, together with the relatively low ratio of methyl groups to methylene groups at 2960
and 2930 cm−1 , suggest a highly aromatic structure with little alkylation or chain branch-
ing. Taken as a whole, the spectra suggest that the oil/wax comprises mainly unchanged
lengths of polyester chain, with changes in functional group where chain scission has
100 100
80 80
Relative intensity
60 60
40 40
20 20
0 0
4000 3000 2000 1600 1200 1000 600
Wavelength (cm−1)
Figure 11.6 Fourier transform infrared spectra of the oil derived from the pyrolysis of
mixed plastics
0.6
a
0.4
0.2
Absorbance
1.0
b
0.6
0.2
0.3
c
0.2
0.1
3000 2000 1000

Wavenumber (cm−1)
Figure 11.7 Fourier transform infrared spectra of the oils/waxes derived from the
pyrolysis of polyester resin (a), phenolic resin (b) and epoxy resin (c)
300 P.T. WILLIAMS
occurred. As scission is most likely at the oxygen-containing groups [26, 43], one would
expected to find a range of oxygenated functional groups present in the oils.
The oil derived from the phenolic resin used in a composite plastic sample produced
a strong, more clearly defined hydroxyl peak at 3381–3385 cm−1 . The spectra showed
large groups of peaks attributable to aromatic rings. A very strong peak at 1244 cm−1
and a less strong peak at 1379 cm−1 were attributed to C–O stretching/O–H bending
interactions observed in phenols [41]. Strong peaks at 2925 and 2854 cm−1 caused by
asymmetrical and symmetrical stretching of the C–H bond indicated a high proportion
of methylene groups, whilst the proportion of methyl groups was comparatively low,
indicating a relatively low degree of aromatic alkylation or aliphatic chain branching.
These data therefore suggest that these samples were predominantly comprised of phenol,
phenol derivatives and short lengths of the polymer chain.
The oil/wax from pyrolysis of epoxy resin composite produced similar spectra to those
seen from the phenolic sample [18]. The hydroxyl stretch peak was broader, suggesting
the presence of carboxylic acid groups, although no carbonyl groups were present to
support this supposition. The ratio of methyl groups to methylene groups was higher than
in the phenolic sample, suggesting greater alkylation of the phenolic units or branching
of aliphatic chains than in the former case. These results are consistent with the structure
of typical epoxy resins.
2.3.2 Molecular Weight Range of Pyrolysis Oils/Waxes

The molecular weight (MW) range of an oil/wax gives an indication of the boiling point
range of the product which is a useful parameter in petrochemical process engineer-
ing to determine the compatibility of the recycled plastic product with the conventional
petrochemical feedstocks derived from crude petroleum oil. Molecular weight range is
determined by, for example, size exclusion chromatography, which is also known as gel
permeation chromatography.
Figure 11.8 shows the molecular weight distribution for the waxes derived from the
fluidized-bed pyrolysis of various plastics. There was no wax produced for the pyrolysis
of polyvinyl chloride. The molecular weight range for the oils for polyvinyl chloride,
together with the analysis of the oils for polyethylene terephthalate and polystyrene are
shown in Figure 11.9. Table 11.7 shows data for the molecular weight range of oils and
waxes derived from the pyrolysis of single plastics in a fluidized-bed reactor using a
refractive index (RI) detector [19]. The MW distribution is usually determined as number
and weight average MW, in addition the polydispersity of the oils was also calculated.
The number average molecular weight Mn is defined as the average molecular weight
according to the number of molecules present of each species [44]. The weight average
molecular weight Mw is the sum of the product of the weight of each species present and
its molecular weight divided by the sum of the weights of the species. The difference
in the values of Mn and Mw indicates the polydispersity of the sample; the closer the
two measured average molecular weights, the narrower the molecular weight distribution.
Single compounds have a polydispersity in the range 1.0–1.1.
Table 11.7 shows that there was a shift to higher molecular weight distribution for
the waxes compared to the oils, which is apparent when the number and weight average
data of Table 11.7 are examined which show a distinct increase in value for the waxes
PS
25
PET
PVC
20
Wt%
15
10
10 100 1000 10000

Molecular Weight (Da. )
Figure 11.8 Molecular weight distribution of the oils derived from the fluidized-bed
pyrolysis of polystyrene, polyvinyl chloride and polyethylene terephthalate
PS
20 PET
HDPE
15 PP
Wt% LDPE
10
10 100 1000 10000

Molecular weight (Da.)
Figure 11.9 Molecular weight distribution of the waxes derived from the fluidized-bed
pyrolysis of high-density polyethylene, low-density polyethylene, polypropylene,
polystyrene and polyethylene terephthalate
compared with the oils. The waxes for the polyalkene plastics HDPE, LDPE and PP show
a similar molecular weight distribution, ranging from a molecular weight of 100 to over
2000 Daltons with a peak molecular weight of approximately 1100 Da. Polystyrene wax
showed a much lower molecular weight distribution from 80 to 190 Da. However, the
main product from polystyrene pyrolysis was an oil which had a molecular weight range
from 60 to 250 Da. Styrene has a molecular weight of 104 which accounts for the mostly
low molecular weight nature of the oil sample. The molecular weight distribution of the
pyrolysis oil from PVC was very wide, ranging from 60 to over 2000 Da, indicating that
the polymer degradation had produced very high molecular weight compounds present
in the oils. No wax was formed with PVC. Oil derived from PET pyrolysis gave a
molecular weight distribution from 60 to approximately 800 Da. Table 11.7 also shows the
302 P.T. WILLIAMS
Table 11.7 Molecular weight data for oils and waxes from the fluidized-bed pyrolysis of indi-
vidual plastics at 550◦ C [19]. (Reproduced by permission of the Energy Institute)
Product HDPE LDPE PP PS PVC PET

Oil
Mn 416 422 103 203 191
Mw 629 659 111 420 233
Polydispersity 1.51 1.56 1.08 2.07 1.22
Wax
Mn 731 556 682 200 191
Mw 1024 959 1067 284 221
Polydispersity 1.40 1.72 1.56 1.41 1.16
Mn = Number average molecular weight (Da)

Mw = Weight average molecular weight (Da)
polydispersity, which reflects the deviation of the molecular weight distribution from the
Gaussian distribution of an ideal single compound. A higher polydispersity for a sample
indicates a broader range of molecular weight distribution, reflecting a wider range of
compounds present in the sample. The data suggest that the oils are all quite complex,
containing a complex range of compounds. The polydispersity shown in Table 11.7 for
the pyrolysis oil derived from polystyrene indicates that it very high in styrene, since the
recorded polydispersity for a single compound is close to 1.0.
Figure 11.10 shows the molecular weight distribution for the oils and Figure 11.11 for
the waxes derived from the fluidized-bed pyrolysis of the plastic mixture in relation to
pyrolysis temperature. The oils show a higher proportion of low-molecular-weight species
compared with the waxes and a clear bimodal distribution for the oils and waxes. The two
peaks occur at molecular weights of about 120 and about 1200 Da., depending on whether
500°C
12
550°C
600°C
Wt% 8 650°C
700°C
10 100 1000 10000

Figure 11.10 Molecular weight distribution of the oils derived from the fluidized-bed
pyrolysis of mixed plastics in relation to pyrolysis temperature
the analysis is for oil or wax and also dependent on temperature. At higher temperatures
of pyrolysis, the wax breaks down to produce an oil product and gas. The polyalkene
plastics, HDPE, LDPE and PP gave peak molecular weights in the higher molecular
weight region whereas the other plastics found in the mixture, PS, PVC and PET gave
oils and waxes with peaks in the lower molecular weight region. Consequently, the lower
fraction of the molecular weight distribution of the mixed plastic product is mainly due
to PS, PVC and PET whilst the higher fraction of the molecular weight distribution is
due mainly to HDPE, LDPE and PP.
Figure 11.12 shows the molecular weigh distribution of some examples of petroleum-
derived fuels for comparison. The molecular weight distribution of the plastics are similar
500 °C
12
550 °C
600 °C
8
Wt%
10 100 1000 10000

Molecular Weight (Da. )
Figure 11.11 Molecular weight distribution of the waxes derived from the fluidized-bed
pyrolysis of mixed plastics in relation to pyrolysis temperature
Kerosene
Diesel
12
LFO
MFO
HFO
Wt% 8
10 100 1000 10000

Figure 11.12 Molecular weight distribution of petroleum-derived fuels

304 P.T. WILLIAMS
to those of the refined petroleum fuels. For example, the oil derived from polystyrene
and polyethylene terephthalate are similar to diesel fuel (gas oil) and the oils from the
polyalkene plastics (HDPE, LDPE and PP) are similar to medium fuel oil. The waxes
from the feedstock recycling of HDPE, LDPE and PP have been refined for use in the
petrochemicals industry [45]. The wax produced from the pyrolysis of mixed plastic waste
can be mixed with the naphtha fraction of petroleum oil at inputs of up to 20% [45]. The
resultant mixture can then be fed to a conventional steam cracker without significantly
altering the existing process to produce ethene and other alkenes which are then used to
make new plastic polymers. The pyrolysis recycled plastic feedstock replaces naphtha or
gas oils used in the conventional process. Alternatively, the oil/wax can be refined in a
conventional fluidized catalytic cracker to produce gasoline and thereby replace petroleum
gas oils [45]. It was reported that the oil/wax product from plastics pyrolysis was of high
purity and would be easily accepted into the refinery process.
2.3.3 Fuel Properties of the Oils/Waxes from the Feedstock

Recycling of Plastics
The oils derived from pyrolysis of plastics have the potential to be used directly as fuels.
However, to act as direct substitutes for established petroleum-derived fuels requires
detailed analysis of their fuel properties in comparison with those of petroleum refined
fuels. Table 11.8 shows the fuel properties of oils derived from the pyrolysis of various
plastics [46, 47]. Table 11.9 shows comparative data for refined petroleum fuels [48].
The analysis of oils for their fuel properties involves a range of standard ASTM tests.
For example, flash point is determined by ASTM D93, calorific value by ASTM 129-64,
Table 11.8 Fuel properties of oils derived from the pyrolysis of various plastics
Property PE1 PP1 PS1 Nylon1 PP 50%1 Polyester 2

PE 43% styrene
Nylon 7% copolymer
Flash point (◦ C) 33.6 27.8 26.1 34.8 26.0 26.0
Pour point (◦ C) 2.7 −39 −67 −28 −5.0
Water content (ppm) 0.18 0.13 0.67 2500 310
Ash (wt%) 0.013 0.010 0.006 0.018 0.001 0.53
Viscosity (cst 50◦ C) 2.19 1.9 1.4 1.8 1.485 3.93
Density (kg/m3 ) 0.858 0.792 0.960 0.926 0.799 0.83
Cetane rating 56.8 12.6 54.3
Carbon (wt%) 86.1
Hydrogen (wt%) 7.2
Sulphur (wt%) 0.01 0.01 0.01 0.01 0.013 0.0
Initial B.Pt (◦ C) 75
10% B.Pt (◦ C) 93
50% B.Pt (◦ C) 189
90% B.Pt. (◦ C) 354
CV (MJ/Kg) 52.3 53.4 50.4 44.4 46.3 33.6
1
Reference [46]
2
Reference [47]
3
cst at 40◦ C
Table 11.9 Fuel properties of petroleum-derived fuels [48]
Fuel test Kerosene Gas Oil LFO HFO

Carbon residue (%) <0.15 <0.35
Viscosity
40◦ C (cs) 1.2 3.3 21 30
Water content (%) 0.05 0.1
Density (kg m−3 ) 0.84 0.78 0.89 0.95
Ash content 0.01 0.02
Flash point (◦ C) 40 75 79 110
Carbon (%) 87.1 85.5
Hydrogen (%) 13.6 12.8 12.4 11.8
Sulphur (%) 0.1 0.9 1.4 2.1
Initial boiling point (◦ C) 140 180 200 252
10% boiling point (◦ C)
50% boiling point (◦ C) 200 300 347
90% boiling point (◦ C) 315
CV (MJ kg−3 ) 46.6 46.0 44.8 44.0
LFO = light fuel oil

HFO = heavy fuel oil
ash content by ASTM D482-74, distillation range by ASTM D86, relative density by
ASTM D1298 and viscosity by ASTM D445.
The flash point of the oils derived from the pyrolysis of various plastics was low
compared with petroleum-derived fuels, being less than 35◦ C in all cases. For comparison,
diesel fuel has a required minimum flash point of 75◦ C and light fuel oil 79◦ C. The flash
point of a liquid fuel is the temperature at which the oil begins to evolve vapours in
sufficient quantity to form a flammable mixture with air. The temperature is an indirect
measure of volatility and serves as an indication of the fire hazards associated with storage
and application of the fuel. The low flash points of the oils may be expected since the
oils typically represent an unrefined oil with a mixture of components having a wide
distillation range. The pour point of a liquid fuel is the lowest temperature at which the
oil is seen to flow and as such is an indication of the flow characteristics of the fuel. The
viscosity of the plastics pyrolysis oils were similar to that of gas oil (diesel fuel). The
viscosity of a fuel is an important property since it affects, for example, the flow of the
fuel through pipes and other plant items, the atomization of the fuel in spray combustion
systems and the performance and wear of diesel pumps. The density of the plastics
pyrolysis oils was high compared with, for example, heavy fuel oils. The sulphur content
of the oils was significantly lower than the petroleum refined fuels. The distillation range
of the plastics pyrolysis oils reflects the fact that the oils are unrefined and consequently
would be expected to have a wide range of boiling points for the components of the
oil. This was also shown by the molecular weight distributions of the pyrolysis oils. The
petroleum refined fuels have boiling point ranges consistent with their derivation, that is
from the fractional distillation of crude petroleum oil.
The calorific value of the plastics pyrolysis oils was between 33.6 and 53.4 MJ kg−1
depending on the composition of the original plastic polymer. The calorific value was
high apart from the oil derived from the polyester/styrene copolymer resin used in the
manufacture of composite. This was attributable to the high oxygen content of the original
306 P.T. WILLIAMS
polyester used in the formulation of the copolymer and which would result in a high
oxygen content of the derived pyrolysis oil. The high oxygen content in the oil being
responsible for the lowered calorific value.
2.3.4 Chemical Feedstock Potential of the Oils/Waxes from the Feedstock

Recycling of Plastics
Feedstock recycling of plastics produces a hydrocarbon oil/wax product which has the
potential to be used as a chemical feedstock. The oils and waxes derived from the pyrolysis
of the polyalkene plastics, HDPE, LDPE and PP, produce an almost exclusively aliphatic
oil and wax. For example, Figure 11.13 shows the gas chromatogram of the wax derived
from the fluidized-bed pyrolysis of HDPE. Typically the waxes have a carbon number
range up to about C60 , whereas the oils would be lower, typically peaking around C20 .
Figure 11.13 for the wax in fact shows a bimodal distribution of carbon numbers, peaking
at C14 and C30 . Examination of the wax in detail shows that it consists of a series
of alkanes, alkenes and alkadienes (Figure 11.14). Gas chromatography has a limited
range of resolution and data on the molecular weight distribution would suggest that
much higher carbon number aliphatic compounds are present in the waxes. No significant
production of aromatic compounds was detected in the waxes derived from the pyrolysis
of HDPE, LDPE or PP in a fluidized-bed reactor at 550◦ C or in a fixed-bed reactor [7, 19].
However, Kaminsky et al. [9], using a fluidized-bed reactor at 740◦ C, reported very high
levels of benzene at 19.2 wt% of the original polymer for the pyrolysis of polyethylene.
In addition, they reported 18.2 wt% of benzene for polypropylene at 760◦ C pyrolysis
Tetracosene-1
Nonene-1
Octatetracontene-1
0.0 20.0 40.0 60.0 80.0 100.0

Time (mins)
Figure 11.13 Gas chromatographic analysis of the wax material derived from the
fluidized-bed pyrolysis of HDPE
alkane-1
n-alkane
alkadiene
20.32 24.25 28.17 32.10 36.03 39.95

Time (mins)
Figure 11.14 Detailed analysis of the gas chromatographic analysis of the wax material
derived from the fluidized-bed pyrolysis of HDPE showing the alkadiene, the alkene-1
and the n-alkane
temperature. However, Kaminsky et al. [9] used a fluidized bed where the pyrolysis gas
is partly recycled to provide the gas for fluidization and in addition the temperatures tend
to be higher than some other workers. The recycling of the pyrolysis gases at higher
temperatures may lead to increased concentrations of certain aromatic compounds, in
particular benzene.
The thermal degradation mechanisms of the polyalkene plastics leading to the formation
of various reaction products has been investigated by a range of researchers. It is suggested
that the thermal degradation of HDPE and LDPE occurs via random scission to yield
a wide spectrum of hydrocarbon fragments which may contain any number of carbon
atoms [49, 50]. The C–C bond is the weakest in the HDPE and LDPE structure. However,
during the degradation process the stabilization of the resultant radical after chain scission
leads to the formation of carbon double bonds, C = C, in the structure [51]. The large
number of compounds with carbon double bonds are shown by the higher concentration
of alkenes in the resultant pyrolysis oil/wax. The thermal degradation of polypropylene
has also been assigned to a random scission reaction which leads to the formation of a
large number of hydrocarbon species. Because the polypropylene is similar in structure
to HDPE and LDPE thermal degradation also results in a series of alkanes, alkenes
and alkadienes [52]. However, because of the presence of the CH3 side chain, different
hydrocarbons may also form in addition to those outlined for HDPE and LDPE,
Pyrolysis of polystyrene produces an oil very high in concentration of the monomer,
styrene and also other aromatic compounds. Figure 11.15 shows a typical gas chro-
matogram for the pyrolysis oil produced from the pyrolysis of polystyrene, showing
308 P.T. WILLIAMS
Benzene
Styrene
Styrene Dimer
Trimethlybenzene
Dimethyl Fluorene
Toluene
Xylene
Phenanthrene
Napthalene
Methyl Fluorene
2.45 11.97 21.50 31.02 40.55 50.07
Time (mins)
Figure 11.15 Gas chromatographic analysis of the oil material derived from the flu-
idized-bed pyrolysis of polystyrene
the high concentrations of styrene in the derived oils. For example, Kaminsky et al. [9]
used a fluidized-bed reactor at 520◦ C for the pyrolysis of polystyrene and reported a
styrene concentration of 76.8 wt% of the original polymer. Other workers have also shown
that styrene occurs in very high concentrations in polystyrene-derived pyrolysis oils. For
example, Scott et al. [8] using fast, fluidized-bed pyrolysis found a higher styrene yield
of 76.2 wt% at a pyrolysis temperature of 532◦ C. Similarly, Buekens and Schoeters [23]
also reported a styrene yield of 76 wt% from the fluidized-bed pyrolysis of polystyrene
at 600◦ C. Bouster et al. [24] reported high yields of styrene with a maximum of 78.7
wt% for pyrolysis of polystyrene at 800◦ C. Nishizaki et al. [53] showed a lower yield
of styrene of 50 wt% for the fast pyrolysis of polystyrene in the temperature range of
450–600◦ C. Williams et al. [16] also reported lower styrene yields of 56.1 wt% in the
oil derived from the fluidized-bed pyrolysis of polystyrene at 600◦ C. Other compounds
present in significant concentrations are the styrene dimer and trimer. In addition, the
oils contain a significant proportion of toluene, xylene and alkylated benzenes, indene
and indane and naphthalene [9, 16]. The thermal degradation mechanism for PS has been
shown to be first via chain scission and then random scission [54]. This results in the
formation of the styrene monomer and also styrene dimer, trimer and tetramer [55]. Other
hydrocarbons formed by the degradation process have been identified as benzene, toluene,
ethylbenzene and methylbenzene [54, 55].
The pyrolysis of PVC produces a highly aromatic oil in addition to hydrogen chloride
yields of more than 50 wt% [7–9, 14, 19]. The oil contains mainly aromatic compounds.
Benzene has been identified as the main aromatic compound at 22.1 wt% in the oil
from the fluidized-bed pyrolysis of PVC [19]. Benzene has also been identified as the
main product of PVC pyrolysis by Lattimer and Kroenke [32]. Montaudo and Puglisi [39]
identified benzene and also naphthalene and some other polycyclic aromatic hydrocarbons
in the thermal degradation product of PVC. The thermal degradation mechanism of PVC
is initiated by a dechlorination reaction resulting in the formation of hydrogen chloride
as was discussed previously. The vinyl structure of the plastic may indicate that aliphatic
products may be a consequence of the thermal degradation, however, PVC pyrolysis
clearly produces a mainly aromatic oil. The process of the elimination of a chloride
atom from the structure results in the formation of a carbon double bond in addition
to hydrogen chloride [55]. Further carbon double bonds are formed as more hydrogen
chloride is evolved from the resultant chain. Eventually the chain undergoes cyclization
to yield aromatic and alkylaromatic compounds [55].
Thermoset plastics have also been pyrolysed with a view to obtain chemicals for recy-
cling into the petrochemical industry. Pyrolysis of a polyester/styrene copolymer resin
composite produced a wax which consisted of 96 wt% of phthalic anhydride and an oil
composed of 26 wt% styrene. The phthalic anhydride is used as a modifying agent in
polyester resin manufacture and can also be used as a cross-linking agent for epoxy resins.
Phthalic anhydride is a characteristic early degradation product of unsaturated thermoset
polyesters derived from ortho-phthalic acid [56, 57]. Kaminsky et al. [9] investigated
the pyrolysis of polyester at 768◦ C in a fluidized-bed reactor and reported 18.1 wt%
conversion to benzene.
3 CONCLUSIONS
Pyrolysis of plastic waste has the potential to produce an oil or wax with potential uses
in the petrochemicals industry. The process also produces a hydrocarbon-rich gas with
a high calorific value which may be used to provide the energy requirements for the
pyrolysis process. Key process parameters are the composition of the original plastic
polymer, the temperature of pyrolysis, the fast removal of products from the hot zone of
the reactor to minimize secondary reactions and the design of the reactor. The process may
be optimized to produce a high calorific value gas or an oil/wax product. The oil/wax ratio
is also dependent on a range of process parameters, including, temperature, condensation
system and temperature and type of reactor. Oils from the pyrolysis of plastics have
properties which are similar to petroleum-derived fuels. Waxes have a high purity and
may be refined at the petroleum refinery to produce high-grade liquid fuels. Depending
on polymer type, the oils may also contain valuable feedstock chemicals for use in the
petrochemicals industry.
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12
Composition of Liquid Fuels

Derived from the Pyrolysis
of Plastics
MARIANNE BLAZSÓ
Institute of Materials and Environmental Chemistry, Chemical Research Center,
Hungarian Academy of Sciences, Pf. 17, H-1525 Budapest, Pusztaszeri út 59–67, H-1025
Budapest, Hungary
1 INTRODUCTION
The increasing demand for recycling plastics waste raises the question of how and to what
kind of products can be converted. Pyrolysis proved to be a suitable feedstock recycling
technique, converting the polymer material of waste into monomers, fuels or other valu-
able materials by thermal cracking processes. This method can be applied to transform
both thermoplastics and thermosets, moreover, it is suitable for the treatment of mixed
plastic wastes as well. Depolymerization of condensation polymers (polyester, polyamide,
polyurethane) can be carried out through milder chemical pathways (methanolysis, gly-
colysis, hydrolysis, aminolysis), so pyrolysis is not the best choice for their recycling.
Nevertheless, any type of plastic material may be present in plastic fractions of communal
and other not thoroughly preselected wastes.
The quality of the product is of primary importance in developing a recycling tech-
nology converting plastics into fuels by pyrolysis. Today the characterization of a liquid
fuel from any sources is obviously based on the qualification methods and standards of
fuels from mineral oil. The properties of the pyrolysis-derived fuels from plastics are
expected to be similar to conventional fuels (energy content, viscosity, density, octane
and cetane number, flash-point, etc.). However, in addition to the familiar ranking values
it is necessary to know more about the chemical composition of the plastic pyrolysis oil,
because of the peculiarities as follows:
316 M. BLAZSÓ
• There are a considerably larger variety of compositions of the plastic pyrolysis oil than
that of petroleum-related oils because of the diversity of the chemical composition
and structure of the source plastics.
• Organic additives (filler, plasticizer, flame retardant, antioxidant, colorant, etc.) or their
thermal fragments also appear among the pyrolysis products of plastic wastes.
• Certain components are recognized as responsible for instability or low volatility of
pyrolysis oil and for the production of reactive or harmful compounds upon combus-
tion (forming soot, environmentally unfriendly gases).
• In some plastics several kinds of chemical reaction may take place under pyrolysis
that could be severely influenced by the reaction conditions, leading to considerably
differing pyrolysis oils.
Thus, for the development of polymer waste recycling technologies it is helpful to be
aware of the chemical composition of the pyrolysis products of those polymers which are
typical components of plastic wastes.
In this chapter it will be demonstrated that there is a strict relation between the chemical
composition of plastics and their pyrolysis oil, but the relationship is not well understood
in many cases due to the fact that the products are determined by both the source and
the pathway of decomposition. The ranking values of pyrolysis oils derived from plastics
may be estimated on the basis of the correlation of major oil characteristics and chemical
composition and structure of component compounds.
2 EXPERIMENTAL METHODS
Laboratory-scale pyrolysers can be used for producing oils for analytical purposes. Many
scientific and technical publications report on the pyrolysis of well-characterized poly-
mers in open or closed reaction vessels, furnace-heated tubes, fixed-bed and fluidized-bed
reactors. The pyrolysis products are generally analysed off-line, being condensed in
cooled traps.
Chemical analysis of pyrolysis oil can be performed using the same methods as
applied to characterize petroleum related oil: various chromatographic tools such as high-
resolution gas chromatography (HRGC) [1], high-performance liquid chromatography
(HPLC) [2], multidimensional GC and HPLC [3], infra red (IR) and nuclear magnetic
resonance (NMR) [4] spectroscopic methods. Mass spectrometry (MS) is the best choice
for detecting the components separated by chromatography when qualitative analysis is
essential. This option is indispensable for the identification of plastics pyrolysis products
because of their variability.
Important properties of the pyrolysis-derived oils may be predicted from the informa-
tion obtained by fast, hyphenated analytical instruments. Pyrolysis products are analysed
on-line in a broad range of volatility from gases to heavy oil components by a micropy-
rolyser coupled to GC/MS (Py-GC/MS). Such a highly informative examination can be
accomplished in less than one hour. The critical temperatures, which should be effective
for pyrolysis may be read from the weight loss curve obtained by thermogravimetry (TG)
upon gradually heating up the plastic sample. The evolution profile of the volatile ther-
mal decomposition products can be monitored by coupling a thermobalance to a mass
spectrometer (TG-MS) or to Fourier transform infra red spectrometer (TG-FTIR). In the
LIQUID FUELS FROM PYROLYSIS 317
followings the optimal temperature range for liquid production obtained in TG will be
given for each representative polymer discussed, moreover a pyrolysis gas chromatogram
(pyrogram) will be shown which were obtained using the same pyrolysis and GC/MS
conditions.
3 CHEMICAL COMPOSITION OF PYROLYSIS LIQUIDS

3.1 RELATION OF MAJOR OIL CHARACTERISTICS AND CHEMICAL
FEATURES OF COMPONENT COMPOUNDS
The compositional analysis is an essential part of the quality evaluation of petroleum-

derived fuels. The concentration of different compound types such as paraffin, isoparaffin,
olefin, naphthene and aromatic are routinely determined by gas chromatography (PIONA
analysis), and can be rapidly measured by proton NMR spectroscopy.
Some fuel properties have long been known to be interrelated with chemical compo-
sition: density and aromatic content, viscosity and distillation range, cetane number and
aromatic content. Correlation studies applying various statistical computational methods
revealed the contribution of chemical structural units of organic compounds to the various
physical properties of hydrocarbon fluids, such as octane and cetane number, flash point,
cloud point, etc.
Octane and cetane number are used to measure fuel performance of gasoline and diesel
oil, respectively. The research octane number (RON) is broadly estimated from the chem-
ical composition of the fuels determined with the help of high-resolution GC [5, 6], FTIR
spectroscopy [7] and NMR analysis [8, 9]. Cetane number prediction is generally based
on the concentration of aromatic compounds and density values of oils. However, the
estimation is more reliable – and also applicable to synthetic diesel oils – when a more
detailed chemical composition characterization from GC/MS and NMR are taken into
account [10, 11]. Structural group contribution methods have been published for predict-
ing the flammability characteristics of pure hydrocarbon fluids as well [12, 13]. Flash
point estimated with this method was found to be in better agreement with experimen-
tal values than that calculated from boiling point with rough estimation equations. The
approach described by Cookson et al. [14] for correlating fuel composition and boiling
characteristics with fuel properties is based on information readily obtainable from 13 C
NMR spectroscopy and gas chromatography, and proved to be successful in accounting
for changes in fuel properties as a function of boiling range. The abundance of large
linear alkanes (> n-C24 ) in paraffinic crude oils increases their tendency to wax crystal-
lization, which can be demonstrated by a linear correlation between the concentration of
this hydrocarbon family and the crude oil cloud point [15].
Although these analytical approaches were specially developed for petroleum-derived
gasoline and diesel oil, the concept of them is applicable to the same boiling fraction of
plastic pyrolysis oil [16, 17]. Unfortunately we have not got enough experimental data for
the estimation of usual fuel characterization values when the pyrolysis oil contains not only
hydrocarbon components, but also oxygen-, and nitrogen-containing ones. Nevertheless,
the suitability of a plastic waste pyrolysate as a fuel is generally predictable on the basis
of the knowledge of the chemical composition and structure of the pyrolysis oil at various
boiling ranges. Py-GC/MS analysis of a plastic provides fast, one-run information on the
318 M. BLAZSÓ
chemical composition of pyrolysis products over the whole range of volatility from gases
to heavy oils. In the following, results obtained by this method on various plastics will be
reported and interpreted from the point of view of possible utilization of the pyrolysis oil.
3.2 THERMAL DECOMPOSITION REACTIONS OF POLYMERS
The composition of the pyrolysis products is primarily determined by the means of dis-
integration of the macromolecule to the molecules of gas, oil, and solid residue. Thus to
anticipate the pyrolysis oil composition of a plastic material, the chemical composition and
structure of the polymer and its thermal decomposition reactions should be consistently
considered. Typical thermal decomposition pathways of the various polymer kinds are
abundantly treated in the relevant scientific literature [18–20]. Thermal decomposition of
the polymer component of a plastic material is expected to begin at the weakest chemical
bonds of the macromolecule. However, there are decomposition pathways which require
lower energy than the direct breakage of the bonds, when rearrangement over four or six
neighbouring atoms leads to the elimination of a volatile compound or to the scission of
the macromolecular chain.
Elimination of carbon dioxide from carboxyl, water from alcoholic hydroxyl, carboxylic
acid from alkanoate, and hydrogen chloride from chlorine side groups or chain ends are
typical thermal decomposition reactions in the temperature range 250–350◦ C. Hydrogen
chloride is an important product of poly(vinyl chloride) because every second carbon atom
of the hydrocarbon polymer chain is chlorine substituted. But hydroxyl, alkanoate and
free carboxylic acid groups normally occur only at the ends of the macromolecular chains
in customary plastics, thus the contribution of their elimination to the volatile pyrolysis
products is negligible.
The relatively low thermal stability of aliphatic polyester, polyamide and polyurethane,
decomposing in the temperature range 250–450◦ C, is due to the rearrangement of the
ester, amide or urethane linkages along the macromolecular chain, leading to linear
fragments when single linking groups are reorganized. One of the newly formed macro-
molecular ends will be terminated by a carboxylic, imino or isocyanate group, respectively,
and the other by a vinyl or a hydroxyl group (Scheme 12.1). The imino group is fast dehy-
drated to nitrile in polyamide, while decarboxylation of the terminal group leads to an
alkyl chain end in polyester, and that of the labile carbamic acidic group to a terminal pri-
mary amino group in polyurethane. Cyclic monomer or oligomers may be eliminated by
the rearrangement of the atoms of a pair of ester or amide linkages in aliphatic polyester
or polyamide, respectively, as indicated in Scheme 12.2 for polyester. Oligomer cycle
formation takes place similarly in the aliphatic polyether or polyester soft segments of
thermoplastic polyurethane.
Radical breakage of certain weak chemical bonds may occur already at around 300◦ C,
however, the more typical temperature range is above 400◦ C for this kind of disintegration
of organic compounds. Free radicals formed by thermolysis are unstable fragments of high
energy content; their recombination or termination by reaction with another radical or
radical trap may stop the process. Alternatively, a radical chain reaction proceeds by the
repetition of a reaction in which a free radical attacks a stable molecule causing its decay
and producing a new reactive radical. Free radical decomposition is the most frequent
reaction type taking place during the pyrolytic recycling of plastic wastes.
Scheme 12.1 Thermal scission of aliphatic polyester, polyamide and polyurethane

through rearrangement of six or four atoms
Scheme 12.2 Ester exchange in polyesters through intramolecular rearrangement of

two ester groups
320 M. BLAZSÓ
Scheme 12.3 Free radical decomposition of saturated hydrocarbon chain polymers

through random cleavage. X=H, methyl, phenyl or chlorine in PE, PP, PS or PVC,
respectively, 2-1, when X=H (in PE)
In saturated hydrocarbon chain polymers homolytic scission of a C–C bond leads to

two macroradicals that may be primary (1) or secondary (2) one shown in Scheme 12.3. A
typical free radical attack is the hydrogen abstraction, i.e. the transfer of the radical site to
another molecule or in to a neighbouring section of the same molecule. Scheme 12.3 illus-
trates the transfer of a primary radical (1) to a tertiary carbon atom of another molecule.
The β-scission of the mid-chain radical results in a vinyl-group-terminated polymeric
chain (3) and a new secondary macroradical (2). This kind of radical chain reaction cuts
the macromolecules randomly in to oligomer chains terminated either by methyl or by
vinyl groups. The hydrogen abstraction by a terminal macroradical may be more probable
from those carbon atoms of its own coiled chain which are easily approachable due to a
favourable conformation. The oligomeric compounds formed through this decomposition
route are of smaller molecular mass than the products of the random chain scission. The
repetitive β-scission of a terminal radical producing vinyl compounds and reproducing the
macroradical represents the radical depolymerization of the polymer chain to monomer
in vinyl polymers.
The breakage of the polymer chain is the most probable at the allyl position to double
bonds, forming primary macroradicals in unsaturated hydrocarbon chain polymers. The
deplacement of the primary radical site is carried on through the rearrangement of the
C=C double bonds, producing monomer or cyclic dimer and reproducing the primary
macroradicals (4 and 5) according to Scheme 12.4.
The free radical reactions in aromatic or partly aromatic polymers and phenolic resins
are not chain reactions. There is not much opportunity in these macromolecules for
rearrangement facilitating a continuing decomposition. In general there are not enough
hydrogen atoms available to stabilize the free radicals produced by the cleavage of alky-
lene, ester, ether or amide linkages connecting the aromatic rings into macromolecules. In
this way only a part of the thermal fragments are volatilized, and those radicals that are
Scheme 12.4 Free radical decomposition of unsaturated hydrocarbon chain polymers

through rearrangement of bonds at the macroradical end. X=H in BR, X=methyl in NR.
5-4, when X=H (in BR)
not able to abstract a hydrogen recombine with other radicals, forming a carbonaceous
residue. The aromatic rings are generally not cleaved in pyrolysis reactions, however from
phenolic moieties carbon monoxide could be split off above 600◦ C.
As a consequence of the variety of thermal decomposition pathways, the composition
of the pyrolysis products may be controlled by the temperature when the plastic is made
up of different polymers or when the constituent polymer decomposes through varying
routes at different temperatures.
4 PYROLYSIS PRODUCTS OF PACKAGING WASTE PLASTICS
Waste plastics composition varies with collection area, sorting methods and time period,
moreover several waste constituent polymer types occur in various waste categories.
Nevertheless each customary plastic material will be discussed only in one of the three
waste group included in this chapter.
The majority of packaging plastic materials consists of polyolefins and vinyl polymers,
namely polyethylene (PE), polypropylene (PP), polystyrene (PS) and poly(vinyl chloride)
(PVC). Obviously, these polymers have many other applications not only as packaging
materials. Chemically they are all composed of saturated hydrocarbon chains of macro-
molecular size; their typical thermal decomposition pathway is free radical one initiated by
the homolytic scission of a backbone carbon–carbon bond. In spite of the basic similarity
of the initial cleavage, the decomposition of the hydrocarbon macroradicals is strongly
influenced by the nature of the side groups of the main chain.
The general formula displayed in Scheme 12.3 indicates that the chemical composition
of the repeating unit of the polymer (a section of the chain of two carbon atoms) cor-
respond to that of the monomer, where X designates hydrogen and chlorine atom in PE
and PVC, methyl and phenyl group in PP and PS, respectively. Since the chemical bond
between carbon atoms of the saturated hydrocarbon chain is weaker than that connecting
hydrogen, methyl or phenyl group to the chain, PE, PP and PS thermal decomposition
begins with homolytic scission of the polymer chain. Cleavage of the X side group
322 M. BLAZSÓ
occurs only in those vinyl polymers in which the bonding to the substituent is weaker
than the backbone C–C bond. In PVC the Cl–CH(CH2 )2 –bond strength (356 kJ mol−1 )
is somewhat lower than that of C–C along the chain (370 kJ mol−1 ) [21], thus chlo-
rine is cleaved first. Moreover, the breakage of a chlorine bonding to a tertiary carbon,
Cl–C(CH2 )3 –at an accidental branching point, or at an allyl position to a double bond,
Cl–CH(CH2 )(CH=CH)–representing a defect point of PVC, requires even less energy
than the cleavage of the regular chlorine substituents.
4.1 POLYOLEFINS
The reactions of the alkyl macroradicals produced by the scission of the saturated hydro-
carbon polymer chain (illustrated in Scheme 12.3) depend on their reactivity and on that
of the available reaction partners. It could be expected that radical depolymerization, i.e.
β-scission of the primary macroradical will likely take place, however practice contra-
dicts to this expectation in the case of polyolefins. The yields of light olefins evolving
by solely thermal decomposition in conventional reactors are rather low compared with
those of liquid products. Primary saturated hydrocarbon radicals (1) are more reactive
than secondary ones (2), thus thermal decomposition of PE, in which the polymer chain
breakage results in primary radicals only, differs considerably from that of other poly-
olefins, in which both primary and secondary radicals are formed in the initial breakage,
and the mid-chain β-scission leads to secondary radical as illustrated in Scheme 12.3. Any
hydrogen atom along the polyethylene chain is equally abstractable by the free radicals,
however, in other polyolefins the hydrogen is more easily detached from tertiary carbon
atoms than from the secondary ones, because the energy required for the cleavage of a
C–H bond in hydrocarbons decreases in the following order [21]:=CH–H > –CH2 –H
> –CH(CH2 )–H > –C(CH2 )2 –H.
4.1.1 Pyrolysis Products of PE

PE pyrolysis advances at the maximal rate between 420 and 500◦ C leading to an imposing
series of straight-chain hydrocarbons. The yield of hydrocarbon gases and solid residue
normally stay low compared with liquids in conventional reactors. In the pyrogram of
a HDPE sample displayed in Figure 12.1 the first peak (at 2 min retention time) covers
C1 –C5 hydrocarbons. The next peaks from C6 to C12 include the boiling range of gasoline
(in the retention time interval 2–10 min in the pyrogram), then the further peaks corre-
sponding to straight chain hydrocarbons from C13 to C19 give the boiling range of diesel
oil (retention time 10–18 min). The heavy oil and wax components from C20 on up to
the end of the pyrogram constitute seemingly the major part of PE pyrolysate. Although
GC/MS total ion chromatographic peak areas are not truly proportional to the masses
of the corresponding compounds, a rough estimation of the contribution of the various
boiling ranges to the total pyrolysate can be made based on the relative peak areas of the
pyrogram obtained by Py-GC/MS.
In the magnified detail of Figure 12.1 triplets of compounds of the same carbon num-
ber are distinguished, the highest of the three GC peaks is 1-alkene and the two smaller
peaks of lower and higher retention time correspond to α, ω-alkadiene and n-alkane,
Figure 12.1 Py-GC/MS chromatogram of HDPE at 500◦ C. Cx denotes 1-alkenes of x

carbon atoms
respectively. The formation of these types of compounds from a saturated hydrocarbon

chain is well described by a free radical mechanism [22]. Among the thermal decom-
position reactions of the primary polyethylene macroradical anticipated [23] only those
will be detailed in the followings which contribute to the formation of the generally
obtained product distribution. As outlined in the previous part, the primary macroradicals
formed by random breakage of the PE chain may abstract hydrogen from any carbon
atoms of a macromolecule in sufficient vicinity in the polymer melt. The result of this
reaction is a methyl terminal group and a secondary macroradical. The latter decomposes
by β-scission, leading to the breakage of the attacked macromolecule, dividing it in to a
vinyl-group-terminated and a primary-radical-terminated fragment. Since the initial reac-
tant – the primary radical – is reproduced, the chain reaction will continue and produce
equal number of methyl and vinyl terminal groups in the fragments of the gradually
decreasing molecular mass, which can be only alkanes, 1-alkenes and α, ω-alkadienes in
1:2:1 relative yields. In principle the process should result in a random distribution of
the linear hydrocarbon fragments over a carbon atom range covering volatilizable com-
pounds. The slight positive deviation of peak heights from a statistical distribution of the
hydrocarbon homologous series of 1-alkenes at C6 , C7 , C10 , C11 , C14 , C15 C18 , C19 is due
324 M. BLAZSÓ
to the superposing contribution of backbiting of the primary macroradical in to its own
chain at preferred carbon atoms due to the conformation of the polymer coil in the melt
[23]. Note that the higher-molecular-mass section of the product distribution is missing in
the pyrogram because the given GC conditions are not satisfactory for the analysis of the
components over C28 . In a mass spectrometer (under vacuum) the distribution has been
reported [24] to go up to C50 .
The knowledge of the mechanism leads us to the conclusion that from PE we may not
expect branched hydrocarbons solely by thermal decomposition, that is why the octane
number of pyrolysis-derived gasoline from PE is expected to be low (RON value of 20
was reported in a noncatalytic pyrolysate of LDPE [25]). Anyway, the contribution of the
gasoline boiling range to the total pyrolysate yield cannot be very high, as pointed out
above. The cetane number of PE pyrolysis diesel oil should be high due to its composition
of exclusively linear chain hydrocarbons. However, the pour point and cloud point will
be low because of the high concentration of wax. The yield of isoalkanes is negligible,
even from LDPE which contains some short side chains. The production of aromatic
and polyaromatic compounds that occur at above 700◦ C from PE could increase both
the relative yield of the gasoline and diesel oil and the octane number, while decrease
cetane number. However, the aromatic and polyaromatic components of fuels are not well
tolerated for environmental protection reasons.
The gasoline obtained when pyrolysing 100 g PE waste in a closed autoclave of 1 L
volume at 420–450◦ C for 2 h [26] was reported to give a relatively high research octane
number of 80.9, but the aromatic content was also high 16.7 wt% among the pressurized
conditions. The diesel oil of the same pyrolysate was characterized by 28.7 wt% aromatic
content, 41◦ C ignition temperature, −11◦ C cloud point and a cetane index of 32. In a
semi-batch reactor HDPE was pyrolysed with a nitrogen flow at 440–460◦ C for 4 h [27]
and the resulting thermolysis products had 2.5 wt% aromatic <22◦ C flash point, 10◦ C
cloud point, 0◦ C pour point, and cetane index of 58.2. The product was catalytically
hydrogenated in both cases in order to reduce the alkene content responsible for the
instability of PE pyrolytic fuels.
4.1.2 Pyrolysis Products of PP

Polypropylene decomposes between 400 and 470◦ C. The pyrogram of an isotactic PP
displayed in Figure 12.2 shows that the most important components of the pyrolysate are
trimer, tetramers and pentamers of propene, boiling in the gasoline range. The oligomers
of propene are isoalkenes joining the propene units at the second and third carbon atoms
similarly to PP. Propene gas and n-pentane are eluted under the first and second peak of the
pyrogram, the third peak corresponds to the dimer of propene (2-methyl-1-pentene). The
second part of the pyrogram (above 13 min) comprising the oil and heavy oil boiling range
is populated by the peaks of higher oligomers a series of which are α, ω-isoalkadienes
(denoted by asterisk).
The observed pyrolysis product distribution of PP is developed by a free radical mech-
anism [28, 29] which begins with the homolytic breakage of the polymer chain drawn
in Scheme 12.3 where X represent a methyl group in this case. Primary macroradical 1
is formed only in the initial step, thus its decomposition plays a minor role in PP. Sec-
ondary macroradicals may decompose to propene by depolymerization reproducing 2, or
Figure 12.2 Py-GC/MS chromatogram of isotactic PP at 500◦ C. Px denotes oligomer of

x propene units; peaks labelled* are dienes
abstract hydrogen, transferring the radical site to a tertiary carbon atom of an other macro-
molecule or that of its own chain. The intermolecular radical transfer of 2 is followed
by the β-scission reaction drawn in Scheme 12.3, resulting in a vinyl terminal group 3
and reproducing 2. This chain reaction produces n-propyl and 2-methylvinylene terminal
groups in the fragments, which can be isoalkanes, 1-isoalkenes (oligomers) and α, ω-
isoalkadienes. The series of peaks above pentamer represent these fragment compounds
in the pyrogram of PP in Figure 12.2. The considerably superior yield of trimer, tetramers
and pentamers to that of the larger oligomers indicates the contribution of another reaction.
Intramolecular radical transfer of a secondary macroradical to a tertiary carbon atom of its
own chain leads to these oligomers, drawn in Scheme 12.5. The two possible directions
of β-scission explain the occurrence of n-pentane among the wholly isoalkanoic products
of PP.
In the pyrolysis process of PP the intramolecular radical transfer is preferred to the
intermolecular one, thus the low oligomer formation predominates. Consequently the
pyrolysis oil of PP is much more volatile than that of PE, decomposing mainly through
intermolecular radical transfer. The difference of the backbone structure of the products
of these polymers is more important from the point of view of fuel properties. The
isoalkanoic structure of PP is held in the thermal decomposition products, in this way the
octane number of the pyrolysis oil might be high. In a batch reactor [26] the gasoline
fraction (44–220◦ C) of the pyrolysis oil obtained from 100 g PE and PP mixture at
440◦ C has an octane number of 88.6 with 5.6 wt% aromatic content, and the diesel oil
(151–347◦ C boiling point range) had 56◦ C ignition temperature, −4◦ C cloud point and
a cetane index of 59.5. Pyrolysing waste PP in an 1 L autoclave at 430◦ C for 20 min
326 M. BLAZSÓ
Scheme 12.5 Intramolecular radical transfer and oligomer formation in vinyl polymers
under nitrogen atmosphere of 3.5 MPa [30], the RON value of the liquid boiling <150◦ C
was found to be 53. When mixed with 16% of PE and PS the observed RON was 56 for
this fraction, and for an oil boiling <270◦ C it was 45. A mixture of 1:1:1 of the three
polymers under similar conditions gave a liquid boiling <150◦ C of 58 RON, and an oil
boiling <270◦ C of 40 RON. When PE was the major component of the mixture (70%) the
two fractions of the pyrolysate have got as low a RON value as 24 and 20, respectively.
4.2 VINYL POLYMERS
In the general formula of the hydrocarbon chain polymers in Scheme 12.3 the vinyl
polymers contain a nonalkyl X substituent. The size and the chemical composition of
the substituent influence the reactions of the secondary macroradical, the main reactive
competitor of the thermal decomposition process in vinyl polymers. A bulky substituent
such as the phenyl group in PS may hinder the intermolecular radical transfer by shield-
ing the easily abstractable hydrogen atoms [31] while at the same time a phenyl group
is able to give a higher stability to the secondary macroradicals by resonance over the
aromatic ring. The secondary macroradical plays the main role in the pyrolysis pro-
cess of several vinyl polymers [19, 28] which is either depolymerized to monomer
or transferred to the third and fifth carbon atom from the radical end of the macro-
molecule evolving dimer and trimer after β-scission, respectively, reproducing the sec-
ondary macroradical in a chain reaction as drawn in Scheme 12.4. The β-scission may
also proceed in the other direction along the macroradicals, leading to small radicals
and vinyl-terminated macromolecules in this case. The volatile radicals abstract hydrogen
atoms, and the radical site is transferred to another macromolecule continuing the chain
reaction.
Division of the side groups from the main chain occurs only in those vinyl polymers in
which the bonding of the substituent to the chain is weaker than the backbone C–C bond.
The radical of the cleaved substituent draws hydrogen from the neighbouring carbon atom
and is eliminated, for example as acetic acid from poly(vinyl acetate), or as hydrogen
chloride from PVC.
4.2.1 Pyrolysis Products of PS
Polystyrene (PS) has somewhat lower thermal stability than the polyolefins, its pyrolysis
goes on between 380 and 450◦ C without producing gases or leaving a remarkable amount
of residue after total conversion. In spite of the fact that the majority of the carbon atoms
are assembled in phenyl side groups in this polymer, a negligible amount of benzene is
formed at that temperatures, because the Caryl –Calkyl bond connecting the phenyl group to
the polymer chain is stronger than the bond of alkyl carbons along the chain. The pyrogram
of PS contains three dominant components, styrene (bp 145◦ C) in the gasoline boiling
range, styrene dimer in the diesel oil range, and styrene trimer boiling at 400◦ C. This
pyrolysis product distribution suggests that the intermolecular radical transfer is negligible
in PS. Among the decomposition pathways of the free radical mechanism in hydrocarbon
chain polymers, the intramolecular processes dominate. The lack of those products, which
were originating from the β-scission in the direction of volatile radical formation, confirms
the supposition that intermolecular hydrogen abstraction is obstructed in PS.
The pyrolysate of PS could be better used as feedstock than as fuel, because of its high
aromatic content and low storage stability. The high aromatic content of PS pyrolysis
oil helps to compensate the low octane number of PE oil. Pyrolysing waste PS in an
autoclave at 430◦ C [30], the light liquid fraction boiling <150◦ C and the oil <270◦ C had
98 and 89 RON, respectively. When PS was only 70% in a waste mixture containing PE
and PP as well, RON values were decreased to 80 and 66, respectively. From a mixture of
PE and PS at 440◦ C gasoline of 95.8 octane number was obtained in a batch reactor [26],
however, the aromatic content was 56.7 wt%. The diesel oil fraction (170–360◦ C boiling
point range) contained nearly as much aromatics and had ignition temperature 58◦ C,
cloud point −8◦ C and a cetane index of 50. From a plastics-derived liquid produced by
the pyrolysis of a mixed plastics feed consisting of HDPE, PP and PS the naphtha fraction
(boiling range up to 205◦ C) had a RON of 84.8 with a composition of 25% aromatics,
54% paraffin and 21% olefin [16].
4.2.2 Pyrolysis Products of PVC

TG analysis of poly(vinyl chloride) indicate that thermal decomposition is carried out
in two distinct decomposition steps between 280 and 350◦ C, then 410 and 490◦ C. In
the first step dehydrochlorination and benzene formation goes on simultaneously. In a
second step of decomposition alkylaromatic and polyaromatic compounds are produced
through aromatic ring formation [32] and around 8–15% carbonized solid residue remains
after pyrolysis. Figure 12.3 shows the pyrogram of PVC, where the two main peaks are
hydrogen chloride and benzene that originate from the dehydrochlorination step. The
other peaks all correspond to aromatic compounds, one- and two-ring alkylaromatic ones
in the gasoline boiling range, with two- and three-ring alkylaromatic ones in the diesel
oil boiling range.
PVC is a vinyl polymer where X is a chlorine atom in the general formula of Scheme
12.3, but its thermal decomposition follows a quite different pathway from that of PS,
starting with division of the side groups from the main chain. When a chlorine atom is
cut off from a defect point (tertiary carbon atom or allyl bond), it abstracts the hydrogen
atom from the next carbon atom, then hydrogen chloride is eliminated, together with the
328 M. BLAZSÓ
Figure 12.3 Py-GC/MS chromatogram of PVC at 500◦ C
Scheme 12.6 Thermal decomposition reactions in PVC
formation of a double bond along the polymer chain, as shown in Scheme 12.6. The
next chlorine atom, being at an allyl position to the newly formed double bond, will be
split easily and hydrogen chloride elimination continues in a chain reaction, leaving a
series of conjugated double bonds behind, transforming the saturated hydrocarbon chain
of the polymer to a conjugated polyene. Through this process the polymer can be nearly
quantitatively dechlorinated at as low temperature as around 300◦ C.
Plasticizer is added to PVC in many applications. Most frequently di(2-ethylhexyl
phthalate) is used, boiling at 230◦ C, thus it may be evaporated from the molten PVC at
the dehydrochlorination stage, if the pyrolysis is carried out first at a lower temperature
in order to get rid of the chlorine prior to higher temperature pyrolysis. At above 600◦ C
the phthalic ester decomposes and its fragments, phthalic acid anhydride, 2-ethylhexanol
and 3-methylheptene are condensed in the gasoline boiling range of the PVC pyrolysate.
Thus concentration of oxygenates and aliphatics in the pyrolysis oil of plasticized PVC
can be considerably increased due to high plasticizer content.
4.3 POLYESTERS
Among polyesters synthesized from 1,4-benzenedicarboxylic acid and aliphatic diols,

poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) are the most
frequently applied ones. Hydrolysis is evidently the easiest chemical recycling technique
of polyesters, however they may be mixed with other waste plastics, thus it is useful to
know the properties of their pyrolysis product.
4.3.1 Pyrolysis Products of PET

Thermal decomposition of polyesters of terephthalic acid proceeds between 380 and
450◦ C, leaving about 20% of carbonized residue. In the pyrogram of PET displayed
in Figure 12.4, in addition to the carbon dioxide peak there are sharp peaks correspond-
ing to esters and broad peaks of aromatic carboxylic acids. The thermal fragments seen
in the chromatogram are all derived from a reaction involving six-atom rearrangement of
the ester linkage and the ethylene unit, analogous to that drawn in Scheme 12.1a. In PET
the successive formation of a free carboxylic acid and an ethenyl ester-group-terminated
macromolecular fragment leads finally to mono- and diethenyl terephthalate (denoted as
ET and ETE in Figure 12.4), which are the main components in the diesel oil boiling range
of the pyrolysate. Partially decarboxylated carboxylic acid products of the same reaction
are benzoic acid and ethenyl benzoate (EB), which boil in the gasoline range. The two-
aromatic-ring fragments of PET, ethylenedibenzoate (BEB) and benzoyoxylethylethenyl
terephthalate (BETE) are already heavy oil components.
The main inconvenience of PET pyrolysate is related to the aromatic carboxylic acid
components having high melting points (i.e. benzoic acid melts at 122.4◦ C, much higher
than n-C24 at 54◦ C).
5 PYROLYSIS PRODUCTS OF AUTOMOTIVE WASTE PLASTICS
Automotive plastic waste components are, in addition to PP and PVC, styrene copolymers,
rubber, polyamides and polyurethanes.
5.1 STYRENE COPOLYMERS
Plastics copolymerized from styrene, butadiene and acrylonitrile offer a wide applica-
tion scope, thus high-impact polystyrene (HIPS, styrene–butadiene copolymer), styrene–
330 M. BLAZSÓ
Figure 12.4 Py-GC/MS chromatogram of PET at 500◦ C. B, E and T denote benzoate,

ethylene and terephthalate units, respectively, in ester-type compounds
butadiene rubber (SBR), poly(acrylonitrile-co-styrene) (SAN), and poly(acrylonitrile-co-

styrene-co-butadiene) (ABS) may be present in municipal, automotive and electronic
plastic wastes as well.
In HIPS the butadiene content is in general low, the chemical structure of the polymer
kept of vinyl type, thus the pyrolysis product distribution is very much like that of PS.
However, some negligible components of PS pyrolysate such as toluene, α-methylstyrene,
and 1,3-diphenylpropane are markedly produced from HIPS. These compounds originate
directly from those volatile radicals which have been produced by the β-scission of the PS
chain end. Presumably the intramolecular radical transfer necessary for the stabilization
of the volatile radicals is facilitated due to the presence of butadiene segments in the
copolymer.
5.1.1 Pyrolysis Products of ABS

The pyrolysis liquid production range of ABS extends from 380 to 470◦ C similarly to
that of PS, and the decomposition goes on in a single step with 1–2% solid residue.
According to the pyrogram of ABS displayed in Figure 12.5 the pyrolysate contains
monomers, dimers and trimers, as expected from a vinyl polymer. Since the copolymer is
composed of acrylonitrile and styrene segments, the main components of the pyrolysate
are acrylonitrile in the gaseous phase, styrene in the gasoline boiling range, dimers and
those trimers which are composed of two acrylonitrile and one styrene units in the diesel
oil boiling range, styrene trimer and the other set of trimers which are composed of one
Figure 12.5 Py-GC/MS chromatogram of ABS at 500◦ C. A and S denote acrylonitrile

and styrene, and these units in dimers and trimers
acrylonitrile and two styrene units in the heavy oil range. The same slight differences
can be observed in the composition of the pyrolysate of SAN and ABS as in that of
PS and HIPS described above. The pyrolysis product distribution is consistent with the
same free radical decomposition mechanism that has been described for PS. Although
the presumption explaining the minimal contribution of intermolecular radical transfer
by the hindrance of the bulky phenyl group [31] is not confirmed. The nitrile group is
not as large as phenyl, and about the half the substituents are nitriles in ABS. Even so
the same extent of hindrance is reflected in the product distribution of ABS as in that
of PS.
The hybrid dimers and trimers of ABS all contain nitrile groups, thus their robust
contribution to diesel oil and heavy oil boiling range may be strongly disadvantageous
for the utilization of oil products as fuels, because of NOx formation under combustion.
At the same time the gasoline with boiling range beginning at above the boiling point of
acrylonitrile (77.3◦ C) contains only a low concentration of acrylonitrile dimer as nitrogen-
containing component.
5.2 RUBBER PLASTICS
The polymers of rubber plastics have unsaturated hydrocarbon chain structure, since they
are polymerized from alkadienes. The general formula of poly(1,3-butadiene) or butadiene
rubber (BR) and polyisoprene or natural rubber (NR) is drawn in Scheme 12.5, where
X is hydrogen in BR and methyl group in synthetic polyisoprene or NR. The free rad-
ical mechanism of thermal decomposition starts by homolytic scission of the alkyl C–C
bonds. Two primary macroradicals (4 and 5) are formed for which the rearrangement
332 M. BLAZSÓ
of the nearest double bond is an easy way of stabilization, splitting off a monomer and
reproducing 4 which continues the chain reaction. Interaction of the macroradical with
the second-nearest double bond, resulting in its rearrangement also takes place, forming a
ring of six atoms (see Scheme 12.5) producing cyclic dimer and reproducing 5. Through
the interaction of the macroradical with further double bonds of its own chain, higher
oligomers are also formed similarly.
5.2.1 Pyrolysis Products of NR
Polyisoprene, either synthetic polymer or natural rubber, decomposes to liquids between

340 and 430◦ C. The pyrogram of NR displayed in Figure 12.6 shows that there are
two major individual components in the gasoline boiling range, isoprene, the monomer
and limonene, the cyclic dimer. The relative contribution of the higher oligomers to
the pyrolysis oil should not be underestimated [33]. Humps of trimers and tetramers in
the diesel oil boiling range, and even pentamers and hexamers in the heavy oil range,
are observed in the pyrogram under which a group of oligomer isomers of the same
molecular mass are eluted in the pyrogram. The higher oligomers are not totally separated
by GC, most probably because of the occurrence of several conformational isomers. The
product distribution in the pyrogram indicates that NR pyrolysis reactions conform with
the decomposition mechanism of the polymer chain outlined above.
The isoalkene structure of the majority of the oil components confirms the good gasoline
quality of pyrolytic fuel from NR. Nevertheless, from tyre waste other components are
also evolved related to the vulcanizing agent and additives.
Figure 12.6 Py-GC/MS chromatogram of natural rubber at 500◦ C. ix denotes oligomers

of x isoprene units
5.2.2 Pyrolysis Products of BR and SBR
Polybutadiene has a considerably higher thermal stability than polyisobutylene. BR is
pyrolysed between 370 and 480◦ C in TG, and only 3% residue is left. The pyrogram of
BR is analogous to that of NR, in addition to the important peaks of monomer (butadiene)
and cyclic dimer (dipentene, i.e. 4-ethenylcyclohexene), groups of higher oligomers appear
at higher retention times. The decomposition temperature range of poly styrene–butadiene
rubber (SBR) is roughly the same as that of BR. In the pyrogram of SBR styrene is also
an important component besides BR oligomers, but the other aromatic compounds such as
benzene, toluene, xylenes occur in similarly small concentrations in the pyrolysis liquids,
as in that of BR and NR. The concentration of aromatic compounds in the pyrolysis oil
increases with pyrolysis temperature, at the same time hydrogen evolves at above 600◦ C
from tyre waste.
The important contribution of styrene makes the gasoline of SBR pyrolysate, rather
aromatic while the oil boiling range is like that of BR.
Pyrolysing waste tyres in TG, three weight loss stages are reported [34]: 200–330◦ C,
330–400◦ C and 400–500◦ C. The first step corresponds to the thermal decomposition of
the mixture of oils, moisture, plasticizers and other additives, the second one to that of NR
and the third one to the decomposition of BR and SBR content of the tyre. The pyrolysis
conditions influence strongly the resulting oil [35].
An oil of low flash point in the range 14–18◦ C, and of 41–43 MJ Kg−1 gross calorific
value has been obtained in batch pyrolysis [36] of automobile tyre waste. In a pilot plant
with semi-continuous feeding [37] the liquid yield of tyre waste decreased seriously with
increasing temperature, and it was always lower in an atmosphere containing oxygen that
in nitrogen.
5.3 POLYAMIDES
Among the several kinds of polyamides composed of the large variety of acyclic and
aromatic amino carboxylic acids or diamines and dicarboxylic acids, two Nylons are the
most extensively applied in many fields. Nylon 6 and Nylon 6,6 are found in various
waste streams, they may be present in pyrolysis recycling feeds as well.
Amide group scission (termed as cis-elimination mechanism) and intramolecular rear-
rangement of two amide groups, leading to cyclic compounds [20] are the main pyrolysis
reactions in acyclic polyamides. The former reaction is outlined in Scheme 12.1b and the
ester exchange drawn in Scheme 12.2 is analogous to the latter one.
5.3.1 Pyrolysis Products of Nylon 6

Polyamide-6 (PA-6 or Nylon 6) decomposes between 410 and 490◦ C predominantly to
ε-caprolactam which is its cyclic monomer. The intramolecular rearrangement of a pair
of amide groups separated by five methylene units is geometrically favoured in the coiled
polymer chain of PA-6, thus the seven atomic monomer ring is easily formed. Cyclic dimer
and its dehydrated derivatives are also produced through a rearrangement reaction analo-
gous to ester exchange shown in Scheme 12.2. Amide group cleavage by cis-elimination,
resulting in 5-hexene nitrile makes only a minor contribution to the pyrolysis of Nylon 6.
334 M. BLAZSÓ
The pyrolytic recycling of Nylon 6 is attractive for recovering the valuable monomer
from a waste consisting only of this polymer, although catalytic recovery of caprolactam
seems to be a more suitable process [38]. When this polymer is present as only one of the
components of a mixed waste it should be taken into consideration that the constituents
of Nylon 6 pyrolysis liquid are nearly all nitrogen-containing compounds, namely small
amounts of alkane and alkene nitriles boiling in the gasoline range, ε-caprolactam in the
diesel oil boiling range, and cyclodiamides in the heavy oil range.
5.3.2 Pyrolysis Products of Nylon 6,6
The pyrolysis temperature range of PA-6,6 is essentially the same as that of PA-6.
However, the thermal decomposition product distribution of the two Nylons are quite
dissimilar. There are several peaks in the pyrogram Pa-6,6 displayed in Figure 12.7.
Two important peaks correspond to compounds formed through the rearrangement of
amide groups according to the reaction in Scheme 12.1b, i.e. hexanedinitrile and N -5-
hexenyl-1-cyanopentanamide. Cyclic diamide (1,8-diaza-2,9-diketocyclotetradecane) and
its dehydrated derivative are the products of the rearrangement of two amide groups (sim-
ilar to Scheme 12.2). Cyclopentanone is known as a characteristic pyrolysis derivative of
the adipic (hexanedioic) acid moiety of polyamides [39], moreover, some ε-caprolactam
has been generally reported as a minor side product of the thermal decomposition of
various aliphatic polyamides.
The pyrolysis liquid of Nylon 6,6 contains alkadienes and cycloalkenes in addition
to cyclopentanone in the gasoline boiling range, furthermore this fraction also involves
hexanedinitrile and even alkylamines. The components of the diesel oil boiling range
Figure 12.7 Py-GC/MS chromatogram of Nylon 6,6 at 500◦ C

are all amide compounds, the majority of which contain a vinyl group. The heavy oil
components are cyclic amides. In spite of the various nitrile and amino-group-containing
pyrolysis products, relatively low hydrogen cyanide and ammonia emissions have been
reported from Nylons in pyrolytic processes [40].
5.4 POLYURETHANES (PU)
Pyrolysis could be considered as an unsuitable way of recycling for polyurethanes because

the liquid product is extremely viscous and can solidify over time [41]. The main reason
of the severe instability of polyurethane pyrolysate is the reactivity of the diisocyanate
component, the regained polyurethane-forming reactant. The other component of ther-
moplastic polyurethanes is either a polyether or a polyester which could lead to stable
pyrolysis liquid if the reactive diisocyanate is eliminated from it.
The thermal decomposition of polyurethanes can be explained by two principal mech-
anisms [42] as shown in Scheme 12.1c and d. The dissociation of the urethane linkage
yields products with isocyanato and hydroxyl end groups. The latter groups are dehydrated
at higher temperatures to yield compounds with vinyl groups. Through the rearrangement
of the bonds of the urethane linkage a carbamic acid group and a vinyl group are produced,
the former one decomposes to amine end group and carbon dioxide. Cyclic polyester or
polyether oligomers are formed by intramolecular exchange reactions in the soft segments
(analogously to the reaction drawn in Scheme 12.2).
5.4.1 Pyrolysis Products of Polyester-segmented Polyurethane

Polyester-segmented PU undergoes decomposition to volatiles in two steps from 280 to
340◦ C and to 420◦ C. The nitrogen content of the polymer diminishes in the first step
[43] because diisocyanate, the main nitrogen-containing thermal decomposition product
is evolving at around 300◦ C. The thermal decomposition of the flexible polyester segment
takes place in the second step at higher temperature. The pyrogram of a PU composed
of diphenylmethane diisocyanate (MDI), 1,4-butanediol and poly(butylene adipate), is
displayed in Figure 12.8. The components of the gasoline and diesel oil boiling range
are various oxygenated hydrocarbons, the fragments of the polyester. The only nitrogen-
containing product compound is the isocyanate component of PU, which is MDI in the
heavy oil range of the presented pyrogram. The lowest temperature decomposition prod-
ucts of PU (MDI and some cyclic ester dimer) are derived from the breakage reaction of
the urethane linkage drawn in Scheme 12.1c; MDI with two isocyanate groups and cyclic
dimeric ester, which is cleaved from the hydroxyl group terminated polyester segment by
intramolecular ester exchange. The other mechanism supported by pyrolysis-MS exper-
iments [42] leading to aromatic amine (shown in Scheme 12.1d) does not contribute to
the volatile products of fast pyrolysis displayed in the pyrogram of Figure 12.8. Pyrolysis
of the ester segment of PU is fragmented to vinyl-group-containing esters by reaction
(a) in Scheme 12.1 (butadiene, butenyl hydrogen adipate, dibutenyl adipate) and cyclic
esters by ester exchange reaction (Scheme 12.2). Tetrahydrofuran and cyclopentanone are
the products of cyclic decomposition of the butanediol and adipic acid moieties of the
polyester, accompanied by decarbonylation and decarboxylation, respectively.
336 M. BLAZSÓ
Figure 12.8 Py-GC/MS chromatogram of polyester-segmented PU at 500◦ C
When PU is based on more volatile diisocyanates than MDI, such as HDI (hexam-
ethylene diisocyanate) or TDI (toluene diisocyanate), these compounds spoil the gasoline
or diesel oil boiling fraction of the pyrolysis oil, respectively. It is possible to elim-
inate the reactive and toxic diisocyanate products from the pyrolysis oil, either in a
lower-temperature pyrolysis step or with the help of an adsorbent [41].
The octane number of the gasoline fraction composed of the aliphatic polyester frag-
ments could be predicted by taking into account the linear and cyclic oxygenated saturated
hydrocarbon nature of the components.
5.4.2 Pyrolysis Products of Polyether-segmented Polyurethane
Thermal decomposition of PU with polyether soft segments produces volatiles in two

steps similarly to that of polyester-segmented PU from 280 to 350◦ C and to 430◦ C,
however the second step covers a slightly higher temperature range. Only diisocyanate
is formed in the first step, aliphatic polyether decomposition products are accumulated
in the pyrolysate above 400◦ C. The pyrogram of a PU composed of diphenylmethane
diisocyanate (MDI), 1,4-butanediol and poly(tetrahydrofuran) is displayed in Figure 12.9.
The peak of MDI is more dominant in the pyrogram of polyether-segmented PU than in
that of polyester-segmented one, because polyether is fragmented in to more compounds.
In addition to the series of cyclic oligotetrahydrofurans (the corresponding peaks are
indicated in the pyrogram) several other types of oligoether components are present in
each boiling fractions of the pyrolysis oil. The gasoline boiling range contains more
alcoholic compounds (butanol, butanediol and tetrahydrofuranol) than the higher boiling
fractions.
Figure 12.9 Py-GC/MS chromatogram of polyether-segmented PU at 500◦ C. Cx denotes

cyclic oligotetrahydrofuran of x tetrahydrofuran units
MDI is derived from the breakage reaction of the urethane linkage drawn in Scheme
12.1c, the polyester product are formed by intramolecular rearrangement of ether bonds,
eliminating cyclic oligomers, and by radical breakage of the polyester chain to partly
unsaturated linear oligoethers.
The fuel properties of the pyrolysis oil of an aliphatic polyether-segmented PU could
be predicted by taking into account the linear and cyclic oxygenated saturated and olefinic
hydrocarbon nature of the components. Elimination of the reactive and toxic diisocyanate
from the pyrolysis oil of PU in a lower temperature pyrolysis step is easier in the case
of polyether soft segment, because of the larger temperature difference of decomposition
steps compared to that of polyester-segmented PU.
6 PYROLYSIS PRODUCTS OF ELECTRONIC WASTE PLASTICS
Electrical and electronic devices are made utilizing several various types of plastic mate-
rials, thus when discarded their waste is difficult to recycle. The plastics employed in
housing and other appliances are more or less homogeneous materials (among others PP,
PVC, PS, HIPS, ABS, SAN, Nylon 6,6, the pyrolysis liquids of which have been discussed
above). However, metals are embedded in printed circuit boards, switches, junctions and
insulated wires, moreover these parts contain fire retardants in addition to support and
filler materials. Pyrolysis is a suitable way to remove plastics smoothly from embedded
metals in electrical and electronic waste (EEW), in addition the thermal decomposition
products of the plastics may serve as feedstock or fuel. PVC, PBT, Nylon 6,6, poly-
carbonate (PC), polyphenylene ether (PPO), epoxy and phenolic resins occur in these
metal-containing parts of EEW.
338 M. BLAZSÓ
There is a common feature of the polymer composition in PC, PPO, epoxy and phe-
nol–formaldehyde resin, all contain phenoxy moieties in their repeating unit. Hence, it
is not unexpected that the major pyrolysis products of these plastics are phenols. The
reason of the production of phenolic compounds is the higher bonding energy of the
C–O linkage in the phenoxy moiety related to that of other bonds along the polymer
chain.
6.1 POLYCARBONATE
Aromatic moieties and carbonate groups alternate in the chain of this type of polymer.
The oxygen atom is more strongly linked to the aromatic ring than to the carbonyl
carbon in the carbonate group [21], thus the thermal cleavage of the weaker C–O bond
results in phenoxy radicals and carbon dioxide [44]. The phenoxy radical either becomes
a phenolic chain end or a phenolic compound by abstracting a hydrogen atom. If the
aromatic moiety of the macromolecule has not enough available hydrogen for abstraction,
the combination of the free radicals leads to polyaromatization and yields carbonaceous
residue.
6.1.1 Pyrolysis Products of PC

Volatile production occurs from polycarbonate by entirely thermal decomposition between
450 and 550◦ C yielding about 25% solid residue as well. The pyrogram of the most com-
mon aromatic polycarbonate, poly(bisphenol A carbonate) is displayed in Figure 12.10.
Alkylphenols and phenol are the main constituents of the boiling range 180–250◦ C and
Figure 12.10 Py-GC/MS chromatogram of bisphenol A polycarbonate at 600◦ C

bisphenol A and phenylalkylphenols from 300 to 380◦ C from this PC in which the aro-
matic constituent is composed of two phenylene ring linked with an isopropylidene group.
There is not enough available hydrogen in this polymer to stabilize all radicals, and so a
considerable proportion of the polymer is carbonized.
6.2 EPOXY RESIN
Diglycidylether bisphenol A (DGEBA)-type epoxy resin is generally used in printed cir-

cuit boards, and is easily made flame retardant by involving brominated bisphenol A
segments as well in the polymer chain. These thermosetting polymers have low thermal
stability in spite of their aromatic structural building elements and their network macro-
molecular structure. The cleavage of the ether link connecting the diglycidyl segments
to the aromatic rings is facilitated by a geometrically favoured intramolecular interaction
and yields phenol and methyl ketone ends at the scission of the macromolecule shown
in Scheme 12.7. The breakage of the C–C bond between the phenol ring and the tertiary
carbon of isopropylidene group leads to phenol and isopropenylphenol by disproportion.
6.2.1 Pyrolysis Products of Flame-retarded Epoxy Resin

Volatilization of epoxy resin by thermal decomposition occurs between 330 and 390◦ C,
and a residue of 10% is left. The pyrogram of an epoxy resin flame retarded by incor-
poration of tetrabromobisphenol A segments is displayed in Figure 12.11. Phenol and
isopropenylphenols are the main components of the boiling range 180–280◦ C, and bisphe-
nol A compounds between 300 and 420◦ C. The tetrabromobisphenol A segments are
decomposed similarly to the regular epoxy ones, yielding brominated bisphenol A com-
pounds, although bromine is also partially cleaved from the phenol rings, leading mostly
to mono- and dibrominated compounds. The breakage of the bisphenol segments results
not only in phenol and isopropenylphenol, but also to the corresponding brominated com-
pounds, the GC peaks of which are indicated in Figure 12.11 by asterisks. The relative
yield of the lower boiling range to the higher one can be considerably increased by
Scheme 12.7 Epoxy chain cleavage through intramolecular rearrangement

340 M. BLAZSÓ
Figure 12.11 Py-GC/MS chromatogram of brominated epoxy resin at 450◦ C. Peaks

labelled* are 2-bromophenol and 2-bromo-4-isopropenylphenol, respectively
increasing the pyrolysis temperature, which promotes the breakage of the bisphenol seg-
ments. It must be taken into consideration that the brominated phenols are precursors
of polybrominated dibenzodioxins (PBDD), thus dehalogenation is essential before using
this pyrolysis oil as a fuel.
6.3 PHENOL–FORMALDEHYDE RESIN

In this polymer phenolic rings are linked through methylene bridges at ortho (2 and 6)
or para (4) positions. Branching points are those phenol units which are linked to other
phenoic moieties at three carbon atoms, namely at 2, 4 and 6 positions. In a resin where no
reactive methylol groups have been left after curing the only possibility for intramolecular
interaction requiring relatively low energy is the condensation of two phenolic rings
of two phenols connected at ortho–ortho positions. Apart from some water elimination
occurring throughout the thermal decomposition of phenol–formaldehyde resin [45] the
disintegration of the macromolecule is a free radical process. The scission of the methylene
bridges produces aryl and phenylmethyl radicals, both require hydrogen for stabilization
and evolution of volatile molecules. Neither phenolic hydroxyl nor the original alkyl
substituent groups are cleaved by pyrolysis below 600◦ C, thus the pyrolysis product
compounds are all phenols and similarly substituted as the starting material of the resin
[46]. In the pyrolysis oils of phenol–formaldehyde novolacs having no branching points
bisphenol compounds are also present.
6.3.1 Pyrolysis Products of Cured Phenol–Formaldehyde Resin

The thermal production of volatile compounds progresses in the temperature range
450–620◦ C in phenol–formaldehyde resin. From novolacs about 20%, while from cured
Figure 12.12 Py-GC/MS chromatogram of cured phenol–formaldehyde resin at 600◦ C
resins 30–50% carbonized residue is also formed. The pyrogram of a cured resin is shown
in Figure 12.12. As expected from a free radical scission at the methylene bridges, only
2-, 4-, and 6-methylphenols are components of the liquid, which has a boiling range
between 180 and 220◦ C. From phenol–formaldehyde novolac higher boiling products are
also expected in the range 180–220◦ C. Benzene, toluene and xylenes could be produced
at higher temperatures, but at the same time polyaromatic hydrocarbons (PAHs) are also
formed.
ACKNOWLEDGEMENT
This work was supported by the Hungarian National Research Fund (OTKA contract no.
T047377).
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13
Production of Premium Oil

Products from Waste Plastic by
Pyrolysis and Hydroprocessing
S.J. MILLER
ChevronTexaco, 100 Chevron Way, Richmond, CA 94802, USA
and
N. SHAH AND G.P. HUFFMAN

University of Kentucky, Consortium for Fossil Fuel Science, 107 Whalen Building, 533 S.
Limestone St, Lexington, KY 40506-0043, USA
1 BACKGROUND
In the US, plastics is the largest growing waste stream, rising from less than 5 wt% of total
municipal solid waste (MSW) in 1980 to over 11 wt% today. In 2001, of approximately
25 million tons of waste plastic, only about 1 million tons were recycled [1]. In California
and elsewhere, waste plastic is a major issue due to the growing cost of landfilling. Even
plastic which is collected and separated often gets sent to landfills due to lack of a
sufficient market [2]. While state law in California has set a recycle rate at 25%, the
rate has actually been declining in recent years, from 24.6% in 1995 to only 17.9% in
1999 [3].
Of the waste plastic not recycled, about 43% (or about 11 MM ton/yr) is polyethylene
(Figure 13.1), with most of this in containers and packaging [1]. Polyethylene plastic is
found in two main forms: high-density (HPDE) and low-density (LDPE). Major uses for
HDPE include rigid containers such as bottles, as well as agricultural film. Major uses
for LDPE include flexible films such as grocery and dry cleaning bags.
This chapter presents a summary of research on the conversion of waste plastics to
premium oil products performed in the United States in the period from approximately
1993 through 2000.
346 S.J. MILLER ET AL.
PET
Other
10% PVC
19%
6%
PS
9%
HDPE
19%
PP
14%
LDPE
23%
Figure 13.1 Plastics in municipal solid waste
2 CONVERSION OF WASTE PLASTICS TO TRANSPORTATION FUELS
A multi-year research program on the production of liquid transportation fuels from waste
polymers and the co-processing of waste polymers with coal to produce liquid fuels
was carried out by a group of academic, industrial and government scientists under the
sponsorship of the US Department of Energy, Office of Fossil Energy. Much of the lab-
oratory research was conducted by the Consortium for Fossil Fuel Science (CFFS), a
five-university research consortium with participants from the University of Kentucky,
Auburn University, the University of Pittsburgh, the University of Utah and West Vir-
ginia University. Industrial participation was provided by Hydrocarbon Technologies, Inc.
(HTI), where pilot-scale and continuous tests were conducted; Consol, where specialized
analytical techniques were employed; and Mitretek Corporation, where economic anal-
yses were performed. Research conducted at the US DOE National Energy Technology
Laboratory (NETL, Pittsburgh) complemented work in the academic and industrial sectors.
Subsequent to the research performed under sponsorship of DOE, ChevronTexaco spon-
sored research at the University of Kentucky and at their corporate laboratories that was
focused on the conversion of waste plastic (principally polyethylene) into lubricating oil.
This chapter presents a summary of the DOE-sponsored research conducted by the Uni-
versity of Kentucky and of the research conducted jointly by ChevronTexaco and the
University of Kentucky.
3 DIRECT LIQUEFACTION AND CO-PROCESSING OF WASTE PLASTIC
Much of the research in the US was based on direct liquefaction technology to convert
waste plastic into oil products. This work has been summarized in several symposia of the
Division of Fuel Chemistry of the American Chemical Society [4–6], a special issue of
Fuel Processing Technology [7], and an IEA review of research on the co-processing of
wastes with coal by a variety of processes prepared by Davidson [8]. A significant amount
of research and development has also taken place in Germany [9, 10]. In Germany, a
liquefaction plant capable of converting 80 000 tons of waste plastic per year into oil
products was developed by Kohleöl-Anlage Bottrop, GmbH (KAB), a subsidiary of Veba
Oil. This facility was operated for several years with support from the Duales System
PREMIUM OIL PRODUCTS 347
Deutschland, or DSD, which is the organization established by the German packaging
industry to deal with the strict recycling laws in that country.
The liquefaction of commingled waste plastic typically yields 70–90% oil, 5–20%
gas, and 5–10% solid residue. A significant amount of research has been conducted on
the catalytic direct liquefaction of plastic [11–16]. Extensive work has been done using
solid acid catalysts and metal-promoted solid acid catalysts, which generally improve oil
yields and oil quality. At temperatures above 440◦ C, however, thermal and catalytic oil
yields are comparable. No solvent is required, but good results have been obtained using
mixtures of waste oil and petroleum resid with plastic. The reactions can be carried out at
low hydrogen pressures (∼100–500 psig) and with low hydrogen consumption (∼1%).
4 PYROLYSIS AND HYDROPROCESSING
Although direct liquefaction of waste plastic looked promising, problems associated with
impurities (paper, aluminum, etc.) and chlorine derived from PVC caused operational dif-
ficulties. Consequently, it currently appears that the first step of any feedstock recycling
process for waste plastics or tires should be pyrolysis, which allows much easier sepa-
ration of solid impurities and chlorine. Research on pyrolysis of post-consumer plastic
has been carried out by Kaminsky and co-workers [17, 18], Conrad Industries [19, 20],
and Shah et al. [21]. Shah et al. [21] conducted pyrolysis experiments on relatively dirty
post-consumer waste plastic obtained from the DSD. The pyrolysis oils were then sub-
jected to hydroprocessing to convert them into high-quality transportation fuels (gasoline,
kerosene, diesel).
As discussed in detail elsewhere [22], the waste plastic collected by the DSD is sub-
jected to several dry shredding and cleaning steps that reduce the nonplastic residue to
typically 4–5 wt%. The cleaned waste plastic is then processed into a pelletized form.
The pyrolysis treatments on the DSD waste plastic pellets were performed as a function
of temperature in a batch mode reactor (Figure 13.2) [21]. After placing the waste plastic
in the reactor and flushing the system with an inert gas, the reactor was lowered into
the floor furnace. The furnace was then heated from room temperature to the pyrolysis
temperature in 15–20 min and held at that temperature for 1 h before cooling back to
room temperature. The yields of oil, gas, and solid residue are shown as a function of
the pyrolysis temperature in Figure 13.3. Oil yields approaching 80% were obtained at a
pyrolysis temperature of 600◦ C.
Hydroprocessing of these pyrolysis liquids was carried out at 450◦ C (200 psig H2
pressure, cold, 60 min), both thermally and catalytically (1 wt% HZSM-5). The results
obtained by simulated distillation (simdist) analysis of the resulting liquids are illustrated
in Figure 13.4, which shows the percentages of liquid product in the gasoline (IBP-
200◦ C), kerosene (200–275◦ C), and heavier oil fractions (275◦ C-FBP) in the pyrolysis
oils before and after thermal and catalytic hydrotreatment of the pyrolysis liquids derived
from DSD plastic; the pyrolysis temperatures are indicated along the x-axis. These results
show that the lighter boiling point fractions are increased significantly by hydrotreatment
at 450◦ C. The percentage of heavier pyrolysis liquids increases with increasing pyrolysis
temperature due to the fact that higher-boiling oils are more quickly volatized at higher
temperatures and therefore have less chance to undergo further cracking in the pyrolysis
Heating
tape
Inline
condenser
Inert gas
Cold water Pressure
valve
Waste Gas to vent

plastic
Cooling
water Liquid nitrogen
coil trap
Floor furnace
Condensate
Figure 13.2 Schematic of batch mode laboratory plastic pyrolysis reactor
90
80
70
60
Oil
Yields (wt%)
50 Residue
Gas
40
30
20
10
0
500 550 600 650 700
Pyrolysis temperature (°C)
Figure 13.3 Oil, gas, and residue yields from DSD plastic as a function of pyrolysis
temperature. (Reproduced by permission of the American Chemical Society)
IBP 200°C 200C–275°C 275°C FBP

100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
0
0
0
00
0
50
52
55
60
70
50
50
52
52
55
55
60
70
70
c6
al
al
al
c
al
al
c
ne
ne
ne
ne
ne
yti
yti
yti
yti
yti
erm
erm
erm
erm
erm
No
No
No
No
No
tal
tal
tal
tal
tal
Th
Th
Th
Th
Th
Ca
Ca
Ca
Ca
Ca
Figure 13.4 Simdist analysis of pyrolysis oil from DSD waste plastic before and after
thermal or catalytic hydroprocessing. (Reproduced by permission of the American
Chemical Society)
zone. Thermal or catalytic hydroprocessing of the pyrolysis liquids improves the yield of
lighter fractions, yielding about 50% of product in the gasoline range and 25–30% in the
kerosene or jet fuel range. Catalytic hydroprocessing using 1 wt% of HZSM-5 catalyst
gave somewhat better yields of light products than thermal hydroprocessing (Figure 13.4).
Chlorine derived from PVC is the impurity of most concern in oil produced from
waste plastic. Because the DSD plastic contained 1.26 wt% Cl, measures were required
to remove it in these experiments. To lower the chlorine content of the oil products,
small additions (2–3 wt%) of sodium carbonate were made to both the pyrolysis and
hydroprocessing reactors to react with HCl released at elevated temperatures. The pyrol-
ysis oils had chlorine contents of approximately 50–70 ppm, while the hydroprocessed
oil products exhibited chlorine contents of only 2–8 ppm.
5 FEASIBILITY STUDY
On the basis of promising laboratory and pilot-scale results, DOE commissioned a feasi-
bility study for a 300 ton per day (t/d) plant to convert waste plastic and/or waste tires into
transportation fuel and to co-process coal with these waste polymers as required [23]. The
principal results of this study were published in Chemtech [22]. Here we present only a
brief summary of the feasibility study results for a 300 t/d plant converting waste plastic
into oil.
A conceptual design for the plant is shown in Figure 13.5. Detailed information on the
estimated capital cost of a 300 t/d plant with this design and its estimated annual operating
costs are available [22]. The experimental results indicate that a conservative estimate of
the oil yield per ton of waste plastic is about 5 bbl/t. Assuming a plant operating at 90%
capacity, this would yield 495,000 bbl/yr.
As part of the feasibility study [22], an economic analysis was performed that was
based on oil prices of $15–25 per bbl, which seemed like a reasonable range at that time.
On the assumption that the 300 t/d plant would receive tipping fees of $20–40 per ton
for accepting the waste plastic, returns on investment (ROI) of 5–20% were predicted.
Currently, oil prices are about $50/bbl. If one assumes oil prices of $30–50/bbl, our
earlier economic analysis would predict ROI of approximately 20–40%, even with zero
tipping fees for waste plastic. However, this is a topic that clearly needs to be revisited
using updated capital and operating costs. Moreover, as discussed in the next section, it
now appears that lubricating oil would be the product of choice from feedstock recycling
of waste plastic and this should have a significant positive impact on the economics.
Hydrogen
Bales of
waste plastic Process heat
Condenser &
Cl scrubber
Shredder Gases (C1 – C4)
& preparation
H2 recovery &
scrubber
Pyrolysis
600°C
Hydrocracker
Residue Pump
Hydrogenation Bottoms
reactor Distillation
columns
(C5 – C30) > C30
Figure 13.5 Conceptual design for a plant converting waste plastic to oil products
6 CONVERSION OF WASTE PLASTIC TO LUBRICATING BASE OIL
Most of the work on feedstock recycling of plastic has focused on conversion of plastic
to transportation fuels. Little has been reported on conversion of waste plastic to higher-
valued products. In this section, research on the conversion of waste polymers such as
polyethylene to high-quality lubricant oils is summarized. A more detailed account of this
research is available elsewhere [24].
There is currently a shift to oils of lower viscosity that reduce engine friction and
thereby improve fuel economy. These oils will be in increasing demand by automakers
to meet government-mandated minimum miles-per-gallon requirements. A second change
is a reduction in oil volatility, which reduces oil consumption and evaporative emissions
into the environment. A strong dependence of diesel particulate emissions on engine oil
volatility has been shown [25].
EPA statistics show that each year in the US, approximately 200 million gallons of
used oil is dumped into the environment [26]. This problem can be largely addressed by
producing oils which are more stable, thereby extending the interval between oil drains
and reducing the amount of used oil which would need disposal. A high viscosity index
(VI) signifies high stability to change in viscosity over a wide temperature range. Oil
having a high VI resists excessive thickening when the engine is cold and, consequently,
promotes rapid starting and prompt circulation; it resists excessive thinning when the
motor is hot and thus provides full lubrication and prevents excessive oil consumption.
Most lubricating base oils produced today have a VI of 95–105 and are called conventional
base oil (CBO). The term ‘base oil’ refers to the lubricating oil before the addition of
additives. Base oils required to meet the future needs discussed above will have to have
a VI >115 and are called unconventional base oil (UCBO).
Since paraffins have low volatility for their viscosity, high thermal and oxidative
stability, and high VI, these new requirements could be met by using oils that are
highly paraffinic. To meet mandated fuel economy and emissions standards plus cus-
tomer demands will require large quantities of these advanced oils within the next few
years.
One technology for preparing the high-VI UCBOs uses a highly selective molecular
sieve catalyst to isomerize waxy feeds to allow the oil to flow at low temperature, where
that ability is measured by the lowest temperature at which the oil will pour, or its
pour point. This technology, first commercialized in the US in the early 1990s [27, 28],
converts wax to oil, allowing production of oils at high yield with high paraffinicity, and
therefore high VI and low viscosity.
7 LUBRICATING BASE OILS FROM FISCHER–TROPSCH WAX

AND WASTE PLASTIC
Fischer–Tropsch (FT) technology converts synthesis gas produced by reforming of methane

or coal gasification into waxy products. Long alkanes (–CH2 –chains) produced by using FT
synthesis are chemically similar to polyethylene. Lubricating oils derived from isomerization
of FT waxes are gaining interest due to increased demand for lubricants with the advanced
performance and environmental benefits described earlier.
Although FT waxes are high in quality, their availability over the next decade is
expected to be limited. Therefore, there is an effort to find other sources of feedstocks
of equal quality to co-process along with FT waxes, both to meet the demand and
decrease the cost of lubricant products. Waste plastic is a potentially significant new
source for such waxy feed. We have performed combined pyrolysis–hydroisomerization
experiments, looking at the following feedstock options:
1. Polyethylene
2. Polyethylene + polyethylene terephthalate (PET), where PET (e.g. soft-drink bottles)
is one of the major non-PE plastics in municipal waste
3. Polyethylene + FT wax
4. FT wax
HDPE and LDPE were obtained from Chevron Phillips Chemical Company. PET was
obtained by cutting up soft-drink bottles. FT wax was obtained from Moore & Munger.
Laboratory pyrolysis of HDPE was first carried out using the batch mode reactor
(Figure 13.2). After flushing the system with an inert gas, the reactor was lowered into
the floor furnace. The furnace was heated from room temperature to the pyrolysis tem-
perature in 15–20 min and held at that temperature for 1 h before cooling back to room
temperature. There was complete conversion of the HDPE in all runs and the reactor was
clean at the end of the run. Several runs were carried out to optimize the temperature and
pressure conditions.
Because there is no control on the residence time in the batch pyrolysis set-up, pyrolysis
at higher temperature allows larger molecular weight species to leave quickly. At lower
furnace temperature, the larger molecules are not vaporized, but spend longer times in the
furnace to undergo further cracking. This is shown by Figure 13.6, which shows the sim-
ulated distillation analysis of HDPE pyrolysis products at 0.1 atmosphere reactor pressure
for various furnace temperatures. It is evident that higher boiling point products desired
100
90
80 500°C
550°C
70
600°C
60
650°C
% OFF
50
40
30
20
10
0
0 100 200 300 400 500 600 700
Temperature (°C)
Figure 13.6 Simulated distillation boiling point distributions of HDPE pyrolysis

condensates
Stirrer motor with
torque
measurement
Inert gas
flush
Tube furnace
Plastic
melt Product
collection
vessel
Heated
gear pump
Figure 13.7 Schematic of continuous laboratory pyrolysis reactor
for lube base oil are produced in greater abundance at the higher pyrolysis temperatures
(600–650◦ C). At higher (atmospheric) reactor pressure, the difference between boiling
point distributions narrows.
To make the process continuous and to achieve better control of residence time (space
velocity) of the process, a second laboratory pyrolysis unit was designed (Figure 13.7).
The feed (approximately 500 g) was placed in a melter vessel equipped with a stirrer
motor with torque measurement and heated under a 4 psig argon blanket. Melted feed
was conveyed by 12 -inch (1.25 cm) OD stainless steel tubing to a heated Parker Hannifin
Zenith gear pump. This pump could deliver metered feeds at temperatures as high as
450◦ C with little dead volume. The feed then went by way of 14 -inch (0.625 cm) stainless
steel tubing to a 25 cc, 12 -inch (1.25 cm) OD, upflow stainless steel reactor in a tube
furnace. Products were collected downstream in a water-cooled collection vessel.
Kinetics were determined using the laboratory pyrolysis unit with the melter/feed vessel
temperature set at about 325◦ C and the pump temperature set at about 300◦ C. By varying
the speed on the gear pump, residence times in the furnace were set. Residence times
used ranged from 1 to 12 min, yielding a HDPE throughput of about 100 to 1200 g/h.
In all cases, gas make was low, not more than a few percent for the 600–650◦ C
pyrolysis runs. Simulated distillation results (by thermogravimetric analysis) on the col-
lected products were used to calculate the wt% conversion to products with boiling
points below 538◦ C (1000◦ F). These showed the conversion to follow close to first order
kinetics (Figure 13.8). The apparent activation energy for the process was 42 kcal/mole
±20 kcal/mole (Figure 13.9), which is within the range of values reported in the litera-
ture [29]. These results indicate that it should be possible to get substantial conversion to
lube oil feedstock at temperatures (500–550◦ C) and residence times (30 min to 1 h.) sim-
ilar to conventional refining processes, but at atmospheric pressure and without co-feeding
hydrogen.
100
100 – conv, %
10
1
0 2 4 6 8 10 12 14
Residence time, min
Figure 13.8 Conversion of HDPE pyrolyzed at 650◦ C at atmospheric pressure to < 538◦ C
boiling fraction as a function of residence time
Ln k, Conversion <1000 °F
2
1
0
−1
−2
y = −21.515x + 24.662
−3
−4
1 1.1 1.2 1.3 1.4
1/T, °K X
Figure 13.9 Ln k versus 1/T determined the activation energy for the process
8 ONE-GALLON-PER-DAY PILOT PLANT
A diagram of the one-gallon-per-day pyrolysis pilot plant is shown in Figure 13.10. Feed-
stock was melted at 260◦ C in a 30-liter feed pot equipped with an air-driven stirrer, and
which had a 10 psi nitrogen blanket. Using a Parker Hannifin Zenith gear pump, the feed
was pumped through a stainless steel preheat coil at 370◦ C and then up-flowed through
a 2.5-cm diameter stainless steel reactor that contained pre-heat and after-heat steel bars
to reduce the reactor volume to 140 cm3 . When plastic without Fischer–Tropsch wax
was run, the feed was diluted 50/50 by weight with a 290–370◦ C hydrocracked diesel to
lower the viscosity to a point at which the feed could be pumped. All pyrolysis runs were
at atmospheric pressure and approximately 1 h residence time (based on plastic and/or
wax), with no added gases.
Product from the reactor was sent to a still, set at about 230◦ C, with nitrogen strip-
ping gas to cut the effluent stream at about 340◦ C. Both overhead and bottoms liquids
were collected in cans on scales. Gas went through a gas meter and gas sampler for
analysis.
4 Way valve
Cooling out
Gas bulb
90 psi air Cooling in
Relief valve
set @15 psi
Ecv Process vent

N2 blanket Zone 6
10 psi max
DC controller Stripper
N2 Gas meter
Air motor Reactor
stripping
Solvent flush
valve
50 psi
relief valve
Feed pot Ovhd
7.5 gal Product can can
Scale
Drain
D/C motor
Drain
Gear pump Zenith
Figure 13.10 One-gallon-per-day pyrolysis pilot plant
8.1 HYDROPROCESSING
8.1.1 Hydrotreating
Hydrotreating of the pyrolyzer stripper bottoms was carried out over a commercial
nickel–tungsten on silica–alumina hydrotreating catalyst at 300◦ C, a liquid hourly space
velocity of 1.5 h−1 , 13.4 MPa total pressure, and 880 standard cubic meters once-through
H2 per cubic meter of feed. At these conditions, cracking of the feed was minimal.
8.1.2 Hydroisomerization
Isomerization of the waxy pyrolyzer stripper bottoms was carried out over a proprietary
wax hydroisomerization catalyst. A commercial Pt–Pd on silica–alumina hydrofinishing
catalyst was used in a second reactor downstream from the first to hydrogenate any
unsaturated compounds to improve thermal and oxidative stability.
8.2 PYROLYSIS PILOT PLANT RESULTS FOR VARIOUS FEEDSTOCKS
Table 13.1 shows the yields and inspections from the pyrolysis run in the one gallon per
day pilot plant with HDPE. The yield of 385◦ C+ product, with an endpoint of about
593◦ C, suitable for lubricating base oil, was 51.4 wt% based on plastic in the feed. At
the conditions of the run, there was only 6 wt% 538◦ C+ in the product, yet only about
5 wt% of the low valued C4- light ends. Minimizing both might be possible through
further optimization.
Table 13.1 Pyrolysis of 50/50 by weight plastic/diesel at atmospheric pressure, and 1 h residence
time
Plastic HDPE HDPE 96/4 HDPE/PET

◦
Temperature ( C) 552 524 524
Yield (wt%)
C1 0.8 0.5 0.2
C2 = 1.8 0.8 0.5
C2 0.9 0.6 0.4
C3 = 2.4 1.2 0.6
C3 0.8 0.5 0.4
C4 = 2.2 0.8 0.6
C4 0.4 0.5 0.2
C1–C4 9.3 4.9 2.9
C5–385◦ C 69.6 69.4 75.9
385◦ C+ 21.1 25.7 21.2
385◦ C+, based on plastic 42.2 51.4 42.4
8.2.1 Polyethylene + PET

The price of baled HDPE with up to 2% impurities has fluctuated from 7–10 cents/lb two
years ago to about 30 cents/lb recently. If the plastic used in the pyrolysis process did not
require this limit, the cost could be considerably lower. (Unseparated waste plastic can be
valued as low as negative 2 cents/lb, which accounts for landfilling cost or tipping fee.)
Consequently, the run with HDPE was repeated, except the plastic was 96 wt% HDPE
and 4 wt% waste polyethylene terephthalate from soft-drink bottles. Pyrolysis yields are
given in Table 13.1, showing a 385◦ C+ yield, based on plastic, of 42.4 wt%.
In the pyrolysis run, C4− was again quite low (about 3 wt%), and the product contained
no 538◦ C+ in the bottoms. Assuming all the C4- came from the plastic would indicate
about 6 wt% of the plastic was converted to gas.
8.2.2 Polyethylene + FT Wax

Pyrolysis was carried out on a feed composed of a 50/50 mixture by weight of low-
density polyethylene (LDPE) and hydrotreated FT wax. Yields are given in Table 13.2,
showing a 385◦ C+ yield of 57.5 wt%. The yield for a broader lube feed, 343◦ C+, was
66.0 wt%. While there was considerable 538◦ C+ in the feed to the pyrolyzer, there was
little 538◦ C+ in the product, which is believed here to be advantageous for low cloud
point. Olefinicity in the pyrolysis overhead was 76 wt% by PONA analysis. The olefinic
overhead liquids from the pyrolysis of both FT wax and LDPE/FT wax were analyzed
using gas chromatography. This showed the cracked product to be almost entirely 1-
normal olefins and normal paraffins.
The pyrolysis bottoms were then hydroisomerized to give a −22◦ C pour point, 4.4 cSt
oil of 154 VI (Table 13.3). The overall 343◦ C+ yield, based on feed to the pyrolyzer, was
44 wt%. Adding the potential lube from oligomerizing the lighter olefinic product from
the pyrolyzer would increase the 343◦ C+ yield to about 59 wt%. However, in this run,
a significant amount of 343◦ C− was in the feed to the hydroisomerization step (10 wt%
based on feed to the pyrolyzer). Had this been sent to oligomerization, the potential
343◦ C+ would be at 67 wt% (Figure 13.11), based on the PONA olefin analysis.
Table 13.2 Pyrolysis of FT wax feeds at 524◦ C, atmospheric pressure, and 1 h residence time
Feed 50/50 LDPE/FT FT wax

wax
Yield (wt%)
C1 0.2 1.0
C2= 0.6 0.6
C2 0.4 2.4
C3= 0.9 0.8
C3 0.7 1.8
C4= 0.9 1.6
C4 0.4 1.3
C1–C4 4.1 9.5
C5–177◦ C 9.9 8.4
177–343◦ C 20.0 21.4
343–385◦ C 8.5 9.6
385◦ C+ 57.5 51.1
Table 13.3 Hydroisomerization of pyrolyzed product from FT wax feeds
Feed Pyr. 50/50 Pyr. 50/50 Pyr. FT wax

LDPE/FT wax LDPE/FT wax
Hydrotreated No Yes No
Yield (wt%)
C1–C2 0 0.1 0
C3 0.5 0.8 0.5
C4 0.9 1.7 1.0
C1–C4 1.4 2.6 1.5
C5–177◦ C 8.7 13.7 10.2
177–343◦ C 32.6 31.7 37.4
343–385◦ C 11.5 11.0 12.4
385◦ C+ 45.8 41.0 38.5
Bottoms
Feed (wt%) 60.9 61.6 64.7
Pour point (◦ C) −22 −15 −14
Cloud point (◦ C) −2 −2 −1
Viscosity, 40◦ C (cSt) 18.70 15.23 12.56
Viscosity, 100◦ C (cSt) 4.416 3.829 3.380
VI 154 150 150
Simulated distillation, ◦ C (wt%)
10 353 329 319
30 396 377 363
50 437 426 407
70 474 470 449
90 516 517 491
Overall 385◦ C+ (wt%) 34.8 31.2 27.6
Overall 343◦ C+ (wt%) 43.7 39.7 36.5
Total 343◦ C+, (including Oligomers) (wt%) 59 55 52
80
70
60
LDPE/FT Wax
YIelds, Wt%
50 FT Wax
40
30
20
10
0
C1–C4 C5–177°C 177–343°C 343°C+
Figure 13.11 Potential yields with isomerization/oligomerization
A portion of the pyrolysis bottoms was hydrotreated to reduce the nitrogen from 8 ppm
to less than 1 ppm. This was then hydroisomerized to give a −15◦ C pour point 3.8 cSt
oil with a 150 VI (Table 13.3). The overall 343◦ C+ yield was 40 wt%, close to that
estimated for unhydrotreated feed at the same pour point.
8.23 FT Wax
FT wax was next run without plastic. Yields through the pyrolyzer are given in Table 13.2,
showing a surprisingly similar product distribution and olefinicity to the run with a 50/50
LDPE/FT wax mix. Again, there was little 538◦ C+ in the product, which was mostly
in the neutral oil boiling range, as shown in Figure 13.12. Hydroisomerization of the
pyrolysis bottoms gave a −14◦ C pour 3.4 cSt oil of 150 VI (Table 13.3). The overall
343◦ C+ yield was 37 wt%. Adding the potential lube from oligomerizing the lighter
olefinic product from the pyrolyzer would increase the 343◦ C+ yield to about 52 wt%.
Had all the 343◦ C− from the pyrolyzer been sent to oligomerization, the potential 343◦ C+
would be about 62 wt% (Figure 13.11). Note that the product distribution in Figure 13.11
is about the same for either FT wax alone or FT wax plus plastic. This suggests, along
with the similar properties found in the isomerized products, that a pyrolysis process could
be developed with a wide flexibility in choice of feedstock mix.
9 SUMMARY AND CONCLUSIONS
This chapter has summarized research conducted on feedstock recycling of waste plastic
into light oil products (∼C5 –C20 ) suitable for transportation fuels (gasoline, jet fuel, and
diesel fuel) and a high value product, lubricating oil. The principal results are summarized
below.
Transportation fuel . For mixed post-consumer plastic (PCP) that contains significant
amounts of paper, inorganics, and chlorine, the best approach appears to be pyrolysis
followed by hydroprocessing. Batch mode pyrolysis at 600◦ C, followed by thermal or
70
60
50 Pyrolyzed
Yield, Wt% 40 Feed
30
20
10
0
C1–C4 C5–343°C 343-538°C 538°C+
Figure 13.12 Pyrolysis of FT wax at 524◦ C and 1 h residence time
catalytic hydroprocessing at approximately 450◦ C under low hydrogen pressures gave oil
yields of approximately 80%, of which 50–55% was in the gasoline boiling point range,
and 20–30% in the kerosene range. Catalytic hydroprocessing using 1 wt% HZSM-5
improved the yields of the lighter products by about 5–10%. The results of a feasibility
study for a plant converting 300 t/d of waste plastics into oil for the transportation fuel
market were briefly reviewed. If oil prices in the range $30–50/bbl are assumed and waste
plastic is available at no cost and without any tipping fees, it appears that such a plant
could achieve returns on investment (ROI) of 20–40%.
Lubricating oil. A new process has been developed for the conversion of waste plastic
and Fischer–Tropsch (FT) wax to lube range molecules that can be hydroisomerized to
low pour point lube base oils of unconventional base oil (UCBO) quality. The process
employs pyrolysis, a thermal, noncatalytic, low-pressure reaction where high-molecular-
weight molecules are cracked to ones of lower molecular weight. The major by-product
is diesel, with little production of C4 − gas. The by-product liquids are highly olefinic and
could be oligomerized to provide additional base oil.
Laboratory experiments were first conducted using a continuous pyrolysis reactor to
establish optimal conditions for lube base oil production from polyethylene (PE). A pilot
plant study was then carried out in a 1-gallon-per-day unit. The main findings included:
1. Potential lube yields were in the 60–70 wt% range, assuming all the olefins (almost
all 1-olefins) could be upgraded to lube. About half this yield would come from
hydroisomerization and half from oligomerization.
2. The product distribution and lube oil quality surprisingly showed little variation,
whether the feed was PE, FT wax, or a combination of the two. Therefore, waste
PE could be co-processed in the same plant as FT wax, increasing product volume
and improving the economics of the process.
3. The pyrolysis process could be carried out at atmospheric pressure, and at a tem-
perature and residence time typical of refinery operations, i.e. 524◦ C for 1 h, with
total conversion of plastic to lube range and lighter product, almost all of which was
538◦ C−.
4. Hydrotreating the feed prior to the hydroisomerization step did not significantly affect
lube oil yield or quality. Eliminating this step could benefit the overall process
economics.
5. When 4 wt% polyethylene terephthalate (PET), derived from used soft-drink bottles,
was added to the PE, no decline in lube quality was observed, with hydroisomerization
giving a 160 VI 5 cSt oil. This indicates that a high degree of separation of the waste
plastic may not be necessary, which would lower the cost of feedstock to the process.
In summary, we have shown that by pyrolyzing waste polymers such as polyethylene,
waxy products similar to those from Fischer–Tropsch processing can be made, which
can then be converted to high-quality lubricant oils via wax hydroisomerization. While a
detailed economic analysis has not yet been carried out, the much higher value of lube
oil relative to transportation fuels suggests that this may be a more viable and profitable
way of disposing of waste plastic, a growing waste stream problem.
ACKNOWLEDGEMENTS
The research on conversion of waste plastic to oil products suitable for transportation
fuels was supported by the US Department of Energy, Office of Fossil Energy, National
Energy Technology Laboratory, under DOE research contract no. DE-FC22-93PC93053.
The post-consumer waste plastic used for this part of the research was provided by
Gerhard Fahrbach and Sabine Melichar of the DSD. Funding for the research on con-
version of waste plastic and Fischer–Tropsch wax into lubricating oil was provided by
ChevronTexaco Energy Technology Company.
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14
The Conversion of Waste

Plastics/Petroleum Residue
Mixtures to Transportation Fuels
MOHAMMAD FARHAT ALI AND MOHAMMAD NAHID SIDDIQUI
Department of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran
31261, Saudi Arabia
1 INTRODUCTION
Plastics have become the material of choice in the modern world and their applications
in the industrial field are continually increasing. Presently plastics are manufactured for
various uses such as: consumer packaging, wires, pipes, containers, bottles, appliances,
electrical/electronic parts, computers and automotive parts. Most post-consumer plastic
products are discarded and end up as mixed plastic municipal waste. The disposal of this
waste has become a major social concern.
Mixed plastic waste (MPW) recycling is still very much in its infancy. Approximately
20 million tons of plastic waste is generated in the United States of America, while about
15 million tons is generated throughout the Europe. With existing recycle efforts, only
7% of the MPW are recycled to produce low-grade plastic products such as plastic sacks,
pipes, plastic fencing, and garden furniture. The current plastic reclamation technology
options are generally grouped into the following four types:
• primary – the processing of plastic for use comparable to the original application;
• secondary – the processing of plastics waste into new products of a lower quality
level;
• tertiary – the chemical or thermal processing of plastic waste to their basic hydrocar-
bon feedstock. The resulting raw materials are then reprocessed into plastic material
or other products of the oil refining process;
• quaternary – the incineration of plastics waste to recover energy.
This chapter deals exclusively with tertiary recycling by pyrolysis and catalytic crack-
ing of plastics waste alone and by coprocessing with petroleum residue or heavy oils to
364 M.F. ALI AND M.N. SIDDIQUI
fuels and petrochemical feedstock for further processing in existing refinery and petro-
chemical units.
2 THE CHARACTERISTICS AND CHEMICAL STRUCTURE OF PLASTICS
Plastics are organic polymers consisting of giant molecules made up of a large number
of repeating units known as monomers. Polymer molecules have molecular weight in the
range of several thousand or more, and therefore, are also referred to as macromolecules.
This is illustrated by the following equation, which shows the formation of the polymer
polystyrene.
CH2 = CH CH2 CH
Styrene n
(monomer) Polystyrene
(polymer)
Polymers are classified according to their structure and degree of polymerization

such as:
(a) Linear polymers – a single linear chain of monomers.
(b) Branched polymers – linear chain with side chains.
(c) Cross-linked polymers – two or more chains joined by side chains (Figure 14.1).
All polymers can be divided into two major groups (thermoplastics and thermosets)
based on their thermal processing behavior. Thermoplastics soften and flow when heated.
Upon cooling, thermoplastic polymers harden and assume the shape of the mold. Examples
of commercial thermoplastics include polystyrene, polyolefins (e.g. polyethylene and
polypropylene), nylon, poly(vinyl) chloride (PVC), and poly(ethylene) terephthalate
(PET). Thermoplastics make up 80% of the plastic produced today and these polymers
are linear or branched in their structure.
Thermosets are polymers whose individual chains have been joined by side chains
(cross-linked). These polymers usually exist initially as liquids; they can be shaped into
Linear polymer Branched polymer Cross-linked polymer
Figure 14.1 Different types of polymer structure

TRANSPORTATION FUELS 365
desired forms by the application of heat and pressure. Once formed, they harden and
cannot be thermally processed or mechanically recycled. Principal examples of ther-
mosets include epoxies, phenol–formaldehyde resins, polyurethanes (PUR), and unsatu-
rated polyesters. Vulcanized rubber used in industry is also an example of a thermosetting
polymer. Thermosets make up the remaining 20% of plastic produced today. Presently,
all plastics are produced from petrochemicals derived from petroleum.
3 THE CHARACTERISTICS AND CHEMICAL PROPERTIES

OF PETROLEUM RESIDUE
Petroleum is a complex mixture of various aliphatic and aromatic compounds, including
sulfur, nitrogen and organometallic compounds. Petroleum residue constitute mostly of the
nonvolatile, high-molecular-weight fractions of petroleum, that remain after the removal
of the distillate fractions with boiling points up to 500◦ C. These compounds may differ
from one another greatly in both polarity and molecular size. The more polar compounds
interact with one another to form molecular associations of varying strengths and sizes.
These polar compounds are insoluble in n-alkanes and are known as asphaltenes. The
asphaltenes contain very high concentration of the detrimental heteroelements (S, N, O
and metals). Structurally, asphaltenes are condensed polynuclear aromatic ring systems
bearing mainly alkyl side chains. The number of these rings in petroleum asphaltenes
can vary from 6 to 15. Because of their condensed structure, asphaltenes tend to be
extremely refractory during processing operations. They are heat labile and are gradually
deposited as coke on the walls of a reactor vessel and also are adsorbed onto the surface
of catalysts. Metals present in asphaltenes also fill up the pores of the supported catalyst
within a short period. These characteristics of the petroleum vacuum residue prevent its
use as a feedstock to fluid catalytic cracking (FCC) or hydrocracking (HC) units.
Table 14.1 illustrates the more important properties of vacuum residues from Saudi
crude oils [1]. The three most important properties from the upgrading standpoint are
sulfur, metals and asphaltenes contents. Sulfur continues to be a problem chiefly because
of environmental objections to sulfur dioxide emissions. Therefore, a primary requirement
is the removal of at least a major portion of the sulfur in the vacuum residue.
4 TECHNOLOGIES FOR PETROLEUM RESIDUE UPGRADING

A number of technologies are available to upgrade distillation residues [2]. Thermal pro-
cessing is the traditional way to treat residues. Examples include visbreaking, flexicoking,
Table 14.1 Typical vacuum residue properties of Saudi Arabian crude oils (∼538◦ C+)
Properties Arabian light Arabian medium Arabian heavy

◦
Gravity ( API) 8.53 6.15 5.60
Sulfur (wt %) 4.16 5.31 5.50
Carbon residue (wt%) 15.2 19.8 22.4
Vanadium + nickel (ppm) 76 92 194
Asphaltene (wt%) 11.5 16.0 19.5
Nitrogen (wt%) 0.29 0.24 0.37
delayed coking, etc. These processes remove carbon as coke, thus increasing the H/C ratio.

2–(CH1.4 )n – −−−→ C + –(CH2.2 )n –
If cracking catalysts are used to support the cracking process, the sulfur and metal
contaminants must be removed upstream since they poison the catalyst, such as in the
residue FCC process [3].
The deasphalting process is also based on carbon removal [4]. However, it uses a
completely different technology. Here, asphaltenes are extracted by solvents from the
heavy ends. Light hydrocarbon (e.g. propane) or supercritical gases are used as solvents.
The resulting deasphalted oil is essentially free of metallic contaminants. The carbon
removal processes yield large amounts of low-value coke or asphalt beside the desired
hydrocarbon products.
None of the different processes has decisive economic advantage over the others. They
are economically feasible only in special situations, when an outlet for the low-value
products is available.
+H2
R–CH2 –CH2 –R −−−→ R–CH2 + R –CH2 −−−→ R–CH3 + R –CH3
catalyst
Addition of hydrogen for improving the H/C ratio leads to better yields of high value
products. Hydrocracking is the process of choice to upgrade crude oils [5]. It breaks
down high-molecular compounds in a cracking step and the fragments are saturated in
situby addition of hydrogen to the points of scission. However, as a catalytic process
hydrocracking is sensitive to catalyst poisons. Therefore the sulfur, nitrogen and metal
contaminant of the feed must be removed upstream in a separate reactor [6]. Although
hydrocracking is well suited for crude oils, it is much less advantageous for upgrading
distillation residues. The highly condensed aromatic compounds in residues do not undergo
hydrogenation easily and even under severe conditions the conversion is only of the order
of 75%. This leads to very short catalyst lifetimes, especially when zeolite based catalysts
are used. Because of the required high investment costs and other disadvantages, the
overall economics of the hydrocracking of residues are not much better than those of the
thermal cracking processes [7, 8].
In conclusion, most of the available technologies to upgrade oil residues are not free
of major disadvantages. Hydrocracking of residues is hampered by short lifetimes of the
zeolite catalysts and increasingly high cost of hydrogen. The carbon removal processes
such as coking, cracking or deasphalting, yield large amounts of low calorie gas, coke or
asphalt, which are difficult to market.
5 TECHNOLOGIES FOR TERTIARY RECYCLING OF MIXED PLASTIC

WASTE (MPW)
Tertiary recycling of MPW is getting a lot of attention as an alternative method to landfill

disposal and mechanical recycling. Tertiary recycling includes both chemical recycling
and feedstock recycling. Chemical recycling implies a change of the chemical structure
of the material, but in such a way that the resulting chemicals can be used to produce the
original material again. Feedstock recycling implies a change of the chemical structure of
the material, where the resulting chemicals are used for another purpose than producing
original material. Various technologies for tertiary recycling, therefore, include all those
processes which attempt to convert MPW to basic chemicals by the use of chemical reac-
tions such as hydrolysis, methanolysis and ammonolysis for condensation polymers and
to fuels with conventional refinery processes such as pyrolysis, gasification, hydrocrack-
ing, catalytic cracking, coking, and visbreaking for addition polymers. However, some of
these options are not suitable for MPW containing a high amount of PVC due to corro-
sion problems arising from chlorine and hydrogen chloride. For this reason the feedstock
recycling technology is grouped into the following three main categories:
1. MPW with a limited chlorine (i.e. PVC content)
2. PVC-rich MPW
3. Specific plastic waste such as PET, PUR and Nylon
The available technology options for these three classes are discussed in the following
sections:
5.1 FEEDSTOCK RECYCLING OF MPW WITH LOW PVC CONTENT
The following technologies have been reported as most promising options for feedstock
recycling of MPW [9].
5.1.1 Texaco Gasification Process (Netherlands, Pilot in the US)

Gasification is a thermal process which uses high temperatures to break down any waste
containing carbon. This technology uses less oxygen than traditional mass-burn inciner-
ation. The pyrolysis process degrades waste to produce char (or ash), pyrolysis oil and
synthetic gas (called syngas). The gasification process then breaks down the hydrocarbons
left into a syngas using a controlled amount of oxygen.
Texaco gasification, based on a combination of two processes, liquefaction and an
entrained bed gasifier, is summarized in the Figure 14.2.
In the liquefaction step the plastic waste is cracked under relatively mild thermal con-
ditions. This depolymerization results in a synthetic heavy oil and a gas fraction, which
in part is condensable. The noncondensable fraction is used as a fuel in the process. The
process is very comparable to the cracking of vacuum residues that originate from oil
recycling process.
5.1.2 Polymer Cracking Process (Consortium Project, Pilot)

This is a fluid-bed cracking process. It was first tested in 1990s. This pilot plant has a
400 tonne per year feed capacity, but runs continuously on a 50 Kg/h scale as it has limited
product storage. The next steps in the development process to follow are optimization
and scale-up.
Off gas
Start-up oil
Syngas
Plastics Liquefaction
Shredding unit
Sulphur
cleanup
Nitrogen Oxygen
Sulphur
Gas cooling
Gasification & cleanup
Ammonia
unit
Slag Waste water

cleanup
Filter cake
Ammonium
chloride
Figure 14.2 Schematic representation of the Texaco process
The decomposition of PVC leads to the formation of HCl, which is neutralized by

bringing the hot gases into contact with a solid absorbent. This results in a CaCl2 -fraction
that has to be landfilled. The purified gas is cooled, most of the hydrocarbon condensed
as distillate feedstock. The remaining light hydrocarbon gas is compressed, reheated and
returned to the reactor as fluidizing gas. Part of the stream could be used as fuel gas for
heating the reactor, but as it is olefin-rich, recovery options are underway.
The process shows good removal of elements such as chlorine. With an input of
10 000 ppm Cl, the products will contain around 10 ppm. This is somewhat higher than
5 ppm requirements for refinery use. Also metals like Pb, Cd and Sb can be removed
to very low levels in the products. All hydrocarbon products can be used for further
treatment in refineries.
5.1.3 BASF Conversion Process (Germany, Pilot but on Hold)

A 15 000 tone per year pilot plant was set up in Ludwigshafen, Germany, in 1994. Due
to the uncertainty of the feedstock waste supply, the pilot plant was closed in 1996. The
BASF process is shown in Figure 14.3. The products of this process are HCl, naphtha,
ethylene, propylene and heavy oils.
5.1.4 Use of Mixed Plastic Waste in Blast Furnaces

In this process MPW is used as a reducing agent, and hence this is generally seen as
a form of feedstock recycling. Recently, the reduction of iron ore has been started with
HCl
Liquefaction Gases
Plastic Pre-treatment and cracking Separation
Oils
High boilers,
residues
Figure 14.3 Schematic representation of the BASF pyrolysis process
Condensate
Wash HCl
Condensates + gas
Gas
MPW Depolymerization VCC-LPH
Depolymerization VCC-LPH
Hydrogenation Syncrude
H2 Cokes production
residue
Figure 14.4 Schematic representation of the Veba Oel process
plastic waste. This new idea of reduction is replacing the old reducing agents such as
coke, coal and heavy oil. An advantage of plastic waste is its low sulfur content compared
with coal. However, plastic waste has relatively high chlorine content due to the presence
of PVC. The main part of the chlorine forms HCl going into solution in the washer. Any
additional metals present in PVC end up either in the product (steel), or in one of the
residue flows from Blast furnaces [10].
5.1.5 Veba Combi Cracking Process (Germany, Operational until 2000)

Veba Combi Cracking (VCC) is a modified process technology of Veba Oel AG which was
first used for coal liquefaction. Coal was converted by hydrogenation into naphtha and gas
oil. The modified VCC process was used to convert vacuum distillation residues of crude
oil into fuel oils containing naphtha, gas oil and heavy distillates. Since 1988 Veba have
started to substitute the petroleum residue feedstock by chlorine-containing waste. The
plant configuration was changed to include a depolymerization section. In the depolymer-
ization section the plastic waste is heated to 350–400◦ C to effect depolymerization and
dechlorination. The products of this process are HCl, syncrude free of chlorine and low
in oxygen and nitrogen, gases and hydrogenated solid residue. Schematic representation
of Veba Oel process is shown in Figure 14.4.
6 COPROCESSING FOR FUEL FROM MIXED PLASTIC WASTE
Coprocessing refers to the combined processing of petroleum residue with other hydrocar-
bon feedstocks. The petroleum residue contains chiefly 75 wt% materials boiling above
500◦ C. The waste plastics are petroleum derived and therefore, provide a hydrocarbon
source that can be used for chemical feedstocks. The feedstocks are mixed and processed
simultaneously with the dual objective of liquefying the solid waste and upgrading the
heavy residue from either the liquefied solid wastes or petroleum oil to the premium fuel
oils boiling lower than 500◦ C.
The coprocessing of waste plastics with coal and other hydrocarbon sources such as
heavy oils, tar mats, and petroleum residue has been reported [11–13]. The results have
shown that adding heavy petroleum residue as a solvent in coprocessing reactions with
waste plastics and coal has some beneficial effect on the reactivity of the system. The
petroleum resid acts as an effective bridging solvent that, when added to coal and waste
plastics, provides a medium for their mutual dissolution. The processing of waste plastics
with coal, however, was found to be problematic, requiring multifunctional catalysts due to
the compositionally diverse nature of the two materials. The petroleum residue, however,
having a composition that includes both aromatic and aliphatic compounds, was found to
be a more compatible material for processing with waste plastics [14, 15].
Catalytic processing of model and waste plastics with light Arabian crude oil residue
was investigated using NiMo/Al2 O3 , ZSM-5, FCC, and hydrocracking catalysts. Reac-
tion systems that were studied included low-density polyethylene (LDPE), high-density
polyethylene (HDPE), polystyrene (PS), and polypropylene (PP). A series of single (plas-
tic/catalyst) and binary (plastic/residue/catalyst) reactions were carried out in a 25 cm3
microautoclave reactor under different conditions of weight and type of catalyst, duration,
pressure, and temperature. The optimum conditions selected were: 1% catalyst by weight
of total feedstock weight, 60 min reaction time, 8.3 MPa of H2 , and 430◦ C [14].
The coprocessing reactions of plastics with residues were followed by the quantitative
measurement of masses of the products that included gas, oil, preasphaltene, asphaltene,
and insolubles. Figure 14.5 shows the schematic representation of coprocessing method
and products separation [15].
The effects of catalyst on the product distribution for selected plastic/residue double-
component systems are shown in Table 14.2. The results show that the presence of residue
increased the overall conversion in the double-component coprocessing reactions com-
pared to the single-component reactions except in the case of polystyrene [14].
The effect of different temperatures and time durations on the product distribution of
LDPE, residue and LDPE/residue are given in Table 14.3. The conversions from LDPE
ranged from 50.0 to 57.3% at 430◦ C, 60 min and from 11.5 to 17.0% at 400◦ C 60 min.
When the time was reduced to 30 min the conversions were 21.5–23.7% at 430◦ C. At
the higher reaction temperature (430◦ C) the amount of hexane solubles (HXs) was high
and the THFs were low. At 400◦ C the amount of HXs produced from the LDPE reaction
was very low and recovery was high, indicating that low-boiling compounds were not
formed. The LDPE/resid system also produced less HXs at 400◦ C than at 430◦ C.
The effect of different catalysts on the conversions and product distribution showed
a significant improvement when the temperature was increased from 400 to 430◦ C. The
catalysts showed greater reactivity at 430◦ C, as indicated by the higher conversion percent.
The LDPE reaction with ZSM-5 (Z) and NiMo (N), were most effective for increasing
LDPE conversion and HXs yields at 430◦ C [14].
The product distribution for the catalytic coprocessing of waste plastics with petroleum
was also reported by our group [14]. High yields of liquid fuels in the boiling range
Plastic + Resid + Catalyst
Time: 30, 60 minutes

Temp.: 300, 400, 430, 500 °C
H2 Pressure: 1000, 1200 Psi
Gases Liquids
wt%
GC analysis Hexane
Solubles
Insolubles (HXs)
wt%
Toluene SIM Distillation
Solubles
Insolubles (TOLs)
wt%
THF
Insolubles Solubles
(IOM) (THFs)
wt% wt%
FT-IR
Figure 14.5 Schematic representation of coprocessing method and products separation
Table 14.2 Effect of catalyst on the product distribution for selected plastic/resid double-compo-
nent systems
∗
Reactants Catalyst Product distribution (%)
H,Z,F or N
Gas HXs TOLs THFs IOM Conversion Recovery
(%) (%)
LDPE/resid H 7.4 65.5 3.2 3.0 20.5 79.1 99.6
Z 8.7 62.5 6.2 3.9 18.0 81.3 99.3
F 5.2 60.2 11.6 4.5 18.0 81.5 99.5
N 3.5 70.7 8.8 1.4 14.6 86.9 97.7
HDPE/residue H 9.2 57.2 10.5 2.8 19.8 79.7 99.5
Z 10.5 55.7 8.9 3.2 21.4 78.4 99.8
F 7.2 63.5 10.5 3.8 14.5 85.0 99.5
N 5.2 65.5 11.8 2.1 13.1 86.9 97.7
PS/resid H 6.5 82.5 4.0 3.0 3.8 96.0 99.8
Z 7.3 80.7 3.5 3.8 4.5 95.3 99.8
F 5.2 84.2 3.0 3.9 3.5 96.3 99.8
N 5.1 83.3 4.8 2.3 2.6 97.4 98.1
PP/resid H 6.5 69.5 6.0 3.4 14.4 85.4 99.8
Z 7.5 70.2 5.7 3.9 12.5 87.3 99.8
F 5.0 64.5 10.3 8.2 10.2 88.0 98.2
N 4.2 66.8 8.9 7.8 10.2 89.8 97.7
∗
H hydrocracking catalyst DHC-32; Z ZSM-5; F FCC catalyst; N NiMo catalyst
Reaction conditions: 430◦ C, 60 min, and 8.3 MPa H2 introduced at ambient temperature
Table 14.3 Effect of reaction temperature and time on the product distribution for reactions with
different catalysts
Reactants Catalyst Product distribution (%)

H,Z,F or N
Gas HXs TOLs THFs IOM Conversion Recovery
(%) (%)
430◦ C, 60 min
LDPE Z 7.2 36.7 8.2 5.5 42.1 57.3 99.7
N 9.6 30.7 6.5 4.0 49.6 50.0 99.6
Residue Z 16.0 71.2 3.8 3.5 5.2 94.5 99.7
N 10.3 71.5 10.2 2.5 5.0 94.5 99.5
LDPE/residue Z 8.7 62.5 6.2 3.9 18.0 81.3 99.3
N 3.5 70.7 8.8 1.4 14.6 86.9 97.7
430◦ C, 30 min
LDPE Z 4.0 16.2 2.0 2.5 74.3 23.7 99.0
N 4.5 12.5 1.5 3.0 78.0 21.6 99.5
Residue Z 9.2 61.5 29.0 70.7 99.7
N 6.5 59.3 34.0 65.8 99.8
LDPE/Residue Z 4.5 31.0 64.0 35.5 99.5
N 2.0 28.9 69.0 30.9 99.9
400◦ C, 60 min
LDPE Z 6.5 10.5 83.0 17.0 100.0
N 2.0 9.5 88.5 11.5 100.0
Resid Z 10.5 52.0 37.5 62.5 100.0
N 7.2 48.7 44.1 55.9 100.0
LDPE/resid Z 3.9 20.4 75.7 24.3 100.0
N 2.0 15.6 82.4 17.6 100.0
100–400◦ C and gases were obtained along with a small amount of heavy oils and insoluble
material [14].
Post-consumer plastic samples consisting of soft-drink bottles, water bottles, water
cups, water bottle caps and yogurt pots were collected. The thermal and catalytic copro-
cessing of these materials was also studied over NiMo catalysts. The reaction products
were analyzed and are given in Table 14.4. The product distributions of these plastic
types were found to have a very high conversion reaction (79.2–95.8%) affording higher
amount of hexane solubles (46–68%). However, when the other three types of catalysts
(ZSM-5, FCC and HC) were used the boiling point distribution of reaction products was
fairly well representative. The boiling point distribution of reactions for LDPE/residue and
HDPE/residue mixtures are shown in Table 14.5. The proportion of material that boiled
in the ranges 300–400◦ C and 400–500◦ C was found to be relatively larger.
In another study, we carried out coprocessing of model and waste PVC using petroleum
residue and VGO using two different reaction processes [16]. In a single-stage pyrolysis
reaction, PVC was processed with petroleum residue at 150 and 430◦ C, under N2 gas for
1 h at each temperature in a glass reactor. The model PVC and waste PVC showed slight
variations in the product distribution obtained from the glass reactor. In the two-stage
Table 14.4 Summary of resid/waste plastic conversion and product distributions
Reactants Catalyst Gas Product distribution (wt%)
HX-S TOL-S THF-S IOM Conversion Recovery
Actual Calculated
Resid/soft-drink NiMo 19.1 45.9 47.9 8.6 9.2 15.2 84.8 98.0
bottle-PET
Residue/yogurt NiMo 12.1 66.5 67.9 11.6 4.3 4.1 95.9 98.6
pot-HDPE
Resid/cap of water NiMo 17.6 67.9 69.3 5.7 3.2 4.2 95.8 98.6
bottle-HDPE
Resid/water bottle-PET NiMo 21.9 50.6 51.8 8.1 6.0 12.2 87.8 98.8
Resid/water cup from NiMo 21.78 54.15 55.05 10.10 8.12 4.95 95.05 99.1
Arabian Gulf-PS
Resid/water cup from NiMo 20.2 57.53 58.23 9.50 7.52 4.55 95.45 99.7
Al-Watania-PS
Reaction conditions: 430◦ C, 60 min, and 8.3 MPa H2 introduced at ambient temperature.
Table 14.5 Boiling point distribution of reaction products for polyethylenes
System Product distribution (wt %) in terms of boiling point

IBP–100 C 100–200◦ C 200–300◦ C 300–400◦ C 400–500◦ C >500◦ C IOM
◦
LDPE/RESIDUE 4.3 12.8 26 25 17.3 14.6

HDPE/RESIDUE 2.8 19 26 18 21.1 13.1
IBP = Initial Boiling Point; IOM = Insoluble Organic Materials
process, model PVC, vacuum gas oil (VGO) and a number of different catalysts were
used in a stainless steel autoclave microtubular reactor at 350◦ C under a stream of N2
gas for 1 h and at 430◦ C under 950 psi (6.5 MPa) H2 pressure for a duration of 2 h.
Significantly different products distributions were obtained. Among the catalysts used,
fluid catalytic cracking (FCC) and hydrocracking catalysts (HC-1) were most effective
in producing liquid fuel (hexane soluble) materials. The study shows that the catalytic
coprocessing of PVC with VGO is a feasible process by which PVC and VGO materi-
als can be converted into transportation fuels. The reaction products obtained from the
coprocessing of PVC and VGO using different catalysts were analyzed and are given
in Table 14.6.
These studies concluded that the coprocessing of waste plastics with petroleum resid
is a feasible process by which plastics and resid materials can be converted to liq-
uid fuels. Reaction temperature and reaction time were found to affect the conver-
sion rate and the production of hexane-soluble material. The hexane-soluble materials
from this initial conversion can be further upgraded to gasoline and other high-value
diesel fuels or chemical feedstock. The rate of conversion in the coprocessing system
depended upon the chemistry and composition of the particular plastic material and
resid. In general, these studies help to demonstrate the technical feasibility for upgrad-
ing both waste plastics and petroleum residue and alternative approach to feedstock
recycling.
Table 14.6 Product distribution from two-stage pyrolysis of PVC and VGO mixture
∗
Experimenta Reactants HXNs TOLs THFs IOM HCl Gas
1 PVC + iron oxide catalyst 6.8 4.3 0.0 36.6 50.6 1.6
2 VGO + ZSM-5 70.5 4.2 0.0 9.5 0.0 15.8
3 VGO + PVC + ZSM-5 61.3 6.5 1.3 10.8 8.3 11.8
(54)
4 VGO + PVC + NiMo 61.5 6.2 1.8 9.8 7.9 12.8
(51.3)
5 VGO + PVC + FCC 65.9 7.1 1.8 10.2 8.1 6.9
(52.6)
6 VGO + PVC + HC-1 65.2 7.9 1.7 10.7 7.8 6.7
(50.7)
7 VGO + PVC + iron oxide catalyst 55.0 8.5 2.6 16.0 7.7 10.2
(50)
8 VGO + PVC + HC-2 59.0 7.1 2.1 13.0 7.8 11.0
(50.7)
9 VGO + PVC + HC-3 60.1 6.7 1.9 14.1 7.6 9.6
(49.4)
1. PVC 10 g, catalyst 0.5 g; 2. VGO 12.5 g, catalyst 1.25 g; 3–9. VGO 12.5 g, PVC 2.5 g, catalyst 1.25 g
Figures in parenthesis under ∗ HCl are % HCl content of PVC
Yield calculation basis wt%
Gas = 100 − (HXs + TOLs + THFs + residue + HCl)
HCl = NaOH titration
Reaction conditions: 1 h at 350◦ C under N2 gas +2 h at 430◦ C under 6.5 MPa H2 gas
7 PYROLYSIS
The chemical decomposition of organic materials by heat in the absence of oxygen is

called pyrolysis, and when these reactions takes place under the hydrogen gas pressure is
some times also referred as hydropyrolysis. Pyrolysis/hydropyrolysis typically takes place
in the temperature range 400–800◦ C and under 500–1500 psi hydrogen gas pressure.
Pyrolysis transforms organic materials into carbonaceous char, a small quantity of oils,
gases and ash. The combustible gases produced during the pyrolysis of organic material
include carbon monoxide, hydrogen, methane, carbon dioxide, water, and more com-
plex hydrocarbons, such as ethane, ethene, propane, propene, butane, butene and other
hydrocarbons.
The temperature and heating rates have considerable influence in the pyrolysis process
and can be controlled to produce desired solid, gas and liquid products. Pyrolysis mech-
anisms for municipal solid waste, tires, plastics sewage sludge and biomass have been
reported by many workers [17–20]. A series of pyrolytic reactions producing varying
amounts of products at different temperatures and heating rates have been reported [21,
22]. Pyrolysis at very slow heating rates coupled with a low final maximum tempera-
ture maximizes the yield of solid (char). A slow or conventional pyrolysis takes place
at moderate heating rates in the range of 20–100◦ C/min and at a maximum temperature
of 600◦ C which produces almost equal amounts of solids, liquids and gases. Whereas a
fast or flash pyrolysis takes place at very high heating rates of about 100–1000◦ C/s at
temperatures below 650◦ C and with fast quenching that leads to the formation of mainly
liquid product. At high heating rates and high temperatures, the oil products quickly break
down to yield a mainly gas product, but this process is totally different from gasification.
Pyrolysis process conditions can be optimized to produce either solid char and gas or a
liquid/oil product [23, 24].
7.1 REACTOR TYPES USED FOR PYROLYSIS
Different types of reactors are utilized for a wide variety of pyrolysis applications, includ-
ing processing of waste plastics. The worldwide waste plastic pyrolysis systems utilize
the fixed-bed designs of vertical shaft reactors and dual fluidized-bed, rotary kiln and
multiple hearth reactor systems. The type of reactor used is chiefly based on material to
be pyrolyzed and expected products from the pyrolysis. Stainless steel shaking type batch
autoclave and stainless steel micro tubular reactors have also been used extensively [14].
Fluidized-bed reactors have been extensively used in producing raw petrochemicals from
the pyrolysis of waste plastics [22, 24].
Due to high viscosity of plastics material the continuous feeding to conventional reactor
systems such as a fixed-bed reactor is problematic. Waste lubricating oils are used as
carriers. Content of plastics above 10 wt% increases viscosity hugely, requiring large
amount of oils. A screw kiln reactor was designed and used in order to overcome these
problems. The residence time can be modified just by varying the screw rate. The reactor
system has been found to be useful for both the thermal and catalytic cracking of waste
plastics [25].
The semi-continuous type of reactor with the large capacity was comprised of a pyroly-
sis chamber, a catalytic cracking chamber and a separation and purifying section. The feed
plastic material was melted and decomposed in the pyrolysis chamber held at the ambient
pressure and at the temperature 723–783 K, and fed to the catalytic cracking chamber.
A reflux condenser was used to separate and purify the products formed in the chamber
and individual factors were obtained using fractional distillation apparatus [26]. Differ-
ent types of reactors are being utilized depending on the type of feed and the expected
products from the pyrolysis.
7.2 CHEMICAL PRODUCTS OF PYROLYSIS
Pyrolysis of waste plastics with petroleum residue produces varying proportion of solid,
liquid and gas products under different conditions [23, 27]. The product gas from pyrolysis
is usually a fuel with a medium to low heating value. The product gas contains carbon
monoxide, which varies from 15 to 30% by volume. Hydrogen is also a part of the product
gas and varies from 10 to 20% by volume. Methane constitutes 2–4% by volume and
adds to the heating value. Noncombustible gases, such as carbon dioxide and nitrogen,
constitute a large part of the product gas. Carbon dioxide varies from 5 to 15% and nitrogen
from 45 to 60% by volume. Higher percentages of carbon dioxide indicate incomplete
reduction of the waste material [27]
The pyrolysis liquids consist mainly of tar, light oil, and liquor. The tar contains
16–25% olefins, 62–80% aromatics, and 3–14.5% paraffins and naphthenes, and the
remainder is organic compounds that have been identified as acids, bases, ketones, and
aldehydes containing from one to eight carbon atoms. The major components of light oil
are benzene and toluene. The boiling point curves obtained from the simulated distillation
(SIM) of oil, hexane soluble, fractions ranged from 70 to 550◦ C, showing the recovery
temperatures at initial boiling point (IBP) 10%, 50%, 90% and final boiling point (FBP).
These distillation cut-off points were used as base line in assessing the extent of con-
version of plastic–resid mixture into the transportation fuels [14]. Pyrolysis of PVC in a
technical-scale fluidized-bed reactor yielded aromatic oils and heating gas [28]. The most
important products were benzene, toluene, xylene and styrene, with a total yield of 31.4%
by weight (referring to the total organic input). Additionally, pyrolysis gas with a high
calorific value of 50 MJ/Kg was obtained.
8 ENVIRONMENTAL IMPACTS OF RECYCLING OF WASTE PLASTICS
The production and disposal of waste plastic products contributes significantly to their
environmental impact. Most plastics are nondegradable and take longer time to break
down when landfilled. With the increased use of plastics in modern life, the landfill space
required by plastics waste is a matter of serious concern. Furthermore, plastic production
requires significant quantities of primarily fossil fuels for both as a raw material and
to deliver energy for the manufacturing process. It is estimated that 4% of the world’s
annual oil production is used as a feedstock for plastics production and an additional
3–4% during manufacture. The overall environmental impact of waste plastics varies
according to the type of plastic used and the production method employed [29].
The production of plastics also involves the use of potentially harmful chemicals under
the name of stabilizers or colorants. Many of these stabilizers/additives have not undergone
environmental risk assessment and their impact on human health and the environment is
currently uncertain and doubtful. Phthalates, as additives, are widely used in the man-
ufacturing of PVC products, and risk assessments of the effects of phthalates on the
environment are currently being carried out. Recent research for the Community Recy-
cling Network casts doubt on whether pyrolysis and gasification are the right processes
for dealing with the residual municipal waste.
Waste disposal contributes towards climate change, for example through the release of
methane from landfill sites or the burning of fossil-fuel-based plastics. Human toxicity is a
measure of the potential risk to health from a plant. Like incineration, pyrolysis and gasi-
fication produce emissions: Air emissions include acid gases, dioxins and furans, nitrogen
oxides, sulfur dioxide, particulates, cadmium, mercury, lead and hydrogen sulfide; solid
residues include inert mineral ash, inorganic compounds, and any remaining unreformed
carbon [30].
9 ECONOMIC EVALUATION
The research on the liquefaction of waste polymers and the coprocessing of waste plastics
with vacuum residue or coal has been a subject of study by many groups at universities
and environmental agencies. A significant amount of effort and funds are being diverted
to develop process technology in order to convert mixed plastics waste from municipal
and industrial waste into a heavy liquid, suitable for use either as petroleum feedstock or
in producing ethylene and propylene, the building blocks of much plastics production.
This section deals with the economic evaluation of the conversion of mixed plastics
waste (MPW) into synthetic crude (syncrude) oil and coprocessing of MWP with vacuum
residue into syncrude. In their feasibility study, Ali and co-workers considered the process
technology developed by Veba Oel AG of Germany the Veba Combi-Cracking (VCC)
option for the processing of MPW [31]. The process data and economic data were taken
mainly from Dijkema and Stougie [32] and Huffman and Shah [33] for this study. All the
cost data were translated to represent the economic analysis for Saudi Arabian conditions.
It is estimated that solid wastes in cities of Saudi Arabia constitute approximately 15
wt% of total solid wastes. It is estimated that around 600 000 ton/yr of plastics are being
consumed in Saudi Arabia. This gives an estimated amount of 90 000 ton/yr of plastic
waste.
The plant configuration developed by Veba includes a depolymerization section to
allow MPW processing in two downstream sections: a condensate processing section
which comprises an alkaline wash and a hydrotreater to obtain a light syncrude of good
quality, and a VCC section where the depolymerizate produced is processed together with
an appropriate amount of vacuum residue (VR) into syncrude, E-gas and hydrogenation
residue. A simplified block flow diagram of the process is shown in Figure 14.6.
The depolymerization section is required to allow continuous MPW feed to the VCC
section. MPW itself cannot dissolve in VR, so direct feeding of MPW to a VCC is
impossible. In the depolymerization section, MPW is broken down into smaller chains,
thereby lowering its viscosity by applying a mild cracking process. The viscosity of the
depolymerized MPW is about the same as the viscosity of VR; hence intimate mixing
with VR becomes easy. A substantial amount of MPW (about 70%) is converted into
condensate; the remaining material is a heavy bottom product that has to be dechlorinated
both for economic as well as environmental reasons. The dechlorination is very effective;
over 99 wt % of chlorine present in MPW is liberated as HCl, which is removed by
alkaline washing.
HCl HCl
Condensate Syncrude 2
Wash Hydrotreater Wash
Condensate
+ (H)Cl E-gas
E-gas
MPW Depolymerizate Syncrude 1

Depolymerization VCC
E-gas Gas
Treatment
Vacuum Residue
Hydrogenation
HWI
Residue
Figure 14.6 Block diagram of Veba option for the processing of MWP
The estimated cost of erecting a MPW processing facility in Saudi Arabia is estimated
to be US$47 790 000 to process 100 000 ton/yr MPW or to produce 73 600 ton/yr of
synthetic crude oil. The price of syncrude oil is taken as $155 per ton.
The production cost of syncrude oil is estimated to be $179 per ton from a 100 000 ton/yr
MPW (only) processing facility. An additional cost of $24 per ton is required to process
MPW in a 100 000 ton/yr facility. However, if the capacity of the plant is increased to
200 000 ton/yr, the production cost decreases to $125 per ton thereby making the project
slightly profitable with a return on investments (ROI) of 5.4% per year.
If the MPW is coprocessed with VR, the production cost of syncrude oil is estimated to
be $133.7/ton from a 100 000 ton/yr (40 000 ton/yr MPW + 60 000 ton/yr VR) processing
facility. The ROI is positive with 3.24% per year, indicating that additional cost is not
required to process these waste materials. Increasing plant capacity to 200 000 ton/yr in
the ratio of MPW : VR as 2:3, the production cost further decreases to $108.2 per ton.
This study concluded that processing of MPW with VR at a capacity of 200 000 ton/yr
(80 000 ton/yr MPW and 120 000 ton/yr VR), is economically feasible for Saudi Ara-
bian conditions. This capacity is adequate in view of the amount of MPW generated in
Saudi Arabia. The internal rate of return (IRR) is about 14.6% with a payback period
of 6.4 years and break-even capacity of 47.6%. Although profitability is not very attrac-
tive, the project is recommended to solve the waste disposal problem of both MPW and
VR. Some assistance should be provided to operate these plants through environmental
protection agencies.
10 CONCLUSIONS
Coprocessing of waste plastics with petroleum residue is a feasible process by which waste
plastics and resid materials can be converted to liquid fuels. Reaction temperature and
reaction time strongly affect the conversion and the production of hexane-soluble mate-
rial. The hexane soluble materials from the initial conversion can be further upgraded to
gasoline and other high-value diesel fuels or chemical feedstock. The rate of conversion
in the coprocessing system depends upon the chemistry and composition of the particular
plastic material and petroleum residue. Finally, these studies help to demonstrate the tech-
nical feasibility for upgrading both waste plastics and petroleum residue and alternative
approach to feedstock recycling.
ACKNOWLEDGEMENTS
The financial support provided by King Abdulaziz City for Science and Technology
(KACST), Riyadh, Saudi Arabia through Project AR-18-22 and KFUPM through SABIC
Grant Project SAB-2002/08 for our work are gratefully acknowledged. The facility support
from the KFUPM is sincerely appreciated.
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30. http://faculty-staff.ou.edu/W/Robert.L.White-1/h res1.htm and references therein.
31. M. F. Ali, M. N. Siddiqui, S. H. H. Redhwi, and F. Rahman (2003). transportation
fuels from the catalytic coprocessing of waste plastics with petroleum resid, Pro-
ceedings Petrotech 2003, Bahrain, 29 September-1 October 2003.
32. G. P. J. Dijkema, and L. Stougie, “Environment and Economic Analysis of the Veba
Oel Option for the Processing of Mixed Plastic Waste”, Interduct, Rotterdamseweg
145, 2628 AL Delft, The Netherlands (1990).
33. G. P. Huffman, and N. Shah, www.RGS.UKY.edu, ‘Feasibility Study for a Demon-
stration Plant for Liquefaction and Co processing of Waste Plastic and Tires’, Con-
sortium for Fossil Fuel Liquefaction Science, 533 S. Limestone street., Rm 111,
University of Kentucky, Lexington, KY 40506 (2003).
PART IV
Reactor Types
15
Overview of Commercial Pyrolysis

Processes for Waste Plastics
JOHN SCHEIRS
ExcelPlas Polymer Technology, PO Box 2080, Edithvale, VIC 3196, Australia
1 INTRODUCTION
The production of gasoline, kerosene and diesel from waste plastics is an emerging tech-
nological solution to the vast amount of plastics that cannot be economically recovered
by conventional mechanical recycling operations.
Plastic pyrolysis involves the thermal degradation of the wastes in the absence of
oxygen/air. It provides for the disposal of plastic wastes with recovery of valuable gasoline
and diesel-range hydrocarbons. During pyrolysis, the polymeric materials are heated to
high temperatures, such that their macromolecular structures are broken down into smaller
molecules, resulting in a wide range of hydrocarbons being formed. These pyrolytic
products can be divided into a noncondensable gas fraction, a liquid fraction (consisting
of paraffins, olefins, naphthenes and aromatics), and solid residues (i.e. char).
Pyrolysis of waste plastics appears simple in concept. However, thermal cracking often
yields low-value mixtures (cocktails) of hydrocarbons having very broad compositional
range, sometimes extending from light alkane gases to coke (Figure 15.1). It is there-
fore necessary to find the optimal pyrolysis conditions and/or the most advantageous
catalyst to obtain marketable products (e.g. diesel fuel or gasoline) from plastic wastes.
Catalytic degradation yields a much narrower product distribution of carbon atom number
and reduces the reaction temperature. Such a mixture of hydrocarbons may be used as
transportation fuels.
Pyrolysis recycling of mixed waste plastics into generator and transportation fuels is
seen by many as the answer for deriving value from unwashed, commingled plastics as
well as managing their desired diversion from landfill.
Pyrolytic recycling of plastic wastes has already been achieved on a commercial
scale, albeit to a limited extent. Nevertheless, the development and improvement of
pyrolysis plastics recycling technologies in recent years has shown great commercial
384 J. SCHEIRS
30
After thermal cracking
After catalytic cracking

Weight proportion (wt%)
20
10
0
10 20 30 40
Kerosene Number of carbon atoms
Gas Gasoline
Figure 15.1 Schematic showing difference in yields and carbon length distribution for
thermal cracking and catalytic cracking. Note different distribution of carbon atoms in
liquid fuels made by thermal cracking and catalytic cracking of polyethylene
potential. The development of bench-scale experiments carried out in laboratories, through

to full-scale pyrolysis processes, have now resulted in a number of technically mature
processes.
Through the use of low-temperature vacuum pyrolysis and cracking catalysts, liquid
fuel yields of up to 80–85% are possible, with the resultant product resembling diesel
fuel, kerosene, gasoline or other useful hydrocarbon liquids. There are now emerging a
number of processes that will take post-consumer plastics and catalytically convert them
into gasoline and low-sulfur diesel fuel. This diesel fuel meets or exceeds both European
and Federal EPA standards for emissions and is designed specifically for the solid waste
disposal industry that has significant investment in diesel-powered equipment. The types
of plastic targeted as feedstock for this project have no commercial value and would
otherwise be landfilled.
A distinct advantage of plastic pyrolysis into fuels as a means of recycling is its ability
to handle mixed and unwashed plastics. Post-consumer plastics are often commingled and
contaminated with extraneous materials such as soil, dirt, aluminium foils, paper labels
and food remnants. While soil, dirt and glue can be removed from post-consumer plastics
by washing, this is a fairly expensive operation and it leads to secondary waste streams
COMMERCIAL PYROLYSIS PROCESSES 385
such as waste-water. Pyrolysis recycling of mixed plastics thus has great potential for
heterogenous plastic waste that cannot be economically separated.
1.1 ADVANTAGES OF PYROLYSIS
The advantages of pyrolysis of waste plastics into liquid fuels include:

• it allows the recycling of waste mixed plastics that cannot be efficiently recycled by
alternative means;
• it permits the recycling of unwashed and soiled plastics (e.g. agricultural plastics,
mulch/silage/greenhouse films and dripper/irrigation tube);
• it enables recycling of plastic laminates, coextrusions and multilayer packaging films,
particularly those with aluminium foil layers that are difficult to recycle using tradi-
tional reprocessing technologies.
Most commodity hydrocarbon plastics are suitable for pyrolysis. Generally the larger the
substituent in the side chain, the easier the plastic can be degraded. The order of increasing
side chain size is polyethylene<polypropylene<polyvinyl chloride<polystyrene.
Problems with many pre-existing plastic cracking technologies include:
• noncontinuous (batch) processes (not commercially viable);
• coking and carbon deposits on heat exchanging surfaces;
• stickiness of sand particles in fluidized-bed processes;
• unsatisfactory fuel quality;
• relatively high sulphur levels (100–700 ppm) in end product.
In the last five years however, a limited number of plastic pyrolysis processes have
been developed to overcome these limitations.
1.2 THERMAL CRACKING
Thermal cracking often yields a low-value mixture of hydrocarbons with a very broad
volatility range that can extend from hydrogen to coke. It is therefore important to deter-
mine the optimal pyrolysis conditions and/or the most advantageous catalyst to obtain
marketable products (e.g. diesel fuel) from mixed plastic wastes.
The pyrolysis product yield and composition are controlled not only by the temperature,
but also by the duration of the residence time. As a general rule of thumb the higher the
pyrolysis temperature, the higher the yield of noncondensable gaseous products and the
lower the yield of liquid fuels such as diesel. The optimum temperature range for the
production of diesel products from waste plastics is 390–425◦ C. Studies in a tubular
reactor have highlighted the importance of short residence time with high-temperature
pyrolysis for obtaining a high yield of light olefins.
There is a dramatic increase in gas yield with increasing temperature of pyrolysis.
While the hydrocarbon pyrolysis product yield increases with pyrolysis temperature, the
yield of the oil fraction is higher at the lower pyrolysis temperatures. The composition
of the pyrolysis oil also changes with pyrolysis temperature, generally containing larger
386 J. SCHEIRS
quantities of aliphatic compounds at the lower temperatures than at higher temperatures
where aromatics are the dominant compounds.
1.3 CATALYTIC CRACKING
The poor selectivity of the thermal decomposition of polyolefins has promoted the devel-
opment of catalytic cracking. Catalytic cracking lowers the pyrolysis process temperature
and lowers the boiling temperature range of the resultant liquid products. The use of
molecular sieves and amorphous silica–alumina catalysts for the cracking of waste poly-
mers into a range of hydrocarbons has been widely studied (see Chapters 3–5, 7, 8).
Catalytic cracking has some distinct advantages over thermal cracking, such as, lower-
ing the cracking temperature, increasing the reaction rate and increasing the production of
iso-alkanes and aromatics which are desirable for diesel fuel. Suitable cracking catalysts
have the ability to both substantially reduce the pyrolysis temperature and control the
pyrolysis products.
Using catalysts does not only lower the activation energy, reduce the energy consump-
tion and improve the process efficiency, but can also improve the selectivity and quality
of the products produced.
Catalysts with acidic surface sites and hydrogen ion donating ability enhance the iso-
merization of products and thereby increase the yield of isomeric hydrocarbons that have
a beneficial effect on the cetane rating and fuel quality. Catalysts having stronger acid
sites of higher density are thus more effective in cracking polyolefins. However, strong
acidity and large pore size both lead to faster deactivation of the catalyst. Pyrolyzing with
catalysts having mild acidity and long life are preferred for the cracking of polyolefins.
A major problem with using catalysts in the pyrolysis of mixed plastics is that of coke
formation deactivating the catalyst over time. The cost of these catalysts also influences
their selection and commercial viability.
The amount of the catalyst to be added to the waste plastic for catalytic cracking is at
least 5% by weight (typically 5–10% by weight).
The problems associated with the use of a catalyst in the pyrolysis vessel are:
• the catalyst is a consumable and therefore adds to the running cost;
• the catalyst can have a short life-cycle due to poisoning/deactivation;
• the catalyst leads to increased levels of solid residue that requires disposal.
Figure 15.1 highlights the differences between thermal and catalytic cracking in terms
of the breath and distribution of carbon chain lengths of the products.
2 FEEDSTOCK OPTIONS
The composition of the plastic feedstock for pyrolysis processes has a direct bearing on the
quality of the resultant fuel products, especially flash point, cetane index, low-temperature
properties and heteroatom content (e.g. sulphur, chlorine and nitrogen).
While condensation polymers such as PET and polyamides can be broken down into
their monomer units by thermal depolymerization processes, vinyl (addition) polymers
such as polyethylene and polypropylene are very difficult to decompose to monomers.
This is because of random scission of the carbon–carbon bonds of the polymer chains
during thermal degradation, which produces a broad product range.
2.1 POLYETHYLENE (PE)
There have been many reports on the thermal and catalytic degradation of high-density
polyethylene (HDPE), as it is one of the main polymers in municipal solid wastes [1].
PE-derived fuel has a very low cetane rating and is very high in linear paraffins and
1-olefins. Paraffins are straight-chain hydrocarbons that are normally present in diesel.
They are the first components to come out of solution as diesel cools. The tendency of
paraffin crystals to aggregate up at low temperatures to form sheets can result in fuel-filter
blockages, ultimately leading to interruption of the fuel flow. Paraffin crystals form in the
fuel, making the gelled suspension appear cloudy. As these suspended flakes pass through
the filter, they gum up its microporous surface.
Due to the high concentration of linear n-paraffin hydrocarbons in fuel derived from
PE, it is desirable to isomerize them in order to lower the cloud point and the freezing
point of the fuel. The branched isomers do not exhibit the same tendency to crystallize
as linear paraffins, so that wax crystals do not form until lower temperatures are reached.
2.2 POLYPROPYLENE (PP)
The liquid products of the pyrolysis of PP contain primarily olefins that resemble the
molecular skeleton of PP (i.e. branched hydrocarbons). A distinguishing feature of PP
pyrolysis is the predominant formation of a particular C9 olefin in the pyrolysis product.
The level of this C9 compound identified as 2,4-dimethylhept-1-ene can be as high as
25%. Also present are C5 olefin, C6 olefin, several C15 olefins and some C21 olefins [2].
The tertiary carbon sites in PP allows for the facile chain cleavage and rearrangements
according to the Rice–Kossiakoff cracking mechanism shown in Figure 15.2. The non-
condensable gas from PP pyrolysis contains elevated levels of propylene, isobutylene and
n-pentane.
Compared with PE, PP produces less coke residue and more liquid products, but with a
higher content of ‘lights’. In the pyrolysis process of PP the intramolecular radical transfer
is preferred to the intermolecular one, thus the low oligomer formation predominates,
skewing the carbon number distribution towards the light end of the distillate spectrum.
Consequently the pyrolysis oil of PP is much more volatile than that of PE, decomposing
mainly through intermolecular radical transfer. The difference in the backbone structure of
the products of these polymers is more important from the point of view of fuel properties.
The isoalkanoic structure of PP is maintained in the thermal decomposition products, thus
the octane number of the pyrolysis oil is typically high.
388 J. SCHEIRS
Radical abstraction Other likely products from
polypropylene
11 9 7 5 3 1
H
10 8 6 4 2
1-pentene
Decomposition steps
11 9 7 5 3 1
10 8 6 4 2
2-methyl-pent-1-ene
11 9 7 5 3 1
+
10 8 6 4 2
2,4,6-trimethyl-non-1-ene
Isomerization by internal hydrogen transfer
11 9 7 5 3
H
10 8 6 4 2,4,6,8-tetramethyl-undec-1-ene
Decomposition steps
11 9 7 5 3
10 8 6 4
Structure for primary polypropylene
11 9 7 5 3 pyrolysis product, identified by GC/MS
+
10 8 6 4 2,4-dimethylhept-1-ene
Figure 15.2 Rice–Kossiakoff cracking mechanism for polypropylene showing that the
pyrolysis products of PP retain a branched structure
2.3 POLYSTYRENE (PS) PYROLYSIS
Neat polystyrene feedstocks will depolymerize in a pyrolysis process to give predomi-

nantly styrene monomer–a liquid fuel with good energy content.
The optimum pyrolysis temperature is 395◦ C to give a recovery ratio of 0.97 (i.e.
1000 kg polystyrene will yield 970 L liquid monomer) and 5 to 10% char residue. Fuel
made from polystyrene feedstock will be high in aromatic character and have an energy
content of 50 MJ/kg and a pour point of −67◦ C. However the flash point is only 26◦ C and
the cetane rating only 12.6. The fuel needs to be blended with polyolefin-derived diesel or
regular diesel in order to upgrade the flash point and cetane rating to within specification.
Polystyrene has somewhat lower thermal stability than the polyolefins and its pyrolysis
can be undertaken between 380 and 420◦ C without producing gases or leaving significant
amount of residue after total conversion. PS cracks to styrene, ethyl benzene, toluene,
trimethylbenzene and some benzene. In spite of the fact that the majority of the carbon
atoms are assembled into phenyl side groups in this polymer, a negligible amount of
benzene is formed (1–3%) at these temperatures. This is because the aryl–alkyl bond
connecting the phenyl group to the polymer chain is stronger than the bond of alkyl
carbons along the chain.
The pyrolysis of PS yields dominating components, styrene (bp 145◦ C) in the gasoline
boiling range, styrene dimer in the diesel oil range, and styrene trimer boiling at 400◦ C.
This pyrolysis product distribution suggests that the intermolecular radical transfer is
negligible in PS. The pyrolysis of PS produces fuel with a high aromatic content and low
storage stability. The high aromatic content of PS-derived oil helps to compensate for the
low cetane number of PE oil.
2.4 PET
Pyrolysis of PET under mild conditions predominantly forms terephthalic acid (TPA).
Since TPA easily sublimes it is often found in the condensing units of pyrolysis plants.
Under high-severity conditions however, little TPA is observed. This is because at
higher temperatures TPA is decomposed into benzene, carbon dioxide and benzoic acid
(Figure 15.3) [2].
O O O O
PET: C C C C
O (CH2)2 O O (CH2)2 O
Low severity pyrolysis
O O O
+ CH2 CH2 +
C C CH3 C
HO OH H
High severity pyrolysis
O
CO2 + + CH4 + CO
C
OH
Intermediate
Product
Figure 15.3 Thermal cracking mechanism for polyethylene terephthalate. Note under
mild conditions terephthalic acid predominates, but under more severe pyrolysis condi-
tions the terephthalic acid decomposes to benzoic acid and benzene
390 J. SCHEIRS
The pyrolysis of PET by Sakata [3] has been found surprisingly to yield no liquid
products. It is widely known that compounds that undergo sublimation, such as tereph-
thalic acid and benzoic acid, are produced by the thermal decomposition of PET and
this causes problems in plastic pyrolysis plants. Interestingly Yoshioka et al. [4] found
that the addition of calcium hydroxide (slaked lime) gives high selectivity for benzene
formation without producing sublimation compounds such as terephthalic acid. The yield
of benzene is around 35 wt% at 700◦ C and a 10.0 calcium hydroxide/PET molar ratio.
2.5 PVC
PVC is not recommended as a feedstock material for pyrolysis. The reasons for this
being that it contains about 57% chlorine by weight which will affect diesel quality
and can produce chlorinated hydrocarbons, and also because it thermally decomposes to
hydrochloric acid that is very corrosive and toxic.
The presence of 1–3% PVC in the feedstock stream results in the product fuel oil
having a total chlorides level of 5000–10 000 ppm. However at the same PVC levels
the total chloride concentration in the diesel can be reduced to less than 10 ppm by the
addition of lime hydrate according to the following reaction:
Ca(OH)2 + 2HCl → CaCl2 + 2H2 O
PVC in the feedstock stream in limited amounts can thus be tolerated if a HCl removal
process based on calcium hydroxide (slaked lime) injection is used. This is essentially a
form of in situscrubbing in the pyrolysis reactor itself. This method is used by a number of
pyrolysis processes since the fuel oil end products need to be low in chlorine to minimize
engine corrosion problems. In the pyrolysis of commingled plastics, lime can be added to
the input material and the PVC content reduced down to 2–3% in order to avoid deposits
of CaCl2 in pipework. The chlorine content of the final diesel should not exceed 10 ppm.
It has been demonstrated that oil recovered from PVC-containing plastic feedstock can
be used as a fuel. Cost is the main obstacle since it requires a large amount of slaked lime
to neutralize the HCl gas that is produced by the thermal cracking. Table 15.1 shows the
effect that slaked lime has on reducing the chlorine content of fuel oil derived from the
pyrolysis of PE (55 wt%), PP (28 wt%) and PS (17 wt%) at a decomposition temperature
of 420◦ C.
Table 15.1 Effect of slaked lime addition on the pyrolysis of

plastic containing 1% PVC. (Reproduced by permission of Masa-
taka Tsukada)
Slaked lime added Total chlorine in fuel HCl in fuel

(%) (mg/L) (mg/L)
0.0 1139.3 490
1.2 72.5 26
2.0 54.2 20
As shown in Table 15.1, adding 1–2% of slaked lime enables the desired level of
chlorine in recovered fuel to be achieved, thereby allowing the fuel to be suitable as a
diesel fuel. However some chlorine still remains. There is always a small percentage of
moisture existing in the waste plastic. It is later separated out and condensed as water.
This water reacts with chlorine species in the fuel and produces hydrochloric acid.
2.6 HALOGENATED POLYMERS
Since the pyrolytic recycling of waste plastics containing halogen atoms (e.g. Cl, Br, F)
poses special problems, the pyrolysis process can incorporate a special halogen elimi-
nation step such as dehydrochlorination. Hydrogen chloride, evolved from PVC during
heating, can be fixed by metal oxides (e.g. calcium oxide) to form the corresponding
metal chlorides. Electronic scrap contains high levels of halogenated flame retardants as
well as various metals and fillers in addition to plastic materials. The pyrolytic recycling
of the mixed plastics from electrical and electronic waste solves a number of problems
such as dehalogenation of the product (see Chapter 20).
2.7 PLASTIC FEEDSTOCK SPECIFICATION
Plastic feedstock specifications are extremely important in order to obtain satisfactory

and consistent fuel quality (see Table 15.2). A rigid ‘incoming feedstock specification’
(IFS) ensures that limits are placed on ‘critical’ contaminants. The critical contamination
is based around the so-called ‘hetero-atoms’. These are listed below in order of priority:
• S (e.g. vulcanized rubber and S-containing sources such as food preservatives);
• Cl and Br (e.g. PVC, PVDC and brominated flame retardants);
• N (e.g. nylon, ABS, PU foam)
Periodic feedstock audits also need to be conducted to ensure the IFS are being adhered
to.
Table 15.2 Properties of fuel produced by pyrolysis of various plastic feedstocks. (Reproduced
by permission of Masataka Tsukada)
Fuel property PE PP PS Nylon PP 50%, PE 43%,

NYLON 7%
Flash point (◦ C) 33.6 27.8 26.1 34.8 26.0
Pour point (◦ C) 2.7 −39 −67 −28 −5.0
Water content (ppm) 0.18 0.13 0.67 2500 310
Ash (wt%) 0.013 0.010 0.006 0.018 0.001
Viscosity (cSt at 50◦ C) 2.190 1.9 1.4 1.8 1.485
Density (g/cm3 ) 0.858 0.792 0.960 0.926 0.799
Cetane rating 56.8 12.6 54.3
Sulphur (wt%) 0.01 0.01 0.01 0.01 0.013
Nitrogen (ppm) 0.2 0.2 0.2 6400 1750
Energy content (kJ/kg) 52 263 53 371 50 365 44 403 46 270
392 J. SCHEIRS
Table 15.3 Typical Input Specifications (from BP’s Grangemouth Pyrolysis Plant)
Property Specification
Polyolefins (LDPE, LLDPE, HDPE, PP) 80 wt.% (min 70%)
Polystyrene (GP-PS, EPS, HIPS) 15 wt.% (max. 30%)
PET 3 wt.% (max. 5%)
PVC 2 wt.% (max. 4%)
Total plastic content 95 wt% (min. 90%)
Ash 2 wt.% (max. 5%)
Moisture 0.5 wt.% (max. 1%)
Metal pieces Max. 1 wt.%
Size 1–20 mm
Fines (sub 250 µm) Max. 1 wt%
Bulk density 400 kg/m3 (min. 300 kg/m3 )
Typical input specifications for BP’s Grangemouth pyrolysis plant are shown in
Table 15.3.
3 OPERATIONAL CONSIDERATIONS
The development of commercially viable plastic pyrolysis processes has up to now been
hindered by the need to engineer around various process problems such as reactor fouling
by carbon deposits, poor heat transfer of molten plastics, the requirement for integrated
fractionation of products, separation of water and suspended carbon from the liquid fuels
and integrated desulphurization.
3.1 PREVENTING COKING
One of the main technical barriers to the pyrolysis of plastic wastes is the formation
of carbon (coke) deposits in the reactor. The coking deposits over the heat exchanging
surfaces of the reactor and deactivates catalysts (if used). In this regard, PE and PP
are preferred feedstocks over PS due to the high coking potential of PS. Batch reactors
with mixers can generally be run only semi-continuously, since after a few days of
operation they must be stopped for cleaning and coke/char removal. Carbonaceous coke
that accumulates on the inside walls of the pyrolysis vessel can lead to poor heat transfer
to the plastic. The char is generally removed by scrapers attached to the agitator shaft.
The char is a solid carbonaceous residue that is black, brittle and porous and resembles
coke with its honeycomb structure and metallic lustre.
Scraped surface heat exchangers (SSHE) have been used as tubular reactors for plas-
tics pyrolysis. SSHE overcome coking and carbon deposits forming on heat exchanging
surfaces when the plastic pyrolyzes to hot gases. A tubular reactor with a special inter-
nal screw mixer has been developed in Poland [5]. The purpose of the specially shaped
internal mixer is to mix the molten plastic and to scrape coke from the internal surface
of the tube reactor. The advantage of these systems is the continuous coke removal from
the reactor tubes.
The Thermofuel process uses a simple pot (kettle) design with an internal mixer/scraper
that extends up the walls of the chamber to continuously remove the coke deposits. Some
pyrolysis processes (e.g. Smuda) have a means for withdrawing the thermal cracking
residue from the lower portion of the thermal pyrolysis vessel. The powdered coke or
solid residue that forms on the bottom of the vessel can be removed on an intermittent
basis either by an auger positioned in the floor of the pyrolysis chamber or through a
hollow agitator shaft by a vacuum extraction system. It is critical that the char removal
process incorporates an ‘airlock’ that prevents oxygen ingress into the pyrolysis vessel.
3.2 PREVENTING CORROSION
In general, halogen-containing polymers (e.g. those containing Br and Cl) are not accept-
able feedstock for pyrolysis because they would necessitate the use of special alloys to
prevent corrosion and pinholing of the plant components (e.g. condensor coils).
3.3 TANK/KETTLE REACTORS
Discontinuous (batch process) and continuous (alternating batch or cascade) stirred tanks
reactors are generally used in commercial-scale melt-phase pyrolysis plants. These units
are relatively simple, basically consisting of a large stainless steel vessel with indirect
heating (either flame or hot air), a large stirrer and possibly internals such as baffles to
enhance mixing and heat exchanger surfaces. Internals however may gradually become
coated with coke and other impurities and are therefore generally avoided [6].
3.4 REFLUX
Reflux describes the process by which the heavy end of the hot pyrolytic gases are
selectively condensed and flow back into the pyrolysis chamber for further cracking. Seth
and Sarkar [7] compared the effects of degradation with and without a reflux on the MWD
of the product. They found that when polypropylene is heated in an inert atmosphere and
the volatile products are condensed, the molecular weight distribution (MWD) of the
product obtained is very wide. In addition, this product is very waxy, has poor flow
properties, and is unusable as a liquid fuel. To improve the product quality, ZSM-5 and
other catalysts are usually used in the recycling process. However, these catalysts are
costly. On the other hand, if the higher boiling fractions of the volatiles evolved due to
degradation are not allowed to escape, then the MWD and chain length distribution of
the final liquid product can be improved.
3.5 PROBLEMS WITH BATCH PYROLYSIS
Problems with batch pyrolysis plants are often mechanical in nature and are related to
residue extraction problems, coking/fouling of heat exchanging surfaces, corrosion by
394 J. SCHEIRS
aggressive products, clogging of condensors and ducts by waxes and other solidified or
sublimed products (e.g. terephthalic acid) [6].
3.6 CONTINUOUS SYSTEMS
Extruders are often used in continuous pyrolysis plants for supplying a molten stream
of plastic to the main pyrolysis vessel. The extruder may also be vented to eliminate
HCl (from PVC) and water vapour from the waste plastics. In contrast to conventional
extrusion, there is no need to build up high melt pressure or to shear the polymer. These
pyrolysis extruders are more like heated augers than polymer processing equipment.
3.7 FLUIDIZED-BED PROCESSES
For large-scale continuously operating pyrolysis plants, a fluidized-bed reactor has numer-
ous advantages such as improved heat transfer to the plastic, continuous dosing of catalyst
and continuous coke removal. Fluidized-bed processes are however not efficient when
applied on a relatively small scale.
Fluidized-bed processes are either bubbling or internally circulating. The fluidized-bed
reactor is very versatile for the pyrolysis of polyolefins. Nevertheless one of the problems
with fluidized-bed pyrolysis of post-consumer plastics relates to the stickiness of the sand
particles (the fluidization medium) that becomes coated with fused plastic. In order to
solve these problems, new reactors have been proposed, such as the conical spouted bed,
the conical rotary reactor, a sphere circulation reactor and a reactor with mechanical
particle stirring.
3.8 FLUID-BED COKING
Fluid-bed coking is a continuous version that delays coking. Here the cokes are formed on
fludized coke particles that are circulated between the coking unit where the endothermic
pyrolysis reaction takes place and the regenerator in which the coke particles are reheated
by partly burning off.
3.9 FLUID CATALYTIC CRACKING (FCC)
Fluid catalytic cracking (FCC) has been used since the 1950s to turn heavy distillates
(vacuum gas oil) into a series of light and dense fractions. The FCC catalysts can also be
used as pyrolysis catalysts.
3.10 CATALYTIC CRACKING
It has been found for the catalytic cracking of a plastic mixture consisting of LDPE
and ethylene–vinyl acetate (EVA) copolymer (86/14 w/w), that nanometer sized HZSM-
5 was more active at cracking this plastic mixture at 420◦ C than the mesoporous catalyst
Al-MCM-41. This was ascribed to the occurrence of cross-linking reactions, leading to a
fast deactivation of the mesoporous Al-MCM-41 catalysts by coke fouling [8].
4 ENGINEERING DESIGN ASPECTS
4.1 PYROLYSIS CHAMBER DESIGN
The pyrolysis and/or catalytic cracking process is generally carried out in a continuous
stirred tank reactor (CSTR) also called a chamber or vessel. Pyrolysis vessels generally
have a dished or cone bottom for strength. Flat-bottom vessels tend to distort readily,
especially at process temperatures of 390–425◦ C. The floor of the vessel is either conical
or torispherical. The torispherical shape of the bottom of industrial vessels allows the agi-
tator/scraper to be placed very close to the bottom, making this impeller/tank configuration
very efficient for suspending heavy dispersions and minimizing coking and fouling of the
base. A typical stirred tank pyrolysis vessel is shown in Figure 15.4. A torispherical or
conical base allows the solid residue or coke to accumulate at a central point for removal.
Pyrolysis vessels can range from 3 to 20 m3 in volume. Towards the upper end of the
size range, heat transfer limitations occur and it is necessary to use heat exchanging pipes
internally to assist with heat transfer. The problem with an array of heat exchanging pipes
internally however is that they are susceptible to fouling and coking by a carbonaceous
residue.
3a
10 2 3
6 5 7
11
1
12
4
8
Figure 15.4 A schematic of a typical continuous stirred tank pyrolysis process. Legend:
1 pyrolysis vessel with internal agitator; 2 catalyst chamber; 3 plastic feedstock hopper; 4
char auger to remove solid residue; 5 agitator drive motor; 6 lower temperature sensor;
7 upper temperature sensor; 8 burner for furnace; 9 feed auger for plastic feedstock; 10
condenser cooling jacket; 11 condenser; 12 oil recovery tank (adapted from Saito, K. and
Nanba, M., United States Patent 4,584,421 (1986) ‘Method for thermal decomposition of
plastic scraps and apparatus for disposal of plastic scraps’)
396 J. SCHEIRS
4.2 PYROLYSIS VESSEL CONSTRUCTION
Pyrolysis vessels are generally made from SS316 or 9Cr 1Mo steel. Maximum corrosion
allowance should be made for the pyrolysis chamber as the metal will potentially be
exposed to hydrochloric acid and hydrobromic acid that can cause pinholing of SS304.
The pyrolysis chamber needs to have a relief valve or PSV (pressure safety valve) to vent
to a safe location in case of a sudden pressure build-up.
4.3 AGITATOR SPEED
In kettle-type pyrolysis systems the melt is agitated to ensure good heat transfer, heat
distribution and to keep char particles from caking out. Stirring of the melt in a pyrol-
ysis vessel greatly accelerates the heat transfer process. In the Thermofuel process the
agitator currently runs at 6–7 rpm. In the Smuda process in Korea the agitator speed
is 30 rpm. Higher agitator speeds are clearly beneficial in ensuring better heat transfer,
heat distribution and anti-coking. In the Fuji Process the melt in the pyrolysis cham-
ber is not stirred, but instead recirculated via a centrifugal blender to a melting pot and
back again.
Curved-blade impellers are generally used in CSTR pyrolysis vessels. Generally the
gap between the scraper and the vessel wall is between 6–9 mm to allow for thermal
expansion effects.
4.4 BURNER CHARACTERISTICS
The pyrolysis chamber is generally heated with a high velocity gas burner. In order to
avoid hot-spots, an impingement plate is used such that there is no flame impingement
on the vessel itself. In newer designs however the chamber is heated indirectly with a hot
air burner so that hot spots and flame impingement problems are eliminated.
4.5 INERT PURGE GAS
After filling the chamber it is necessary to purge with inert gas (i.e. nitrogen) in order to
exclude oxygen or alternatively to apply a vacuum. It is customary to purge the pyrolysis
chamber with nitrogen to evacuate any residual air in the vessel before pyrolysis. After
pyrolysis N2 purging is also required to evacuate hydrocarbon gases until the hydrocarbon
levels are low enough (in the order of parts per million) to open the vessel and to
commence air purging.
Instead of using an inert purge gas to blanket the polymer in the chamber the chamber
atmosphere can also be evacuated to remove air/oxygen. Pyrolysis under vacuum reduces
the incidence of secondary reactions in the gas phase in contrast to pyrolysis at atmospheric
pressure. Under vacuum, the residence time of the pyrolysis products is short and so the
secondary reactions are limited.
4.6 DISTILLATION COLUMNS
The pyrolysis gases typically contain a broad boiling point range of materials. Most
state-of-the-art pyrolysis processes that convert waste plastics into liquid fuels send the
pyrolysis gases into some form of separator such as a distillation column; where the stream
is separated into typically at least three fractions – a light, middle, and heavy fraction.
The light fraction contains (e.g. 177◦ C) gasoline range material and gases. The middle
fraction is typically a middle distillate range material, such as the diesel fuels range, (e.g.
177–343◦ C). The heavy fraction is lube oil range material (e.g. 343◦ C).
Distillation columns can have trays or packing. The advantage of packing is that the
column can be smaller in diameter and marginally shorter.
4.7 CENTRIFUGE
In order to remove water and particulate impurities from the liquid fuel products, a liquid
centrifuge is normally employed, running at 12 000 rpm (for example Alfa Lavel 2000
which has a capacity of 1200 L/hr). Such a system gives three-phase separation of diesel,
water and sludge. It is important that the diesel is cooled (using a pipe-in-pipe heat
exchanger for instance) since the centrifuge should not process diesel over its flash point
range (i.e. 60–70◦ C) due to explosion risks.
4.8 SCRUBBER
A wet alkali scrubber is generally employed to scrub acidic impurities from the non-
condensable gas stream. The gaseous, water-soluble inorganic compounds are removed
by scrubbing the noncondensable pyrolysis gas with an alkaline aqueous stream. In the
scrubber, desulphurization and/or denitrogenation and/or dechlorination occurs. Most of
the acidic gases such as HCl, SO2 , SO3 , H2 S, etc. resulting from pyrolysis are absorbed
in the scrubber.
4.9 DECHLORINATION
The plastic feed may contain chlorine in the form of PVC or PVDC. Preferably, a substan-
tial portion of any chlorine in the feed is removed by the addition of a chlorine scavenger
compound to the feed, for example, sodium carbonate or slaked lime (calcium hydroxide)
to the feed. It reacts in the pyrolysis zone with the hydrogen chloride to form sodium chlo-
ride or calcium chloride which becomes part of the residue at the bottom of the pyrolysis
vessel. Preferably, the chlorine content should be removed to less that about 5 ppm.
4.10 HYDROTREATING
Hydrotreating of pyrolysis-derived fuels is particularly desirable as a means of saturating

olefinic end groups (i.e. unsaturation) and for the reduction of sulphur levels to meet
398 J. SCHEIRS
fuel standards. A hydrotreating step is advantageous to improve thermal and oxidative
stability and colour of the liquid fuels. In the Smuda process prior to catalytic isomer-
ization dewaxing, the pyrolysis effluent is hydrotreated to remove compounds such as
N-, S- or O-containing compounds, that could deactivate the isomerization dewaxing
catalyst or produce an unstable fuel oil composition (e.g., colour instability). Hydrotreat-
ing is typically conducted by contacting the pyrolysis effluent heavy fraction with a
hydrotreating catalyst at hydrotreating conditions. A conventional catalytic hydrotreat-
ing process may be used. The hydrotreating is done under conditions to substantially
remove all heteroatoms, while minimizing cracking. Typically, hydrotreating conditions
include temperatures ranging around 190–340◦ C, pressures of from about 400 psig to
about 3000 psig.
4.11 CATALYTIC DEWAXING AND ISOMERIZATION DEWAXING
Dewaxing is required to reduce the concentration of highly paraffinic oils which are
produced from PE-rich feedstocks. The higher-molecular-weight straight chain normal
and slightly branched paraffins present in such fuel cause the fuel to exhibit high cloud
points and high pour points. If adequately low pour points are to be obtained, the waxes
must be wholly or partially removed. In the past, various solvent removal techniques
were employed to remove such waxes, such as propane dewaxing and MEK dewax-
ing, however, these techniques are both costly and time consuming. Catalytic dewaxing
processes are more economical and remove the waxes by selectively cracking the longer-
chain n-paraffins. Both catalytic dewaxing and selective paraffin isomerization dewaxing
technology has been applied to plastic-derived fuels.
Because of the requirement for selectivity, dewaxing catalysts generally comprise an
aluminosilicate zeolite, having a pore size which admits the straight chain n-paraffins but
which excludes more highly branched materials, cycloaliphatics and aromatics. Zeolites
such as ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-38 have been used for
catalytic dewaxing.
Catalytic isomerization dewaxing on the other hand preferentially isomerizes the paraf-
fins, reducing the diesel pour point and cloud point while keeping the high-cetane com-
ponents in the diesel product. It also favourably decreases the boiling range of the fuel
(T95) and produces a higher mid distillate yield.
Isomerization dewaxing is carried out using a large-pore, high-silica zeolite dewaxing
catalyst such as high-silica Y or zeolite-beta which isomerizes the waxy components of
the base stock to less waxy branched chain isoparaffins. Catalytic isomerization dewaxing
uses such large pore zeolites as ZSM-22 or ZSM-23. In this process the n-paraffins
become isomerized to iso-paraffins to form liquid range materials which contribute to a
low-viscosity and low-pour-point product. Isomerization dewaxing is generally a higher-
cost process, but delivers higher yields and better properties at the same level of cloud
point reduction.
Dewaxing catalysts are manufactured by both Akzo Nobel and Mobil. Mobil’s Isomer-
ization Dewaxing (MIDW) first commercialized in 1990 uses a Pt-based zeolite catalyst
to crack and isomerize n-paraffins to iso-parrafins, thereby converting fuel oil to low-
pour-point distillates.
5 QUALITY OF THE OUTPUT FUELS
Many pyrolysis processes produce a petrol fraction with a favourable octane number, but
strong gum-forming tendency due to the presence of mainly branched olefins.
A common method of classification for petroleum is the PONA system (PONA is an
acronym for paraffins, olefins, naphthenes, and aromatics). Paraffins are straight-chain
or branched hydrocarbons in which there are no double or triple bonds between carbon
atoms. Olefins are similar to paraffins, but they contain at least one multiple bond in
their chemical structure. Naphthenes are saturated hydrocarbons, just like paraffins, but
they incorporate a ring of carbon atoms into their chemical structure. Aromatics contain
a benzene ring in their structure.
5.1 UNSATURATION
Similar to petroleum-derived cracking the fractions from plastics pyrolysis can contain
a significant concentration of unsaturated hydrocarbons (especially α-olefins) [9]. The
mono- and diolefin content makes the diesel fuel prone to instability due to polymerization
and the formation of deposits (i.e. gums). Since the plastic-derived diesel fuel has an
appreciable olefins content it is important to subject it to a hydrogenation step (e.g.
hydrogenation over Pd/Al2 O3 at 300–320◦ C and 3 MPa H2 ) which lowers the bromine
number from typical values of 22–28 g Br2 /100 g to less than 0.5 g Br2 /100 g [9].
5.2 CARBON RESIDUE IN THE FUEL
Carbon residue may be present in the diesel fuel in suspended form. The carbon residue
can be removed by ultracentrifuging. In the Smuda process some of the light layered
clays can be carried out of the pyrolysis vessel with the hot pyrolytic gases and can be
entrained in the condensed fuel.
5.3 LOW-TEMPERATURE PROPERTIES
Polyethylene-derived diesel is susceptible to waxing problems. It is not just the molecular

weight (i.e. chain length) that will cause waxing, it is the presence of linear (unbranched)
n-alkane chains (i.e. paraffins) and these are more likely to be formed from PE feedstocks.
Such straight chains can readily fold and pack tightly to form crystals.
The solubility of linear alkanes present in diesel quickly decreases with temperature.
The temperature at which the first crystals appear is called the cloud point and is one of
the most important specifications for fuels concerning their low temperature behaviour.
The utilization of a fuel is restricted to temperatures above their cloud point. Cloud point
measures the temperature at which the wax crystals form a haze. Below the cloud point,
the presence of crystals in suspension impairs the flow, plugging fuel filters. Immediately
below the cloud point the fluid stops flowing, reaching what is known as pour point. The
CFPP test measures the highest temperature at which wax separating out of a sample
400 J. SCHEIRS
can stop or seriously reduce the flow of fuel through a standard filter under standard
test conditions.
The exact temperature at which the cloud point is reached depends on the total n-alkane
content of the fuel, the average size of the n-alkane molecules, their size distribution and
chain structure (e.g. degree of branching). Conventional diesels contain as much as 20% of
long-chain n-alkanes of limited solubility in the fuel. Pyrolysis-diesels from PE feedstocks
can contain more than 40% long-chain n-alkanes. Paraffins crystallize at low temperature
into very thin rhombic plates which can clog filters, transfer lines, and pumps, and can
lead to engine failure at low temperatures.
Two processes are commonly used to produce fuels within a given specification. The
use of additives, such as cloud point depressants, and, fuel blending where a fuel with
an excessively high cloud point is mixed with a low-cloud-point fluid to produce a fuel
that meets the specifications. Most often both approaches are used simultaneously, since
cloud point depressants have a limited action.
5.4 FUEL INSTABILITY
Newly manufactured diesel fuel from waste plastics can sometimes begin to deteriorate
as soon as it is produced. Within days of the diesel fuel being produced it goes through a
repolymerization and oxidation process. This process forms sediment and ‘insoluble gums’
in the fuel caused by the unsaturated fuel molecules (i.e. reactive olefins) lengthening
and linking together. These components then drop to the bottom of the fuel storage
tanks and form a sludge. The fuel also begins to turn dark in colour and develop a
strong smell.
This will result in an increase in asphaltene agglomerations, polymerization and a dra-
matic loss of combustion efficiency. The chemistry of diesel fuel instability involves the
chemical conversion of precursors to species of higher molecular weight with limited sol-
ubility. The conversion process often involves oxidation of the precursors. Fuel solvency
plays a role, since the development of insolubles is always a function of both the presence
of higher molecular weight species and the fuel’s capacity to dissolve them.
‘Dark fuel’ is in general indicative of oxidation and is a sign that the process of fuel
degradation is in a far advanced stage. Hazy fuel is indicative of polymerization of the
fuel. These components sink to the bottom of the fuel tank and form asphaltene also
known as diesel sludge. The fuel begins to turn dark, odorous and in most cases causes
engines to smoke. The engines smoke because some of these clusters in the early stages
are small enough in size to pass through the engine filtration and into the combustion
chamber. As these clusters increase in size, only part of the molecule gets burned. The
rest exits the exhaust as unburned fuel and smoke. With increases in cluster size they
begin to reduce the flow of fuel by clogging filters.
The diesel needs to be ‘stabilized’ with diesel fuel additives that will inhibit ‘diesel
polymerization’ and inhibit oxidation, darkening and agglomeration of certain components
of the diesel. One such effective stabilizing additive is Octel FOA-6. Octel FOA-6 and
FOA-3 are amine-based antioxidants that are recommended for antioxidant protection of
distillate fuels such as diesel. FOA-3 and FOA-6 together with AO-22, generally give their
best performance when added ‘hot and early’ to the fuel, usually to a cracked component
in the run-down from the cracker.
5.5 DIESEL ADDITIVES
Additives are often required to bring the low-temperature properties of the diesel into spec-
ification. The most important parameter for measuring the low-temperature characteristics
of diesel fuel is the cloud point (or more simply, CP) which indicates the temperature
corresponding to the commencement of segregation of wax crystals representing linear
high-boiling paraffins. These crystals, particularly just after starting a diesel engine, block
the filters which protect the injection system. This causes the engine to stop, which then
requires a very elaborate procedure for its restarting.
Other significant parameters related to the low-temperature characteristics are pour point
(PP) and cold filter plugging point (CFPP). These parameters are coded and measured
by the ASTM and DIN methods and generally vary in a mutually coherent manner. The
pour point can be reduced by using additives, but these have no appreciable effect on the
cloud point.
As diesel is cooled, there comes a point at which the waxes begin to separate and
appear as a cloud or haze. The temperature at that point is known as the cloud point.
As discussed in Section 5.3, the cloud point is basically the temperature at which small
wax crystals start to form in the diesel. This is simply performed by placing the diesel
into a fridge and cooling to −5◦ C and then allowing it to come to room temperature.
The temperature at which a thermometer can be inserted into the gelled diesel is the
‘pour point’ and then the temperature at which the crystals disappear is the ‘cloud point’.
Mixing heating oil with diesel fuel has the effect of reducing the cloud point of the diesel.
For example, mixing 23 parts of heating oil to 100 parts diesel (1:4 mixture), reduces the
cloud point by 2◦ C. Kerosene may also be blended with diesel fuel to improve its low
temperature flow performance. The addition of 25 parts kerosene to 100 parts diesel will
lower the cloud point of the diesel fuel by 8◦ C. However kerosene may then bring the
flash point out of the lower specification range.
Diesel made predominantly from polyethylene has a higher proportion of paraffins and
therefore a higher cloud point. The paraffins crystallize as the temperature is lowered,
leading to small visible crystals forming in the diesel. It is these wax crystals that can
plug filters at low temperatures.
The addition of small amounts of cold flow improvers (also known as pour point depres-
sants) brings the pour point of the diesel into the normal range. This can be achieved for
example by addition of 1000 ppm of Callington Haven Roxdiesel Pour Point Depressant.
It has been found that additives such as pour point depressants can lower the pour
point, but not the cloud point. It has been found empirically that styrene monomer can
lower the cloud point since the paraffinic wax crystals are more soluble in the styrene
than in the diesel. Styrene monomer is proposed as a suitable additive to depress the
cloud point.
5.6 STORAGE STABILITY OF PLASTIC-DERIVED DIESEL FUEL
As diesel ages a fine sediment and gum forms in the fuel brought about by the reaction
of diesel components with oxygen from the air. The fine sediment and gum will block
fuel filters, leading to fuel starvation and engine failure. Frequent filter changes are then
402 J. SCHEIRS
required to keep the engine operating. The gums and sediments do not burn very efficiently
in the engine and can lead to carbon and soot deposits in injectors and other combustion
surfaces.
Diesel fuel made from the thermal cracking of plastics is more susceptible to oxidation
and polymerization than refinery-made diesel fuels. This is because plastic-derived diesel
fuels generally have terminal unsaturation (i.e. double bonds) at the ends of the diesel
chains as a result of the β-scission chain cleavage. Over time free radicals that form in
the plastic-derived diesel fuels during storage cause the diesel chains with double bonds
(α-olefins) to polymerize resulting in a sludgy sediment also known as ‘gum’.
Factors which decrease storage life of diesel:
• fuel composition, especially the presence of olefins and styrene monomer in the plastic-
derived fuel;
• exposure to high temperatures;
The ageing process can be accelerated by the following conditions:
• contact with zinc, copper or metal alloys containing them. These metals will quickly
react with diesel fuel to form unstable compounds;
• exposure to dust and dirt containing trace elements, that can destabilize the fuel (such
as copper and zinc).
The expected life of a diesel fuel is indicated by the oxidation stability test (ASTM D-
2276). The test measures how much gum and sediment will be deposited after conditioning
the fuel at 120◦ C in the presence of oxygen for 16 h. It roughly corresponds to a years
storage at 25◦ C. A result of less than 20 mg/L of sediment and gum after the test is
considered acceptable for normal diesel.
In order to improve the stability of synthetic diesels and biodiesels it is necessary
to add free-radical trapping additives known as antioxidants (such as DTBHQ, IONOX
220, Vulkanox ZKF, Vulkanox BKF, and Baynox). Butylated hydroxy toluene (BHT) in
particular prevents oxidation and radical polymerization reactions that can lead to diesel
fuel ageing.
The nominal antioxidant concentration required to give diesel fuel an extended storage
stability and suppress polymerization, is 1000 ppm (i.e. 1000 mg/kg).
HSD Stabilizer (Diesel Stabilizer) additive is a multicomponent, oil soluble formulation,
specially designed to maintain the total sediments level in diesel fuel within the specified
limits, as per ISO 1460:1995. The additive will ensure that the diesel does not deteriorate
on storage and the fuel system is protected from deposit formation and corrosion. The
additive consists of three major components, namely:
Antioxidant. Fuel oils are subject to deterioration due to oxidation and this occurs both
during storage and in service. Oxidation gives rise to formation of gums and sludge.
Olefinic compounds produced by cracking are more susceptible to oxidation. Gum is the
product of a series of oxidation and polymerization reactions. Antioxidants function by
combining with peroxide free radicals and by decomposing hydroperoxides into stable
substances. The antioxidants used in the additive are a combination of sterically hindered
phenol-type antioxidants.
Detergent. The detergent and dispersant, keeps oil insoluble combustion products in
suspension and also prevents resinous-like oxidation products from agglomerating into
solid particles. Thus they prevent formation of deposits on metal surfaces, oil thickening
and sludge deposition. The component used is ethoxylated products of alkyl phenols.
Metal deactivator. Metal deactivator prevents precipitation of metal ion oxidation reac-
tions and precipitation of insoluble metal compounds. Metal deactivator in combination
with other antioxidants, shows strong synergistic effects. Oxygen and moisture present,
diffuse through oil film and cause corrosion. Amine derivative, used in the additive has
good water-displacing properties. They impede sludge formulation, disperse sediments
and reduce corrosion in various fuel systems.
5.7 CHARACTERISTICS OF THE SOLID RESIDUE
The carbonaceous coke formed during plastics pyrolysis is automatically scraped off and
accumulates in the bottom of the pyrolysis chamber where it is reduced by attrition to a
free-flowing black powder. The internal agitator/scraper constantly removes the carbona-
ceous char by-product before it acts as a thermal insulator and lowers the heat transfer to
the plastic. The char residue produced is about 2–3% of the output for relatively clean
polyolefin feedstocks and up to 8–10% for PET-rich feedstocks.
It is difficult to generalize about the chemical composition of the coke stream, since
it is directly dependent on the composition of the feedstock stream, which of course
varies from one location to another. It is to be expected however that the char stream
from a mixed plastic packaging feedstock will be rich in the following elements: Cr, Cd,
Mn, Co, Fe, etc., since compounds containing these metals are used in additives (such
as pigments and catalysts) used in commodity plastics. The carbon matrix has a metal
‘fixing’ effect and binds up the metal ions so that limited leaching occurs after disposal.
The leachability potential of the coke (known as TCLP) needs to be determined before
the coke can be landfilled. TCLP stand for toxicity characteristic leaching procedure.
The TCLP provides a means to determine the potential for waste leaching in a landfill
environment.
5.8 GASEOUS EMISSIONS
Ammonia (NH3 ) and other nitrogen-containing compounds in the fuel gas can lead to
the emission of the oxides of nitrogen (NOx ) in the combustion product gases. Ammonia
is a potential product in all pyrolysis processes whenever protein materials are being
processed. Proteins are collections of amino acids that contain small quantities of the
amine group (NH2 ) attached to a carbon atom. The nitrogen in amino acids would be
the ‘fuel nitrogen’ for protein material if it were used directly as pyrolysis feedstock. A
portion of these amine groups will convert to ammonia during the pyrolysis process and
thus can be released into the fuel gas. The most common way to treat the fuel gas in order
to remove ammonia is to scrub it with water at modest temperature conditions. There can
also be sulphur in the feedstock used for pyrolysis. In the normal range of temperatures
for pyrolysis processes, only a portion of the sulphur is released into the fuel gas. Most
of this sulphur is in the form of hydrogen sulphide (H2 S) that can be removed by an
alkaline scrubbing of the fuel gases.
404 J. SCHEIRS
6 CATALYTIC CRACKING
6.1 CATALYST ACTIVITY AND SELECTIVITY
Zeolite catalysts produce liquid products with a boiling point distribution in the range
of motor engine fuels. The acidic zeolite catalysts (HZSM-5, H-ultrastable Y-zeolite
(H-US-Y)) are more effective in converting polyolefins than the less acidic, amorphous
silica–alumina and mesoporous MCM-41. There are considerable differences in product
selectivities among the various catalysts. For instance, nanosized HZSM-5 zeolite (with
high external surface area and strong acid sites) promotes end-chain scission reactions of
the polyolefins, producing mainly light hydrocarbons (C3 -C6 ); while heavier products are
obtained over mesoporous HMCM-41. Thus indicating that random scission reactions are
predominant as a result of the large pores and mild acidity of this material. From a com-
mercial perspective, the cheaper silica–alumina catalyst give very good selectivity, and
their lower activity can be compensated for by increasing the catalyst to polymer ratio.
The larger pore zeolites (H-Y) show rapid deactivation in contrast to the more restrictive
HZSM-5 and the non-zeolitic catalysts (silica-alumina, MCM-41), since coke deposits can
accumulate inside the channel system of large pores. In contrast, coke deposits only on
the outer surface of the zeolites having narrow pores. Furthermore the catalysts having
weaker acid sites of lower density are better at tolerating coke deposition. For instance,
the mild acidity of clays (and their pillared versions, e.g. pillared montmorillonite) show
good resistance to deactivation by coking.
Walendziewski [10] has reported that the optimum thermal cracking temperature of
waste polyolefins is 410–430◦ C, whereas in the case of catalytic pyrolysis, lower tem-
perature (e.g. 390◦ C) can be used. Higher than 90% yield of gas and liquid fractions with
bp <360◦ C was attained.
Manos [11] studied the catalytic degradation of high-density polyethylene to hydrocar-
bons over different zeolites. The product range was typically between C3 and C15 hydro-
carbons. Distinctive patterns of product distribution were found with different zeolitic
structures. Extra large-pore ultrastable Y-, and β-zeolites, alkanes were the main prod-
ucts with less alkenes and aromatics and only very small amounts of cycloalkanes and
cycloalkenes. Medium-pore mordenite and ZSM-5 gave significantly more olefins. In the
medium-pore zeolites, secondary bimolecular reactions were sterically hindered, resulting
in higher amounts of alkenes as primary products. The hydrocarbons formed with medium-
pore zeolites were lighter than those formed with large-pore zeolites. The following order
was found regarding the carbon number distribution: (lighter products) ZSM-5 < mor-
denite < β < Y < US-Y (heavier products). A similar order was found regarding the
bond saturation: (more alkenes) ZSM-5 mordenite < β < Y < US-Y (more alkanes).
The catalytic cracking of polypropylene waste in a fluidized-bed reactor was reported
by Ji [12]. It gave a yield of liquid product of 50%, the research octane number of the
gasoline produced from plastic waste was 86, and the cetane index of the diesel fuel
produced from the plastic waste was 43.
Modification of ZSM-5 zeolite can result in improved liquid yields and a doubling of the
isoparaffin index of the liquid fuels which indicates higher liquid quality compared with
the parent ZSM-5 zeolite. The high catalytic activity of modified ZSM-5 was explained
by its unique acidic properties with a sharp increase of the number and strength of weak
acid sites and a decrease of strong acid sites [13].
A major shortcoming of zeolite-type catalysts is their sensitivity to hydrogen chloride
and HCl acid, which causes destruction of a catalyst in concentrations above 200 ppm
HCl. Considering the fact, plastic wastes often contains PVC the application of expensive
zeolite-type catalysts is disadvantageous.
6.2 LAYERED CLAY CATALYSTS
A layered silicate clay framework with ordered nickel (or iron) atoms inside can be
used as an effective cracking catalyst. Manos [14] showed that two natural clays and
their pillared analogues were able to completely decompose polyethylene although these
clays were found to be less active than US-Y zeolite their yields to liquid products
were around 70%, compared with less than 50% over US-Y zeolite. Moreover, the liquid
products obtained over the clay catalysts were heavier. Both of these facts are attributed
to the milder acidity of clays, as the very strong acidity characterizing zeolites leads to
‘overcracking’. Furthermore, this milder acidity leads to significantly lower occurrence of
hydrogen transfer secondary reactions compared with US-Y zeolite, and as a consequence,
alkenes were the predominant products over the clay catalysts. An additional advantage
of these catalysts is the considerably lower amount of coke formed.
Another important group of catalytic compounds contain the layered double hydroxides
(sometimes called ‘anionic clays’ or ‘hydrotalcites’). Presently, many researchers study
these materials because of their adsorptive and catalytic properties.
Unlike thermal cracking, the use of catalysts requires less energy and forms valuable
hydrocarbons in the gasoline and diesel ranges, thus eliminating the requirement for further
processing.
Tu et al. [15] report on the catalytic cracking of low-density polyethylene (LDPE) over
three types of base catalysts based on layered double hydroxides (LDH) [15]. LDH con-
stitutes a class of layered compounds, resembling the naturally occurring hydrotalcite,
and are generally considered complementary to the clays in that they contain positively
charged layers and anions in the interlamellar space. Due to the relative ease of their
synthesis, LDHs represent an inexpensive and versatile source of a variety of solid cat-
alysts [16]. The catalytic cracking of low-density polyethylene (LDPE) over the three
LDHs (MgAl, NiAl, and ZnAl) was examined at 350 and 400◦ C. The catalytic activi-
ties and product distributions obtained with these materials were compared with those
corresponding to thermal cracking and cracking over acid solid HY-Zeolite catalyst. All
cracking reactions were performed by a semi-batch operation with polymer to catalyst
ratio of 100:1. Volatile hydrocarbons were collected from a stream of inert helium gas.
Both liquid and gaseous products were analysed by gas chromatogram [15].
At 350◦ C, the thermal cracking of low-density polyethylene was almost negligible
(<1% conversion). The final product after the reaction was that of the melted LDPE,
showing that the thermal degradation of LDPE at 350◦ C was very slow. In all experi-
ments at 400◦ C, the initial LDPE was totally converted to liquid product, gaseous product,
wax and coke. At 400◦ C, catalytic cracking of LDPE over LDH catalysts showed higher
cracking activity than thermal cracking. The liquid yields are: 40 wt% wt. for NiAl,
38 wt% for ZnAl-, 27 wt% for MgAl and 20 wt% for purely thermal cracking. NiAl and
ZnAl-LDHs proved to have better potential catalytic properties for LDPE cracking rather
406 J. SCHEIRS
than MgAl-LDH. Solid HY acid catalyst was also tested to compare the performance of
the LDHs. HY showed similar activity with NiAl and ZnAl-LDH. However, being more
basic in nature, LDHs produced heavier hydrocarbon liquid than the HY. The order was
as follows: (lightest products) HY-Zeolite < NiAl < ZnAl < MgAl < thermal only (i.e.
no catalyst) (heaviest products). In addition, LHDs showed less coking than their HY
counterpart, this is due to the negligible or nonoccurrence of hydrogen transfer secondary
reactions. HY showed a high level of isobutane production, which is indicative of high
level of secondary reactions. The production of isobutane however decreased considerably
as the cracking process progressed, hence HY showed rapid deactivation [15]. Further-
more, all reactions produced considerably lower gaseous products (less than 5 wt%). This
is of great benefit as gaseous products are considered less superior to the more valu-
able liquid product. It was concluded that NiAl and ZnAl LDHs proved to be promising
candidates for the catalytic cracking of polyethylene. Catalytic cracking of LDPE over
these two catalysts produced a high level of valuable hydrocarbons liquid, with very little
gaseous product and coke [15].
6.3 EXTERNAL CATALYSTS
A major problem with using catalysts in the pyrolysis of mixed plastics is that of coke
formation, which gradually deactivates the catalyst. For this reason the catalyst is often
positioned outside the main pyrolysis reactor such as in a second reactor where the pyrol-
ysis oil is upgraded over a suitable catalyst (e.g. zeolite HZSM-5 or Ni-supporting rare
earth metal exchanged Y-type zeolite (REY)) in order to obtain a high quality gaso-
line. For instance a two-stage catalytic degradation of polyethylene using amorphous
silica–alumina and HZSM-5 zeolite catalysts in series has been developed for converting
the polymer into high-quality gasoline-range fuels. Firstly the silica–alumina catalyzes
the degradation of polyethylene into a low quality pyrolysis oil, which is then transformed
into high-quality gasoline on the strongly acidic sites of the zeolite.
6.4 PS CATALYTIC CRACKING
Thermal cracking and catalytic degradation of polystyrene (PS) at 375◦ C over HZSM-5
catalyst yields mainly styrene (over 50 wt% yield). On the contrary, the main products
resulting from the catalytic cracking over HMCM-41 and SiO2 -Al2 O3 are benzene, ethyl-
benzene and cumene, but in proportions lower than 20 wt% [17]. The results obtained
over HZSM-5 zeolite are attributed to both its microporous structure and acid features.
The external acid sites of the HZSM-5 zeolite are practically the only ones active for
PS degradation, since this polymer is too bulky to enter the zeolite micropores. In addi-
tion, competitive cross-linking reactions also take place, which are highly promoted by
the strength and Brönsted nature of the zeolite acid sites. Finally, the superior activity
obtained over HMCM-41 is explained in terms of its uniform mesoporous structure and
its medium acid strength [17].
Similarly the fluidized-bed pyrolysis of polystyrene in the presence of fluid catalytic
cracking (FCC) catalysts was investigated at temperatures between 370 and 515◦ C [18]. In
the catalytic pyrolysis of polystyrene, the product distribution is changed from the usual
main product styrene (61 wt%) (in noncatalytic experiments with simple quartz sand)
to feedstock chemicals (18–26% ethylbenzene, 9–22 wt% benzene: 1–7 wt% styrene,
3–5% toluene) and coke (15–23 wt%).
6.5 CATALYTIC DECHLORINATION
Waste-plastic-derived oil that was prepared by thermal degradation of municipal waste

plastics at 410◦ C was dehydrochlorinated to remove chloroorganic compounds using var-
ious catalysts such as iron oxide, iron oxide–carbon composite, ZnO, MgO and red mud.
The iron oxide catalysts were effective in removing the chloroorganic compounds. MgO
and ZnO catalysts were deactivated during the reaction by HCl, which is produced by the
dehydrochlorination of chloroorganic compounds. Iron oxide and its carbon composite
were found to be stable in the dehydrochlorination of municipal waste plastic derived
oil [19].
A red mud catalyst (waste from alumina production) was evaluated as both a cracking
and dechlorination catalyst for the catalytic degradation of PVC-containing mixtures (such
as PVC/PE, PVC/PP and PVC/PS) by [20]. Using stepwise pyrolysis, over 90% chlorine
in the feed plastic was recovered as HCl gas. A silica–alumina catalyst accelerated the
rate of polymer degradation and lowered the boiling point of liquid products, but the
chlorine content of oil over silica-alumina was also the highest. Red mud and iron oxides
sorbents showed good effect on the fixation of evolved HCl however, they had no effect
on the cracking of polymers.
7 COMMERCIAL PLASTIC PYROLYSIS PROCESSES
7.1 THERMOFUEL PROCESS
In the Thermofuel process, plastic waste is first converted to the molten state and
then ‘cracked’ in a stainless steel chamber (Figure 15.5) at temperatures in the range
350–425◦ C under inert gas (i.e. nitrogen). The hot pyrolytic gases are condensed in a
specially designed two-stage condenser system to yield a hydrocarbon distillate comprising
straight- and branched-chain aliphatics, cyclic aliphatics and aromatic hydrocarbons. The
resulting mixture is essentially equivalent to regular diesel. A process flow diagram of
the Thermofuel process is shown in Figure 15.6.
The essential steps in the Thermofuel pyrolysis of plastics involve:
• uniformly heating the plastic within a narrow temperature range without excessive
temperature variations;
• ensuring the plastic is homogeneous and stirred to prevent hot-spots;
• excluding oxygen from pyrolysis chamber, yet at the same time allowing rapid egress
of the hot pyrolytic vapours;
• constantly removing the carbonaceous char by-product before it builds up on the
pyrolysis chamber walls and acts as a thermal insulator, thereby lowering the heat
transfer to the plastic;
408 J. SCHEIRS
Figure 15.5 Close-up of pyrolysis chamber of commercial plastics pyrolysis plant which
can convert 10 tonne of unwashed, mixed plastics into 10 000 L of diesel fuel per day.
(Reproduced by permission of Ozmotech Pty Ltd)
• reactive distillation, which means the hot pyrolytic vapours can condense and be
returned to the main pyrolysis chamber until the correct carbon chain length is
achieved;
• careful condensation and fractionation of the pyrolysis vapours to produce diesel of
good quality and consistency.
The core technology of the Thermofuel process is the catalytic reaction tower (or
catalytic converter, Figure 15.7). The catalytic reaction tower contains a system of plates
made from a special catalytic metal alloy. The metal plates are positioned so that the hot
pyrolytic gases must travel a tortuous path, in order to maximize contact area and time.
The catalyst chamber is heated to 220◦ C using the exhaust gases (not pyrolysis gases)
from the furnace of the pyrolysis chamber.
The metal catalyst ‘cracks’ paraffinic chains longer than C25 and ‘reforms’ chains
shorter than C6 . This is especially important to convert the α-olefin chains (1-alkenes) to
saturated alkanes. The catalyst ensures that the final fuel has a carbon chain distribution
in the range C8 –C25 peaking at C16 (cetane) (Figure 15.8). The catalytic tower uses tech-
nology borrowed from the petrochemical industry for the hydrogenated of C=C double
bonds, e.g. Raney Nickel or so-called Adams catalyst.
The catalyst is not consumed or poisoned, unlike zeolite type catalysts. The metal
plates do however get fouled with a tar-like residue and terephthalic acid and therefore
the reaction tower needs to be stripped down periodically and the plates polished back to
their pristine form.
Condensers
Cooling pump
Nitrogen 3rd condenser

flow line (scrubber)
Reaction
tower
Nitrogen
monitoring
device
COMMERCIAL PYROLYSIS PROCESSES
Off-gas burner
Alkali dosing
Main Burner tank
chamber Water
Oil recovery tank
Furnace tank
Warm water Reserve

tank tank
Centrifuge Fuel outflow
line
Figure 15.6 Process flow for commercial pyrolysis plant (Thermofuel) for converting waste plastics into diesel fuel. The plastic
is heated to 375–425◦ C and the pyrolysis vapours are catalytically cracked and then selectively condensed. Note that the pyrolysis
vessel is purged with nitrogen gas and that the hot pyrolytic vapours pass from the pyrolysis vessel to the catalytic reaction tower
where they are cracked and reformed to give a high-purity diesel stream. (Reproduced by permission of Ozmotech Pty Ltd)
409
410 J. SCHEIRS
Figure 15.7 Close-up of catalytic reaction tower and condensers of the Thermofuel
process. (Reproduced by permission of Ozmotech Pty Ltd)
HP GC 02389 refdal.d. Channel A: 0.000 to 53.989 Min.

C15
C14 C16
5.6
5.5 C17
5.4 Diesel
5.3
5.2 C18
5.1
5.0 C13 C19
4.9
4.8
4.7
4.6
4.5 C20
4.4
4.3
4.2 C12
4.1
4.0
3.9
Y (× 10^6)
3.8 C21
3.7
3.6
3.5
3.4 C11
3.3
3.2
3.1 C22
3.0
2.9
2.8
2.7
2.6 C10
2.5 C23
2.4
2.3
2.2
2.1
2.0 C24
1.9
1.8 C25
1.7
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
Min
C8 HP GC 023891.d. Channel A: −0.136 to 54.152 Min.
4.9
4.8
4.7
4.6
4.5
4.4 C13
4.3
4.2
4.1 Sample A
4.0
3.9
3.8
3.7
C9
3.6
3.5
Y (× 10^6)
3.4
3.3 C11
3.2
C15 C16 C17
3.1
3.0 C14 C18
2.9 C19
C20
2.8
2.7
C21
2.6
2.5 C22
2.4 C10
2.3 C23
2.2 C12
C24
2.1
2.0 C25
1.9
1.8
1.7
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40
Min
Figure 15.8 Gas chromatogram (GC) of regular diesel (upper) and plastic-derived diesel
(lower). The regular diesel exhibits a series of regular hydrocarbon with a normal dis-
tribution peaking close to C16 (cetane). The plastic-derived diesel was produced by the
Thermofuel process (before fractionation) from a mixture of polyethylene, polypropylene
and Nylon film as feedstock. This fuel sample also exhibits regularly spaced, hydrocar-
bon peaks approximating a normal distribution and peaking at C16 and concluding at
approximately C30 . Also apparent are large peaks at C8 (octane), C9 and C11 . Collec-
tively these additional peaks are ‘light’ hydrocarbons. ‘Lights’ are defined as paraffins
or carbon chains with a length less than C11 , that is, less than 11 carbon atoms long.
(Reproduced by permission of Ozmotech Pty Ltd)
The catalyst chamber is the heart of the Thermofuel process and is directly responsible
for the high quality of the output fuel from this process. The technology in and around
this unit is highly proprietary since competitive processes do not have this type of long-
life catalytic converter. Many other pyrolysis processes add zeolite catalysts directly to
the pyrolysis chamber, however, these are expensive and quickly become fouled and
deactivated.
A single-chamber demonstration plant in Fujioka City, used for running trials and
process development, has been operational since 1996. Inspection of the inside of the
412 J. SCHEIRS
main pyrolysis chamber during a shut-down showed it to be in excellent condition with
minimal scoring or corrosion.
A twin-chamber Thermofuel plant at the Totai Company in Yamanashi Province has
been in operation since 2002. The plant at this site processes post-industrial plastic pack-
aging film based mainly on polyethylene, polypropylene and nylon. The plant operation
is highly automated.
A twin-chamber Thermofuel plant at an agricultural cooperative on the island of Oki-
nawa has been in operation since 2003 (Figure 15.9). This plant processes agricultural
Table 15.4 Thermofuel plants in Japan
Location Description Started

Totai Dual chambers, mixed plastics 2002
Okinawa Dual chambers, agricultural film 2003
Nakamoto One chamber, similar to Totai (mix plastics) 2004
Watanuki Dual chambers, commercial and industrial 1993
waste(recycling)
Tih-Tay Dual chambers, polyethylene from cables 1998
(cross-linked EVA)
Nabari One chamber, industrial waste (packaging) 2004
Fujioka Original pilot plant Now disassembled
Figure 15.9 A commercial Thermofuel plant in Okinawa in Japan which processes

agricultural plastics such as mulch and greehhouse films into diesel fuel to run green-
house boilers for heating, tractors and other agricultural machinery. (Reproduced by
permission of Ozmotech Pty Ltd)
plastics such as mulch and greenhouse film based mainly on polyethylene. The diesel fuel
is used to run greenhouse boilers, tractors and other farm equipment.
Thermofuel-based fuel produces much lower sulphur oxides (SOx ) than conventional
diesel since sulphur levels in the fuel are typically less than 0.01% (100 ppm) as compared
with conventional diesel which has sulphur around 400–500 ppm. SOx emissions for
Thermofuel diesel are thus correspondingly 4–5 times lower than that of conventional
diesel. Furthermore the Thermofuel incorporates an integrated desulphurization plant to
ensure the sulphur content of the diesel produced is always within specification.
Nitrogen oxides (NOx ) emissions from diesel engines run on Thermalysis fuels evalu-
ated at 3000 rpm was found to vary with the load on the engine [21] (Table 15.5)
Generally, the Thermofuel fuel gives lower NOx than conventional diesel, especially at
lower engine load. Particulate emissions from diesel engines run on Thermofuel diesel,
also at 3000 rpm, varies with the load on the engine [21] as shown in Table 15.6.
It is apparent from the above data that Thermofuel diesel produces significantly less par-
ticulates (smoke) at all engine loadings than conventional diesel. This is environmentally
significant, as the particulates formed from diesel combustion contain polycyclic aromatic
hydrocarbons (PAH) which have carcinogenic potential. The hotter burning characteristic
of the Thermofuel relative to conventional diesel is likely to be responsible for the better
burn-out of particulates [21].
In the Thermofuel process the first reaction occurs in the pyrolysis chamber where the
plastic is thermally pyrolyzed, causing random scission of carbon chain lengths. While
secondary reactions occur in the catalytic converter (i.e. catalyst tower) where shorter
carbon chains are reformed and further cracking of longer carbon chains occurs such
Table 15.5 Nitrogen oxides (NOx ) emissions from Thermo-

fuel diesel as compared with conventional diesel
Engine load NOx (ppm) NOx (ppm)

(Thermofuel fuel) (conventional diesel)
1/5 90 150
2/5 180 215
3/5 300 330
4/5 420 400
5/5 500 450
Table 15.6 Particulate engine emissions from Thermofuel diesel

as compared with conventional diesel
Engine Load Particulates % Particulates %

(Thermofuel fuel) (conventional diesel)
1/5 0 0
2/5 0 2
3/5 5 17
4/5 22 40
5/5 43 70
414 J. SCHEIRS
that the carbon chain length distribution in the range from C8 to C25 and peaking at C16
(cetane) is achieved.
In the Thermofuel process, carbon and coke deposits formed during the pyrolysis are
continuously scraped from the pyrolysis chamber walls and reduced to a free-flowing
black powder. Inorganic additives such as cadmium pigments from the plastics also end
up in the char stream. The carbon matrix has a metal ‘fixing’ effect and binds up the
metal ions so that no leaching occurs after disposal.
The noncondensable gas from the pyrolysis reactor is scrubbed of acidic gases in a
water scrubber and then burnt in a noncondensable gas burner. The typical emissions
from this burner are as follows:
Emission type Value

SOx <5 ppm
NOx 198 ppm
Dust density 0.06 g/cm3
Temperature 438◦ C
Water vapour 13%
The above emissions data is for the Totai plant in Japan running a mix of PE (43%),
PP (40%) and nylon (17%).
7.2 SMUDA PROCESS
The Smuda pyrolysis process developed by Dr Heinrich W. Smuda (Figure 15.10a) is

a continuous process where the mixed plastic feedstock is fed from an extruder into a
stirred and heated pyrolysis chamber [22, 23]. The extruder acts as an airlock to exclude
oxygen and also to preheat and melt the polymer, so less energy input is required in the
main chamber. The pyrolysis vessel operates at a constant level of 60% and the headspace
is purged with nitrogen gas. A layered silicate catalyst (5–10% by vol) is added to the
plastic melt to give a catalytic cracking reaction [24]. The fuel from the Smuda process
is both transportation-grade diesel (85%) and gasoline (15%). The gasoline produced by
the process is used in a cogenerator to produce electricity for the process. The diesel has
an average olefin content of 10%, a flash point of 70◦ C and a pour point of −40◦ C. Since
the diesel produced catalytic cracking contains approximately 10% olefin and inhibitor
such as 0.01% BHT is required to suppress polymerization and gum formation [24].
The original Smuda Process is covered by a United States Patent entitled ‘Method
of obtaining liquid fuels from polyolefine wastes’ [22]. The process charges a non-
zeolite metal silicate catalyst directly into the main reactor which reduces the energy
level required to scission the carbon chains of plastics and produces superior and stable-
quality hydrocarbon products. In contrast to fluidized-bed pyrolysis processes, the Smuda
process requires less capital investment and less operating cost. Pyrolytic vapours of the
molten plastic are condensed in a cooler and then separated on a distillation column to give
transportation-grade diesel. The diesel product (the fraction with boiling point in the range
170–300◦ C) shows very good low-temperature properties such as a cloud point and cold
filter blocking temperature (CFPP) of −45◦ C and also very high cetane number of 65 [22].
Figure 15.10 (a) Photograph of the inventor of the Smuda Process, Professor Heinrich
Smuda (right) and the editor Dr John Scheirs (left). (Copyright  J. Scheirs). (b) Pho-
tograph of Smuda stirred-tank reactor (left) and bottom of distillation column (right).
(Copyright  J. Scheirs)
416 J. SCHEIRS
Nickel silicate and ferrous silicate are the preferred catalysts in the Smuda process. The
Smuda catalyst is a layered silicate clay framework with ordered nickel (or iron) atoms
inside. The catalyst is charged at 10 wt% ratio of the plastic feedstock. The catalysts are
based on layered silicates with Lewis acid activity [24]. Catalytic cracking results in very
little noncondensable gas (<1%) and minimal carbonaceous char. The life of the Smuda
catalyst is approximately 1 month [24].
Natural minerals and ores containing transition metal ions, steelmaking slags or metal
plant wastes can be used as catalysts or sensitizers in the plastic material cracking. These
materials include Ni2 O3 , NiO, Fe2 O4 and Co2 O3 .
A number of low-grade transition metal ores (for example, minerals containing nickel
oxides) can be used as catalysts. Smuda has demonstrated that microwave or radiofre-
quency irradiation of a mixture of such ores with a carbon source initiates reduction of the
oxide to metal. With this approach, poisoning the active sites of the catalyst will not be crit-
ical for the process since there will be a constant supply and generation of active catalyst
with the feed material. In addition to well-known catalytic properties of nickel in organic
reactions, it was also shown that Ni on carbon and other supports, catalyzes hydrodechlo-
rination and dehydrochlorination of chlorinated organic waste streams [22–24].
The Smuda process also uses new cracking catalysts based on cobalt resinates which are
cobalt salts of resin acids (mainly abietic acid) such as cobalt abietate and cobalt linoleate
(these are commonly referred to as driers in the coatings industry) and preferably with
admixtures of heavy metal silicates. Smuda has also explored the use of manganese
resinate deposited on an aluminium oxide support to maximize active surface area [23].
In the Smuda process the pyrolysis reactor temperature is 350◦ C and the operating
pressure is 4–5 psi. The pyrolysis gases from the pyrolysis vessel are sent directly to a
distillation column. The distillation column has a typical temperature profile as follows:
top 140◦ C, Sulzer 250Y; middle 322◦ C, Sulzer 350Y and bottom 331◦ C.
The melt is stirred with an agitator running at 30 rpm to keep the catalyst in suspension.
The torque on the agitator is monitored to determine the level of inorganic impurities and
carbon residues that have accumulated. At a preset torque level the polymer melt is
completely pyrolyzed and the carbon residues and impurities are then evacuated from
the chamber using an auger positioned in the base of the vessel. Char removal is only
activated when the vessel is cooled.
The Smuda catalysts, due to their acidic nature, have a low tolerance to alkaline com-
pounds. Accordingly Nylons (which form ammonia) and ABS (which form amines) are
not suitable since these polymers form by-products which are alkaline in nature. PVC
does not pose a problem since the acidic by-products do not deactivate the catalyst [24].
Due to the sensitivity of the catalyst, the Smuda process requires that the plastic feed-
stock be pre-processed and cleaned by mechanical processing (i.e. other than washing). In
this way dirt, food impurities, etc. can be removed before they deactivate the catalyst [24].
An additional problem with the powdered silicate catalyst in the polymer melt is that
carryover (i.e. entrainment) of fine catalyst particles into the diesel stream can occur.
Advantageously, the Smuda Process can tolerate high levels of PET. In catalytic pyrol-
ysis the terephthalic acid is decarboxylated to give benzoic acid and benzoates [24] (see
also Figure 15.3). PET gives fuel with appreciable aromatic content (e.g. level of 10% or
higher). In other competitive processes PET proves problematic due to the formation of
troublesome terephthalic acid (TPA) deposits in the downstream pipework and condensors.
The Smuda process uses a reflux return where longer paraffin chains that condense
shortly after exiting the main chamber are allowed to flow back to the main chamber (the
‘reflux effect’). Also the heavies from the bottom of the distillation column flow back to
the pyrolysis chamber for re-cracking (Figure 15.10b).
In 1997, the world’s largest catalytic cracking plastics recycling plant began operation
by AgRob EKO, S.A. in Zabrze, Poland. The plant has six cracking reactors each with
a volume of 20 m3 and equipped with agitators and internal heat exchangers. The reac-
tors are run in a semi-continuous mode and after cracking approximately 60 tonnes of
waste plastic and spent lubrication oil, they are stopped for cleaning and coke removal
by scraping the internal heat-exchanging surfaces of the reactor. Since the plant runs a
catalytic cracking process with silica alumina catalysts, coke formation is minimized (as
compared with thermal cracking). In 2000, Dr Smuda began an association with a South
Korean company to develop the Smuda Process, - an integrated process for catalytically
converting post-consumer plastics into gasoline and low-sulphur diesel fuel.
7.2.1 Specific Advantages of the Smuda Process

• The process is continuous.
• Vessel is filled with 60% plastic melt and the level is maintained there using a level
sensor.
• Excellent temperature uniformity and control of pyrolysis vessel (chamber is heavily
insulated).
• Solid residue (coke) removal is automatic (by auger).
• Fractionation column ensures the boiling point range of liquid outputs.
• Liquid yield is high (95%) due to low temperatures used (350–370◦ C).
• Heavies from fractionation column are re-fed to reactor.
• Process also incorporates a diesel side-stripper, gasoline stabilizer and fuel dechlori-
nator.
• The process uses a ‘catalytic isomerization dewaxing’ step to preferentially isomerizes
the paraffins, thus reducing the diesel pour point and cloud point while keeping the
high-cetane components in the diesel product.
• Rapid stirring of the melt (30 rpm) ensures proper catalyst distribution and dispersion
as well as satisfactory heat distribution
7.2.2 Specific Shortcomings of the Smuda Process

• Catalyst is consumable and hence has an associated operating cost (∼ US$20/kg).
• Impurities and dirt in feedstock dramatically shorten catalyst life.
• Process requires feedstock pre-processing in order to remove impurities.
• Catalyst is charged into reactor monthly with catalyst activity decreasing over time.
• Catalyst is acidic and is especially deactivated by Nylons and other polymers that
produce alkaline (i.e. basic) by-products.
• Catalyst type (there are some 20 to choose from) is determined by the composition
of the feedstock.
• The only indication of catalyst deactivation is a gradual deterioration in diesel quality.
418 J. SCHEIRS
• The above situation necessitates frequent quality control checks on the diesel.
• There is no centrifuge in the process to remove water and carbon residues from the
diesel.
• Close proximity of multiple heating pipes in larger reactors renders them prone to
coking and fouling.
• The diesel fuel has 10% α-olefin content (i.e. terminal unsaturation or double bonds)
which make the fuel unstable and prone to polymerization (i.e. sludge formation).
• There is no proven track record for producing transportation-grade diesel from the
Smuda Process (Poland plant produces crude oil from plastics which is subsequently
sent to a refinery).
7.2.3 Similarities of the Smuda Process and the Thermofuel Process

• Both use a stirred tank reactor.
• Both use a paddle agitator that also serves to prevent coking.
• Both are fed with molten plastic from an extruder.
• Both use nitrogen purging before the pyrolysis begins.
• Both use low temperature pyrolysis (350–425◦ C).
• Both employ a reflux philosophy where ‘heavies’ are sent back to the reactor for
further cracking.
• Both produce predominantly diesel, along with gasoline, some LPG and a coke residue.
7.3 POLYMER-ENGINEERING PROCESS (CATALYTIC DEPOLYMERIZATION)
A catalytic diesel process (Figure 15.11) is being offered by a German company called
Polymer-Engineering (Bielefeld, Germany). The process was developed by Alphakat
GmbH (Buttenheim, Germany) and Siemens and is described in German Patent DE 100
49 377 C2 by the inventor Dr Christian Koch. The process which has been trademarked as
NanoFuel Diesel produces high-grade stabilized diesel fuel from waste plastics. Further
information can be found at <http://www.globalfinest.com/tech/>. The process converts
waste plastics by catalytic depolymerization at 270–370◦ C in the presence of an ion-
exchanging catalyst (disclosed as a crystalline, highly active Y sodium aluminosilicate
zeolite catalyst). The composition of the end products of the catalytic depolymerization is:
• liquid fuel (diesel) 93–95%
• noncondensable gas 4–5%
• residue <1%
The process uses hot oil (high boiling bunker oil) as the pyrolysis medium to ensure
good thermal conductivity and eliminates the need for an expensive hot melt extruder, as
the plastic flakes melt instantly on contact with the hot oil. The heat required for melting
the mixed thermoplastics is quoted at 0.28 kW h/kg [25].
The catalytic pyrolysis process is characterized by the very high liquid fuel yield and
the low noncondensable gas and solid residue yields in contrast to thermal pyrolysis.
The diesel product from the NanoFuel Diesel process has a cetane number of >56, is
completely desulphurized and the chain-end double bonds are saturated in the process,
Figure 15.11 Overview of the NanoFuel catalytic diesel process process developed
process developed by Dr Christian Koch. The process converts waste plastics by cat-
alytic depolymerization at 270–370◦ C in the presence of an ion-exchanging catalyst
based on a highly active Y sodium aluminosilicate zeolite catalyst. (Courtesy of Poly-
mer-Engineering, Bielefeld, Germany)
thus stabilizing the diesel fuel. The diesel fuel is intended for use as substitute diesel
for transportation. The desired boiling range for the diesel fuel is achieved by the use
of a distillation column above the pyrolysis reactor. The process can convert an input
stream of 1000 kg of mixed polyolefins (LDPE/PP/HDPE) into >900 L of low-sulphur
diesel fuel [25].
The plastic flake and catalyst are fed into the stirred reactor via a feeding chute. The
diesel vapours are produced in the evaporator and sent to the distillation column for diesel
fractionation (Figure 15.12). In the lower part of the reactor the chlorine-bound salts and
420 J. SCHEIRS
Figure 15.12 Schematic of the NanoFuel catalytic diesel process process developed
by Dr Christian Koch. (Courtesy of Polymer-Engineering, Bielefeld, Germany)
spent catalyst are removed from the reactor by an auger positioned at the outlet [25]. An
annotated schematic of the NanoFuel Diesel process is shown in Figure 15.13.
The depolymerization catalyst possesses cations that make it act as an ion exchanger.
Before the hydrocarbon plastics begin to thermally crack, they are dechlorinated and
dehalogenated by neutralization by the ion exchanger.
The ion-exchange catalyst dechlorinates the plastics (e.g. PVC) and therefore avoids
issues with HCl generation and chlorine contamination of the diesel. The company claims
to have processed cable waste consisting of almost 100% PVC and the catalytic depoly-
merization process produced diesel fuel with a chlorine content below the detection limit.
The catalyst needs to be activated before use via ion exchange using soda (sodium
carbonate) and lime (calcium hydroxide) in order to insert the sodium and calcium ions
20
35
24
32
31 25
27 7
32 4 21
32 26
20
29
22
32
11
2 23
29 9
12 39
33
4 13 10
28 6 1
30 3
40 5 8 18
17 16
36
15 14
38
19
34
Figure 15.13 Schematic of the NanoFuel catalytic diesel process plastic-to-diesel plant
from German Patent DE 100-49-377-C2
Legend:
1 reactor; 2 pressure-free tank; 3 oil; 4 inlet; 5 waste catalyst gate; 6 mixer; 7 distillation
line; 8 condensor; 9 connecting pipes; 10 cycle vaporizer; 11 tank; 12 exhaust pipes; 13
swirl spiral; 14 combustion; 15 burner; 16 honeycomb catalyst layer; 17 temperature con-
trol; 18 honeycomb layer; 19 vacuum pump; 20 shredder; 21 regenerator; 22 connecting
pipe; 23 inlet gate; 24 smoulder exhaust; 25 seperator; 26 water treatment; 27 release
tank; 28 pipes to release tank; 29 pipes from release tank; 30 fluid level indicator; 31
pressure release valve; 32 cooler with outlet (withdrawal); 33 liquid separator; 34 tanks;
35 smoke gas exhaust; 36 connecting pipe between catalyst dryer and combustion
chamber; 37 ash exhaust pipe; 38 gas pipe from vacuum pump to combustion chamber;
39 oil pipe from lowest level to entry; 40 return pipe from lower line to reactor. (Courtesy
of Polymer-Engineering, Bielefeld, Germany).
into the zeolite catalyst. The usage rate of catalyst is stated to be 1.5% of the output of
diesel (which is 12 000 L/day) and this equates to 180 kg of catalyst usage per day. It is
the ion exchange capability of the catalyst that enables the considerably lower cracking
temperatures compared with conventional catalysts [25].
422 J. SCHEIRS
The acid cracking catalysts produce carbonium ions by the addition of protons to poly-
olefin chains or by abstraction of hydride ions from hydrocarbon molecules. This is followed
by chain scission, which yields C30 –C50 oligomeric hydrocarbons. Secondary cracking by
β-scission of the C30 –C50 hydrocarbons yields liquid (C10 –C25 ) hydrocarbon fuel.
Specific advantages of the Polymer-Engineering Process include:
• Molecular depolymerization at low temperatures (270–370◦ C) and under virtually
pressure-free (<0.1bar) conditions.
• The ion exchanger catalyst binds the chlorine in the waste plastic to form neutral salts.
The catalyst splits the long-chain hydrocarbons into shorter chains at a maximum
temperature of 390◦ C.
• Virtually no carbon is formed during catalytic depolymerization and therefore no
carbon residue accumulates on heat exchanging surfaces.
Catalytic depolymerization plants (KDV 500) with a capacity of 500 L/h have been
constructed for Germany, Mexico, Japan and Korea while a KDV 150 B plant with a
capacity of 1 500 000 tonne/yr is under construction for Bayern Oil in Germany to treat
vacuum residue [25].
The Polymer-Engineering process is very similar to the Thermofuel system design,
except that the main chamber contains a heavy thermal oil with a high boiling point. The
waste plastic is continuously added as flake and it quickly melts in the thermal oil and
pyrolyzes. The heavy oil is held at 390◦ C and the plastics quickly pyrolyze since it is an
excellent heat transfer medium.
In a related process Arandes et al. [26] dissolved polyethylene and polypropylene in
light cycle oil (LCO) and then catalytically cracked the polymers using a mesoporous
silica (pore size between 3 and 30 nm) in a commercial fluid catalytic cracking (FCC)
unit at 450◦ C. This strategy for upgrading plastics and oils together avoids heat transfer
limitations and other problems inherent to the cracking of molten plastics. The polyolefins
gave fuel with increased content of paraffins and iso-paraffins.
7.4 ROYCO PROCESS
The Beijing Roy Environment Technology Co., Ltd (also known as Royco) has developed
a commercial pyrolysis process for turning waste plastics into oil known as the EZ-Oil
Generator process.
The EZ-Oil waste plastics cracking unit converts waste plastics (e.g. waste plastics
including PP, PE, PS mixed plastics) into oil by low-temperature thermal cracking in the
absence of air and utilizes the output to produce electricity. The system includes a feeding
unit, reaction vessel, distillation tower, solid residue extractor/drying unit, circulation
water unit, oil storage unit, wastewater treatment unit, a scrubbing unit, and power-
generating unit. The company’s Web site is at www.roycobeijing.com.
A 20 t/day plant (6000 t/yr) is equipped with two pyrolysis vessels (with dimensions
of 2800 mm ID and 2000 m height). The vessels are fed with molten plastics by four
extruders each with a capacity of 250 kg/h. The plant runs continuously and can feed
waste plastics and discharge the solid residue while the plant is running. The liquid fuels
are fractionated in a fractionation tower. The plant produces a liquid fuel yield of up to
80% (by weight), depending on the nature of the feedstock.
The majority of waste plastic to oil processors utilize flue gases and other means
to heat their systems indirectly thereby having loss of heat energy. By so doing, these
other systems face problems with costs of operation, coking and inefficient processing
of the waste plastics. The Royco system utilizes a novel heating system based on far
infrared inner heating which dramatically reduces costs, virtually eliminates coking and
is most efficient compared with traditional heating methods. The major advantage of
the far infrared system is that it heats the waste plastics much more quickly and more
thoroughly, thereby shortening the time needed to melt the plastics to the stage where the
hydrocarbon vapours are released. Another significant advantage is that with the inner
heating system, the amount of heat loss is greatly reduced so that the unit runs more
economically and efficiently than other units who use indirect heating sources.
Notable features of the process are:
• The sediments like sand, mud, sludge, etc. are discharged out of the bottom of the
reactor while the plant is running.
• The molten plastic flows into the noncatalytic cracking unit where the liquid is cracked
into gas and fuel oil vapour and then leaves out of the top of the unit to go to the
condenser and fractionating tower.
• A ‘reflux’ is used where ‘lighter’ liquid is injected at the top of the distillation column
and this “strips” by counter-current absorption the heavy components from the rich
vapour rising up the packing inside the column.
• The noncondensable gas from the top of the tower is compressed into liquid gas (LPG)
and dry gas. The liquid gas is high quality.
• The fuel oil mixture from the cracking process is sent through the extraction and
fractionation process where high-grade fuel oils are obtained.
The technology is covered by the following patents:
• WIPO PCT/IB2004/000306 (Pending) ‘Enhanced Oil Recovery From Waste Plastics
Reactor’ (February 2004)
• US 60481826 (Pending) ‘A Reactor and Process for Converting Waste Plastics into
Oil with the FIR Heater’ (December 2003)
• Japan 2002-145569 (Pending) ‘Movable Apparatus and Method for Extracting Fuel
from Waste Plastics and Waste Oil’ (May 2002)
7.5 REENTECH PROCESS

Reentech Limited (Korea) has developed a patented catalytic cracking process
(Figure 15.14) which converts mixed plastics (e.g. PE, PP, PS) into gasoline, kerosene
and diesel fuel [27–31].
The Reentech moving-bed catalytic cracking process enables the continuous prepara-
tion of gasoline, kerosene, and diesel oil from waste plastics. The method comprises the
steps of subjecting a melt of the waste plastics to a first catalytic reaction in which the
waste plastic melt is in contact with a nickel or nickel alloy catalyst to be dehydrogenated
while being thermally decomposed, then subjecting the dehydrogenated and decomposed
waste plastic melt to a fluid catalytic cracking (moving-bed catalytic cracking), fraction-
ating the cracked material into a gasoline-based fraction, a kerosene fraction, and a diesel
oil fraction; and reforming the gasoline-based fraction to produce a high octane number
gasoline [27–31].
424 J. SCHEIRS
Figure 15.14 Photograph of the Reentech catalytic cracking process in Korea. The
Reentech process converts mixed plastics (e.g. PE, PP, PS) into gasoline, kerosene and
diesel fuel. (Courtesy of Reentech, Korea)
The incoming waste plastic melt is brought into contact with a catalyst impeller (prefer-
ably made of nickel or nickel alloy) at a temperature of 350◦ C. to 370◦ C., thereby being
dehydrogenated and decomposed. The downstream process consists of a moving-bed cat-
alytic cracker, in which a melt of the waste plastics and an alumina silicate solid acid
catalyst particles are introduced downward from the upper portion thereof, and cracked
and isomerized, and into which steam is injected through its lower portion to vaporize
nonvaporized gaseous oil present on the catalyst surface. The cracked gases are sent to a
fractionating column to give various hydrocarbon fractions. The fractionating column is
an Aspen fractionating column having a bubble cap tray type [29].
A cyclone outside the moving-bed catalytic column serves to sort only catalyst par-
ticles of a desired size among the catalyst particles dropped to the lower portion. A
nickel–molybdenum catalyst regenerator with an air injector serves to regenerate the cat-
alyst transferred from the cyclone and the regenerated catalyst is then returned to the
moving-bed catalytic cracker [29].
The process yields the following products:
• 75% fuel oil (comprising 55% gasoline, 25% kerosene and 20% diesel);
• 15% noncondensable gas (used as energy in the plant);
• 10% carbon (coke).
The annual capacity of the Reentech plants is 6000 tonne/yr of plastic input yielding
some 4.2 million litres of fuel oil [27].
The gasoline fraction has the following property profile:
• iso-C4, C5 25%
• Aromatics 13%
• olefins 8.6–10%
• benzene 1.4%
• octane number (RON) 91–94
• Reid vapour pressure (RVP) 144 kPa
The Reentech process incorporates the following key process steps:
• melting;
• dehydration and polymer decomposition (first catalytic reaction);
• contact catalytic cracking (second catalytic reaction);
• fractional distillation;
• refining of gasoline fraction;
• addition of additives.
A process flowchart for the Reentech process is shown in Figure 15.15.
The Reentech process uses a moving-bed catalytic cracking step, which is fundamen-
tally the same concept as a refinery fluid catalytic cracking unit (FCCU). The FCCC
converts high-boiling hydrocarbon pyrolysis gases to high-value high octane gasoline and
kerosene/diesel mixture. The FCC unit utilizes a microspherodial catalyst that fluidizes
when properly aerated by vaporized feed in the reactor riser. The term ‘fluid’ catalytic
cracking unit is derived from this characteristic property. The gas–oil feedstock is vapor-
ized by hot catalyst and thermally and catalytically decomposes in the reactor riser to
produce various products. These products undergo additional processing and separation
in the FCCU main fractionator and other vessels downstream of the FCCU reactor. As
a result of the cracking process, carbon (or coke) is deposited on the catalyst. The spent
catalyst is sent to the regenerator, where it is regenerated by burning off the carbon,
utilizing atmospheric air. The regenerated catalyst is then circulated back to the reactor,
where the process is repeated [27–31].
Reentech has adapted fluid catalytic cracking (FCC) for the small-scale refining of PE,
PP, and PS scrap. In FCC, a catalyst is used to accelerate the thermal cracking process.
In this form of cracking, the fractions are heated and then passed over zeolites, certain
types of clay, or other catalysts. FCC is more widely used than thermal cracking because
it requires less pressure and produces higher-octane gasoline. Also FCC can convert the
heavy fractions of the distillation process more efficiently than thermal cracking. In theory,
FCC is particularly suited for the recovery of the fuel value contained in plastic scrap
as gasoline, kerosene and diesel oil. The key to Reentech’s technology is a continuous
catalytic cracking process that Reentech calls contact catalytic cracking that continuously
regenerates the catalyst stream and thus delivers freshly activated catalyst to the catalyst
cracker (Figure 15.16). In contrast, the spent catalyst in a full-scale refinery must be
removed and replaced when the catalyst degenerates. The continuous regeneration of
the catalyst increases the efficiency of the processes, allowing the process to be run
economically on a relatively small scale [27–31]. Figure 15.16 illustrates the principle of
continuous regeneration combined with catalytic cracking.
426 J. SCHEIRS
Waste plastics
Crushing and
sorting Catalyst regeneration
Melting
Catalyst flow
Dehydrating and decomposing

(first catalytic reaction)
Fluid catalytic
cracking (second
catalytic reaction)
Fractionating
Kerosene fraction Gasoline fraction Diesel oil fraction
Reforming (third
catalytic reaction)
Low-pressure
gas separation
First refining
Additive blending
Refining Second refining Refining
Storage tank Storage tank Storage tank
Figure 15.15 Flowchart of Reentech catalytic cracking process. (Courtesy of Reen-

tech, Korea)
The catalyst flow process is as follows:

• regeneration at 700◦ C;
• transport to cracking reactor;
• vaporization of cracking gasoil;
• lifting up to regeneration tank.
The carbon residues of catalytic cracking are separated by a cyclone.
Oil gas
CO2 Distill
Catalyst flow
Gasoline kerosene, diesel
Plastics
O2
Regeneration Catalyst cracking
Reentech Continuous Regeneration of the Catalyst Presents Freshly

Activated Catalyst to the Cracker
Figure 15.16 Schematic of Reentech continuous regeneration of the catalyst which

supplies freshly activated catalyst to the cracker. (Courtesy of Reentech, Korea)
The noncondensable gas separated in the distillation tower is passed through a water
scrubber to remove HCl if PVC is present. Then the NCG is contacted with refrigerated
gasoline to condense some light fractions and finally the gas is passed through a flame
arrestor to a burner in the flame stack.
7.6 HITACHI PROCESS
Hitachi Zosen have developed a stirred tank/kettle pyrolysis process for waste plastic
(Figure 15.17) that is characterized by the following features [32, 33]:
• the ability to handle mixed plastic waste;
• a relatively low pyrolysis temperature;
• the automatic removal of char and extraneous matter;
• double (or triple) condensers;
• production of kerosene and gasoline fractions.
Hitachi Zosen have filed two US patents on their plastic-to-oil technology. The rele-
vant US patent numbers are US 5,584,969 and US 5,597,451 [32, 33]. The first patent
(5,584,969) ‘Apparatus for thermally decomposing plastics and process for converting
plastics into oil by thermal decomposition’ embodies a two-condenser system with an
option for a third.
In the Hitachi Process the low-boiling component of the gas flowing out from the top
of the column of the pyrolysis chamber is cooled and condensed initially in the primary
condenser, whereby kerosene is recovered. The low-boiling component of the gas passing
through the first condenser without condensation is transferred to the second condenser
where it is cooled for condensation, whereby gasoline is recovered. The decomposition gas
portion remaining uncondensed from the second condenser is then sent to the gas combus-
tion furnace by way of the water seal device and burned in the furnace [32, 33]. A mass
428 J. SCHEIRS
13
17 16 23
8
7 18
11 6
9a
5 12 1a
60 10 1
9
15 21
63 63a 9b 19
X 61a 61 X
4
62
2
3 22
20
Figure 15.17 Schematic of the pyrolysis vessel of the Hitachi Process. A notable feature
of the Hitachi Process is that the solid residue (char) is evacuated from the bottom of the
pyrolysis vessel via a suction pipe running down the centre of the hollow agitator shaft.
Legend: 1 pyrolysis vessel; 2 cyclone for solid residue; 3 burner; 4 furnace; 5 feed inlet
to pyrolysis chamber; 6 outlet for pyrolysis gases; 7 slide gate valve; 8 hopper for plastic
flake; 9 agitator shaft; 10 packed seal; 12 agitator drive chain; 13 drive motor for agitator;
15 suction pipe for solid residue; 16 vacuum pipe; 17 vacuum cut-off valve; 18 sealing
flange; 19 valve; 20 suction fan; 21 molten plastic; 22 burner flame; 61 char scraper; 63
agitator paddle [32]. (Courtesy of Hitachi, Japan)
Reclaiming Oil from Waste Plastic (Hitachi Zosen Corp.)

Mixture of waste plastics
PE : 55%
Mixture of waste plastics (60 kg/h) PP : 28%
PS : 17%
Gas
Reaction 3.9 m3/h
Condensation
350 deg. C (6.1 kg/h)
Vaporization
3.7 kg/h
420C, 56.3 kg
carbon residue
(char) Oil
Heating 62 litres/h
Oil
(50.2 kg/h)
17.9 litres/h
Oil yield : 1.03 litres/kg

Gas yield : 0.39 litres/kg (mainly propane)
Fuel efficiency : 0.3 litres/kg
Figure 15.18 Mass balance for Hitachi plastic-to oil pyrolysis process. (Courtesy of
Hitachi, Japan)
Table 15.7 Characteristics of the
fuel produced by the Hitachi Zosen
pyrolysis process
Property Typical value

Specific gravity 0.8
Cetane number 48
Flash point 37◦ C
Aromatic content 23%
Sulphur content 110 ppm
Viscosity 1.50
Calorific value 10 800 kcal/kg
balance for the process is shown in Figure 15.18. The characteristics of the fuel produced
by the Hitachi Zosen pyrolysis process from mixed waste plastics are shown in Table 15.7.
7.7 CHIYODA PROCESS
Chiyoda Corp., Japan, has developed a next-generation technology for liquefaction of

plastic wastes. The new process facilitates reuse of plastic wastes from household refuse
into liquid fuel. In the new method, crushed plastic waste is fed to a dechlorination unit
where PVC and PET are thermally degraded into hydrogen chloride, terephthalic acid,
etc. These gaseous components are separated from the melted liquid plastic and sent
to an incinerator for safe disposal. The melted plastic waste is transferred to a thermal
cracking reactor where it is further heated and converted to vapour-phase hydrocarbons
and residue. The vapour-phase hydrocarbons are charged to a distillation column and
separated as cracked gas, light oil, a middle distillate and heavy oil. A portion of the
middle distillate is recycled to the thermal cracking reactor as vapour phase through the
heating furnace. The heavy oil is mixed with residue from the bottom of the thermal
cracking reactor and the mixture is used as a fuel. The separated light oil can be used
as a feedstock for petrochemical plants or as fuel oil. Cracked gas obtained at the top of
the distillation column is cooled and separated from the light oil and transferred to the
incinerator [34].
7.8 BLOWDEC PROCESS
The Blowdec depolymerization process from Slovakia converts waste plastics into low-
sulphur diesel fuel [35]. The main principle is the processing of waste plastics in a hot
whirling bed of hot sand in the BLOWDEC reactor (Figure 15.19). The plastic is heated
to 430◦ C. The process allows for simultaneous cracking of hydrocarbons and inhibition
of coke formation. The fluidized sand bed products three types of cracking reactions:
mechano-activation; thermal; and catalytic (SiO2 /aluminosilicates). The process is cov-
ered under the US Patent 6,165,349. The process enables the economical conversion
of mixed waste plastics into liquid hydrocarbons, mainly low-sulphur (25 ppm) diesel
430 J. SCHEIRS
4
1 1
4
Mk 3
2 2
3
Sand
(a) (b) (c)

Gaseous products:
Whirling bed Hydrocarbons and water
Waste
inlet
(d) (e) (f)

Treated solids
Principle of the process.
a, b – Basic scheme of the reactor's construction
c – Start up (movement of the reactor rotor)
d – Creation of the whiling bed (sand filling)
e – Heating of the reactor
f – Process run
Description: 1-process chamber, 2-shaft, 3-arm of the blade, 4-blade, Mk-torque
Figure 15.19 Schematic of the reactor of the Blowdec depolymerization process from
Slovakia which converts waste plastics into low-sulphur diesel fuel in a hot whirling
bed of hot sand. The plastic is heated to 430◦ C by the hot sand which also exerts a
catalytic effect that enables simultaneous cracking of hydrocarbons and inhibition of
coke formation [35] (Reproduced by permission of Slovnaft Virup)
with Pensky–Martens flash point of 62◦ C and pour point of −15◦ C, and has the added
advantage of the lack of formation of coke residues on heat transferring surfaces [35].
7.9 CONRAD PROCESS
Conrad Industries (Chehalis, Washington) have demonstrated the pyrolysis of post-use

plastics into petrochemical feedstocks. The plastic most studied was a mixture of 60%
high-density polyethylene, 20% polypropylene, and 20% polystyrene. Yields of liquid
products were in the range 65–75% at 482–510◦ C. Other studies examined the effects
of PET and PVC on the liquid yields. The liquid products were determined to be suitable
feedstocks for further refining, but the economics were not competitive with conventional
petroleum refining in 1994 [36].
7.10 OTHER PROCESSES WITH SEPARATE CATALYST BEDS
The Likun Process (China) uses a two-stage cracking process under normal pressures
where the waste plastics are first pyrolyzed at 350–400◦ C in the pyrolysis reactor and
then the hot pyrolytic gases flow to a catalyst tower where they undergo catalytic reforming
over zeolite at 300–380◦ C. By having the catalyst in the second stage this overcomes the
problems of rapid catalyst deactivation from coke deposits on the surface of the catalyst.
The Fuji Process also uses a two-stage cracking process comprising a main cracking
reactor and a reforming reactor. In the reforming reactor the pyrolysis oil is upgraded to
gasoline, kerosene and diesel.
Such two-step processes are also referred to as cracking–catalytic reforming (CCR)
processes. The catalytic reforming stage of the primary oil product ensures high-quality
diesel or gasoline products are obtained. The catalytic reforming step improves the RON
and the contents of isomer, cycloparaffins and aromatics.
8 CONCLUSIONS
A major advantage of plastics pyrolysis is its ability to handle unsorted, unwashed used
plastic. This means that heavily contaminated plastics such as mulch film (which some-
times contains as much as 20% adherent dirt/ soil) can be processed without difficulty.
Other normally hard to recycle plastics such as laminates of incompatible polymers, mul-
tilayer films or polymer mixtures can also be processed with ease, unlike conventional
plastic recycling techniques. In fact, most plastics can be processed directly, even if con-
taminated with dirt, aluminium laminates, printing inks, oil residues, etc. The viability of
pyrolysis is assured by the lack of other recovery options for such waste plastics besides
landfilling and incineration. The increasing pressure on companies to adopt sustainable
outlets for their end-of-life plastics, the introduction of extended producer responsibility
and product stewardship directives, together with the implementation of legislative mea-
sures to deal with waste plastics are significant drivers which will further increase the
interest and adoption of the pyrolysis route for waste plastics.
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16
Fluidized Bed Pyrolysis of Plastic

Wastes
UMBERTO ARENA AND MARIA LAURA MASTELLONE
Department of Environmental Sciences, University of Naples II, Via Vivaldi 43, 81100
Caserta, Italy
1 INTRODUCTION
1.1 FLUIDIZED-BED TECHNOLOGY FOR WASTE THERMAL TREATMENTS:

THE KEY ROLE OF HYDRODYNAMICS
Gas–solid fluidization is the operation by which a bed of solid particles is led into a
fluid-like state through suspension in a gas. Compared with other methods of gas–solid
contacting (such as fixed beds, rotary cylinders, flat hearths, etc.), fluidized beds have
some rather unusual and useful properties that can lead to desirable characteristics for
waste thermal treatments in general, and for plastic waste pyrolysis in particular. The
reader can refer to some fundamental and exhaustive books for a deepen account of
fluidized-bed reactor engineering [1–4]. Here, it is important to highlight the crucial role
that hydrodynamics plays in the design and operations of a fluidized-bed reactor. All the
physical and chemical processes carried out in fluidized beds are strongly affected by the
quality of fluidization: the heat and mass transfer, the gas and solids mixing, the radial
and axial temperature profiles, the effective gas and solids residence times as well as the
quality of the contact of reactants, all are related to the peculiar features of the fluid bed
hydrodynamics. This implies that some variables, such as the size and density of the bed
particles, the gas fluidization velocity, the height-to-diameter ratio of the bed, the gas inlet
arrangement, the vessel geometry, acquire a key role in determining the overall perfor-
mance of the reactor [1, 5]; as a consequence, their values must be accurately fixed by
fluidization engineering, on the basis of reliable relationships and of results from specific
pilot-scale investigations.
Different types of fluidized-bed reactors are commercially available for plastic waste
pyrolysis. The term fluidization has been used in literature to refer to dense-phase and
436 U. ARENA AND M.L MASTELLONE
lean-phase systems, as well as circulation systems involving pneumatic transport. The
fluidization engineering deals with all these methods of contacting, but the main focus
is on dense-phase systems. Bubbling fluidized beds (BFB) belong to the dense-phase
fluidized beds as long as there is a fairly clearly defined upper surface of the bed:
gas bubbles coalesce and grow as they rise up to the top of the bed and there is
a limited entrainment of fine particles from the unit (captive regime). When gas flu-
idization velocity increases, significantly more than the terminal velocity of the solids,
there is no more distinct upper bed surface while large amounts of particles are car-
ried out of the bed with the gas (transport regime), precluding steady state operations.
This state belongs to the lean-phase fluidized beds: steady state operation is possible
only if entrained particles are collected by a cyclone and then returned to the bed
by means of a downcomer and a non-mechanical valve. These reactors are called cir-
culating fluidized beds (CFB), where the term ‘circulating’ signifies that the particle
separation and return systems are integral and essential components of the reactor con-
figuration. The convincing advantage of overall economy of fluidized-bed contacting is
the explanation of its successful use in industrial operations, even though such success
strongly depends on understanding and overcoming its disadvantages. The following main
advantages can be listed for fluidized-bed reactors utilized for thermal treatments of
waste [1]:
• The rapid and good mixing of solids, which leads to almost uniform isothermal con-
ditions throughout the fluidized bed. This allows an easy and reliable process control.
• The whole reactor of well-mixed solids represents a large thermal flywheel that resists
to rapid temperature changes and avoids formation of cold or hot spots.
• The range of operating temperatures is generally lower than that of other gas–solid
reactors.
• Heat and mass transfer between gas and particles are high when comparing with
those of other gas–solid reactors and there is a very good quality of contact between
reactants of a gas–solid reaction.
• The liquid-like flow of particles allows continuous controlled operations with easy
handling. In particular, the circulation of solids between two fluidized beds makes it
possible to remove or add the high quantities of heat produced or needed in large
reactors as well as to substitute part of the (sticky or agglomerated) bed material with
fresh solids.
• The high process flexibility makes possible to utilize different fluidizing agents, oper-
ating temperatures and gas residence times and to operate with or without a specific
catalyst.
• The lower maintenance times and costs, as immediate consequence of the absence of
moving parts in the hot regions and of the lower operating temperatures. This allows
a wider range of investment alternatives, making fluidized beds suitable for large as
well as for small-scale operations.
Several of these advantages are increased in a CFB reactor: improved gas–solid con-
tact given the lack of bubbles; reduced cross-sectional area given the higher superficial
velocities; more control over suspension-to-wall heat transfer because of the ability to use
the solids circulation flux as an additional variable; less tendency to show particle seg-
regation and agglomeration; superior radial mixing that allows fewer solids feed-points;
higher solids flux trough the reactor [3].
FLUIDIZED-BED PYROLYSIS 437
The main disadvantages that must be taken into account are [1]:
• Friable solids (bed materials, solid reactants as well as catalysts) are pulverized and
entrained by the gas.
• For noncatalytic thermal treatments of waste, the agglomeration and sintering of fine
or sticky particles can require a lowering/rise in operating temperature (that implies
a variation in process performance) or a continuous withdrawal of bed material that
must be substituted with a make-up of fresh material.
• The intensive rapid solid mixing in the reactor leads to a wide range of residence
times of individual particles in the reactor: for continuous operations this gives poorer
performance since the removal of fully reacted particles will inevitably be associated
with removal of unreacted carbon; for catalytic reactions, the movement of porous
catalyst contributes to the backmixing of gaseous reactant.
• Erosion of pipes and vessels by abrasion of bed particles can be serious.
• Scale-up is not always easy to realize: pilot plant is often necessary to verify the
validity of laboratory-scale tests.
For CFB reactors further aspects have to be taken into account: restricted range of
admittable particle properties; increased particle attrition; decreased suspension-to-wall
heat transfer coefficients; more complexity in designing and operating the circulating
loop; higher capital costs.
1.2 FROM PLASTIC WASTE TO FEEDSTOCKS AND ENERGY BY MEANS OF

FLUIDIZED-BED PYROLYSIS
Menzel, Perkow and Sinn presented the first fluidized bed process for pyrolysis of plastics
in 1973 [6]. A series of tests on a laboratory-scale bubbling fluidized bed was performed
in order to evaluate the reliability of fluidization as a more flexible and controllable
technology for plastic pyrolysis. The first batchwise experiments with polyethylene and
other wastes demonstrated that ‘plastic scrap or waste, even when contaminated with
paper or wood, can be processed in a cracking plant in the same ways as crude oil’ [6].
Since 1980, other authors have presented a considerable amount of experimental data
on pyrolysis of plastics in different fluidized beds. In particular, there is the well-known
research carried out by Kaminsky and his colleagues at the University of Hamburg,
Germany [7–14]. Their pyrolysis plant, expanded and upgraded many times from 1980
until now, has been used in several series of experiments with plastics, rubber, tires and
other wastes with the aim of defining the mechanisms of the process and determining the
best operating conditions (in particular, the reactor temperature and the type of fluidizing
gas) allowing the production of yields with high-heating-value gas and BTX-rich oil or
aliphatic oil. Other studies have been published [15–19], referring to experiments carried
out under different operating conditions (batch or continuous feeding, different fluidizing
gas, different plastic waste, bed material with catalytic properties, etc.) and by means of
different reactor apparatus.
Table 16.1 reports a summary of pyrolysis processes for plastic wastes, auto shredder
residues, tires and other wastes carried out with different gas–solid reactors. It can be
deduced that now fluidized-bed technology appears mature and particularly attractive for
438
Table 16.1 Pyrolysis processes for plastic wastes, auto shredded residues and tires along with other wastes
Process Actors involved Technology Process description Input/output Technical status

Akzo Akzo Nobel (NL) Two circulating Fast pyrolysis in a CFB I: shredded MPW with high Pilot (30 kg/h) since 1994.
fluidized beds reactor (700–900◦ C), percentage of PVC, PVC Some tests on a large
where waste is converted cable, pipe scrap scale (200–400 kg/h)
with steam into fuel gas, O: HCl, CO, H2 , CH4 ,
HCl and residual tar, and other hydrocarbons, fly
combustion in the second ash
CFB. The process is
based on the Battelle
process for biomass
gasification
Amoco Amoco Chem. Corp. Catalytic cracking at I: PE, PP, PS, plastic wastes Pilot since 1991
490–580◦ C mixed with vacuum gas
oil
O: naphtha, light mineral oil
gases
AMRA Center of Bubbling fluidized bed Gasification in a BFB of I: polyolefins and RDF Pilot (20–50 kg/h) in
Competence on sand, fluidized by air, shredded at a size Caserta (I)
Env. Risks (I), steam and nitrogen at a <2.5 cm
Univ. of Naples II temperature between 750 O: syngas, energy
(I) and 900◦ C
Battelle Battelle Memorial Two circulating Gasification in a CFB of I: PE, PS, PVC and MPW Pilot (9 kg/h) in Vermont
Inst. (USA) fluidized beds sand, fluidized by steam shredded at a size (USA) since 1992
and nitrogen at a <2.5 cm
temperature between 800 O: ethylene, H2 , CH4
and 1000◦ C
BP polymer BP Chemicals, Elf Bubbling fluidized bed Low-temperature I: clean plastic wastes Pilot (50 kg/h) in
cracking Atochem, DSM, pyrolysis(500◦ C) in a (<2% PVC) Grangemouth (UK)
Enichem, Fina BFB of sand. The product O: mainly waxy
is cleaned from HCl and hydrocarbon products to
fine particles and then be used in existing
fractionated petrochemical plants and
refineries
U. ARENA AND M.L MASTELLONE
BASF BASF AG Melting vessel, Liquid phase pyrolysis in a I: plastic wastes (max. 8% Demonstration (15,000
cracking indirectly heated 3-stage process: PVC) t/y) in Ludwigshafen
liquefaction at 300◦ C in a O: petrochemical gaseous (D) started in 1994 and
stirred kettle; cracking in and liquid feedstocks shut-down in 1996
a gas fired tubular (naphta, aromatic
furnace at 350–480◦ C; compounds, high-boiling
separation of products, oils)
oils (60–70%) and gases
(20–30%), in a
distillation column
Compact Compact Power Ltd Tubular reactor + High-temperature I: MSW, sewage sludges, Pilot (360 kg/h).
Power (UK) fixed bed pyrolysis (800◦ C) of the scrap tire crumb Demonstration (8000 t/y)
shredded waste conveyed O: energy in Avonmouth (UK)
by a screw feeder. Operational: 60,000 t/y in
Fixed-bed gasification of Dargavel (UK)
the char residue.
Combustion of gas from
pyrolysis and gasification
units at 1250◦ C in a high
temperature furnace
DBA Deutsche Rotary kiln, indirectly Low-temperature pyrolysis I: plastic wastes Operational: 6 t/h,
Babcock-Anlagen heated (450–500◦ C) in an O: energy Burgau (D)
indirectly heated rotary
kiln
Eddith Thide Environment Rotary kiln, Drying to reduce moisture I: MSW, sewage sludges Pilot (500 kg/h) in
S.A. (F) and externally heated until 10%. O: energy, CARBOR Vernouillet (F).
Institut Français Low-temperature (coke-like product) Demonstration (1250 kg/h)
du Pétrol (F) pyrolysis (450–550◦ C) in in Nakaminato (J).
an externally heated Operational:
rotating tubular reactor. 20,000 t/y, Hoigawa (J)
Combustion at 1000◦ C 50,000 t/y, Arras (F)
of produced gas with air
coming from the dryer
(continued overleaf )
439
440

Ebara Tsukishima (J) Two internally Pyrolysis in a fluidized bed I: plastic wastes Operational: 4 t/h,
revolving fluidized and combustion of the O: energy Yokohama (J)
beds products (mostly oil) in 3 × 6.25 t/h, Funabashi
the second fluidized bed (J)
reactor
Ebara Ebara Corp. (J), Internally revolving Gasification of the shredded I: ASR, plastic and Pilots (0.3 t/h) in
TwinRec Alstom Power until fluidized bed + waste material in a electronic wastes, sewage Sodeguara (J) and
2002 ash-melting system revolving fluidized bed, sludge, MSW (1 t/h) in Fujisawa
operated at 500–600◦ C, O: energy, ferrous and (J) since 1997.
which separates non-ferrous metals, glass Operational: 19 t/h in
combustible part from granulate Aomori (J), 18 t/h in
inert and metallic ones. Kawaguchi (J), etc. and
Combustion of syngas 60 t/h in Selangor
and char in a cyclone (Malaysia, under
combustor construction)
(1350–1450◦ C) at a low
excess air ratio
Fuji Fuji Recycle Ind., Extruder + fixed bed Extrusion at 300◦ C; mixing I: polyolefines industrial Pilot (400 t/y) in Okegawa
Mobil Oil, Nippon with liquid product wastes City (J) for general
Steel Corp., recycled from the O: gasoline, kerosene, diesel plastic waste
Shinagawa Fuel pyrolysis reactor; Demonstration (5000 t/y)
Corp. thermal decomposition in Aioi City (J) for
in the reactor; catalytic industrial plastic waste
cracking in a fixed bed
reactor using a
zeolite-based ZSM-5
catalyst at 400◦ C
Hamburg- University of Bubbling fluidized bed High-temperature pyrolysis I: shredded plastic wastes Pilot (40 kg/h) at the Univ.
ABB Hamburg (D), (600–800◦ C) in a BFB, (having as low as possible of Hamburg.
Asea Brown Boveri fluidized with liquid-free Cl content) Demonstration (5,000 t/y)
pyrolysis gas or inert O: high yield of olefins, operated in Ebenhausen
BTX-rich oil (D) 1986–1989
(steam + N2 ) gas
Mazda Mazda Motor Corp. Fixed bed Catalytic cracking in a I: ASR Pilot (400 t/y)
fixed bed reactor that O: 60% oil (petrol,
uses a AlCl3 +HCl kerosene)
catalyst at 250–450◦ C
Mitsui R21 Mitsui Eng. and Rotary kiln, indirectly Two-stage process that starts I: MSW and municipal Operational:
Shipbuilding (J), heated with a low-temperature commercial waste, plastic 2 × 110 t/d, Yame
Mitsui Babcock pyrolysis (<450◦ C) in a waste, sludge. Seibu (J)
Energy Ltd (J) rotary kiln and is O: energy, ferrous and non 2 × 200 t/d, Toyohashi
followed by a ferous metals, glass City (J)
high-temperature granulate 2 × 70 t/d, Ebetsu City (J)
combustion (1300◦ C) of 2 × 130 t/d, Koga
the gaseous and solids Seibu (J)

products in an 2 × 105 t/d, Nishi Iburi (J)
ash-melting furnace. The 2 × 105 t/d, Kyohoku (J)
process derives from
Siemens Schwel-Brenn
Process (D)
Nikon Nikon Rikagaku Catalytic cracking at I: plastic wastes of 10 mm Pilot
200–250◦ C and 1bar particle size
with metal catalyst O: 80% oil
Noell-KRC Noell-KRC Energie Externally heated Low-temperature pyrolysis I: MSW, industrial waste Pilot (0.5 t/h) in
und rotary kiln + (550◦ C) in a rotary kiln. slurries, dried sewage Freiberg (D)
Umwelttechnik entrained flow Subsequent gasification sludges Demonstration
GmbH(D) reactor with pure oxygen (at O: syngas, energy (116,000 t/y) in Northeim
flame temperature of (D) for MSW and
1400–2000◦ C and at a dewatered sludges
pressure of 2–50 bar) of
dedusted gas, cooled
condensates and
water-quenched, screened
and pulverized coke-like
residues. Recovery of
obtained syngas or its
combustion in a boiler,
gas turbine or engine
441
442

NKT NKT Res.Center Low-temperature pyrolysis I: PVC wastes (cables, Pilot (200 t/y) since 1998
(DN), Danish EPA (375◦ C) with subsequent flooring, etc.) or MPW to
metal extraction. Light be treated to obtain
plastics are sorted out in almost pure PVC
the pretreatment section O: Metal concentrate (up to
together with sand and 60% lead) for recycling;
metals calcium chloride; coke
and organic condensate to
be used as fuel
PKA PKA Umwelttechnik Rotary kiln, indirectly Drying followed by I: MSW, ASR, industrial Pilot (24 000 t/y) in
GmbH&Co. KG heated low-temperature plastic wastes, spent tires, Aalen-Goldshöfen (D)
(D); PEC-Product pyrolysis (500–550◦ C) in contaminated soil Operational: 3 × 4 t/h,
en Energie a rotary kiln for about O: energy Delfzijl (NL)
Centrale (NL) 1 h. Gasification of
produced gas at 1000◦ C
to obtain CO/H2 -rich gas;
char fines are separately
gasified by oxygen at
1500◦ C
Pyropleq Mannesmann, Rotary kiln, indirectly Low-temperature pyrolysis I: MSW Operational:
Technip (F), heated (450–470◦ C) in a rotary O: energy 2 × 3 t/h, Burgau (D)
WasteGen (UK) kiln, with internal blades, 2 × 6.7 t/h Dortmund
indirectly heated by hot (D) under construction
gases at 550◦ C.
Combustion of the
product gas at 1200◦ C
after a high-temperature
particulate collection
Veba Oel Veba Oel AG in Rotary kiln, indirectly High-temperature I: ASR + vulcanized Operational:
Gelsenkirchen heated pyrolysis (650–800◦ C) elastomers 0.5 t/h, Gelsenkirchen (D)
(Veba Pyrolyse of plastic waste, fed into O: coke (∼80%), oil, gas 12.5 t/h, Ruhr area (D)
anlagen) the rotary kiln via a
screw feeder. Solid cokes
and pyrolytic vapours are
sent to further treatments
in gasification or
hydrogenation plant
Takuma Takuma Corp. (J) Indirectly heated Drying of crushed waste I: MSW, ASR, sewage Demonstration (7,000 t/y)
SBV rotary followed by sludge in Fukuoka (J)
kiln + ash-melting low-temperature O: energy, iron, aluminium Operational:

system pyrolysis (500–550◦ C) in 90 t/d, Kanemura (J) ASR
a rotary kiln for about 2 × 81 t/d, Kokubu
1 h. Combustion of the (J) MSW
pyrolysis gas in a high 2 × 63 t/d, Oshima
temperature combustion (J) MSW
chamber. The process
derives from Siemens
Schwel-Brenn
Process (D)
Toshiba Toshiba (J), Pyrolysis + gasification + I: ASR Operational:
Yamanaka gas cracking 20 000 t/y (J)
Von Roll Von Roll Reciprocating Pyrolysis in a Von Roll I: ASR, plastic wastes, Operational:
RCP Umwelttechnik grate + circulating forward reciprocating MSW 6 t/h, Bremerhaven (D)
AG (CH) fluidized bed grate. Gas and solids O: energy
residue are sent to a
smelting reactor and then
to a CFB furnace
operated at less than
1000◦ C
MPW = mixed plastic waste; MSW = municipal solid waste; ASR = auto shredded residue; BFB = bubbling fluidized bed; CFB = circulating fluidized bed. Rows
in italics are related to fluidized-bed processes. Data have been mainly obtained from [9, 20–24]
443
plastic waste pyrolysis. This comes from several reasons. The very good heat and material
transfer, and the consequent almost constant temperature, provide for uniform products
(that are not constrained in their application) and allow short residence times at moder-
ate temperatures; the suppression of side reactions as cyclization increases the process
controllability; the absence of moving parts in the hot region reduces the maintenance
time and cost; the possibility to apply the process on a relatively small scale increases
the range of investment alternatives. Moreover, the pyrolysis process in a fluidized-bed
reactor appears really flexible, as demonstrated by the pilot-plant and demonstration-scale
investigations that several companies and research groups are carrying out. The aim is
assessing the possibility to obtain different products by operating the reactor at differ-
ent temperatures and with different fluidizing gas. Table 16.2 proposes a taxonomy of
different plastic waste pyrolysis processes that the flexibility of the fluidized-bed reac-
tors makes possible. On the other hand, the disadvantages that are not yet completely
eliminated are the necessity to limit the chlorine content in the inlet stream, the risk of
fluidization worsening as a consequence of solid agglomeration in the bed and the lack of
reliable assessments on the scale and operating conditions under which the full economic
convenience of the fluidized-bed pyrolysis process is obtainable.
Table 16.3 sketches a comparison between the main gas–solid reactors utilized in the
industrial (and demonstration) processes listed in Table 16.1. It again shows the great
potentiality of bubbling and circulating fluidized-bed reactors, particularly when the pro-
cess aims to obtain very valuable products.
2 DIFFERENT STAGES IN THE FLUIDIZED-BED PYROLYSIS OF A

PLASTIC WASTE
2.1 AN OVERVIEW OF PHYSICAL AND CHEMICAL PHENOMENA
The yields of the products obtained from a pyrolysis process in a fluidized-bed reactor
are due to two contributions. The first, called primary cracking, is that of raw material
degradation, i.e. the cracking of molten polymer, which occurs in the dense bed. The
second contribution, referred to as secondary and ternary reactions, is that of reactions
involving the primary volatiles, which can occur partially inside the bed and partially
along the freeboard [16, 19]. These processes are only two of a series of physical and
chemical steps that polymer particles undergo after their feeding into a pyrolyser. The
sequence of steps strongly depends on the reactor type. In a fluidized-bed reactor, the
interactions between the injected polymer particles and the bed material define the peculiar
mechanisms of a series of these steps. Figure 16.1 provides a list of them as deduced by
batchwise and continuous experiments [32, 33], highlights the region of a bubbling bed
where each of them mainly occurs and indicates the paths by which the carbon, under its
different forms of fixed carbon (FC), volatile (V) and elutriable fines (F), moves inside
the reactor.
Figure 16.2 visualizes the same series/parallel sequence of steps, but by following the
fate of a single polymer pellet just after its injection into the hot fluidized-bed pyrolyser.
The pellet is fast heated up by a high-rate heat transfer mechanism that leads external
surface up to the softening temperature (step 1 in Figure 16.2). Several sand particles
Table 16.2 Different pyrolysis processes that can be carried out in a fluidized-bed reactor
Process Temperature Plastic waste Fluidizing gas Output References

range (◦ C)
Low-temperature 450–580 PMMA, PS Nitrogen MMA (98% at 450◦ C); Styrene [9, 13, 25, 26]
pyrolysis for (61% at 515◦ C)
monomer
recovery
Low-temperature 500–600 Single or mixed Nitrogen; liquid-free Broad spectrum of products [9, 14, 16, 26, 27, 28]
pyrolysis for polyolefins pyrolysis gas (C1 –C50 ). The gas yield is
feedstock (HDPE, LDPE, generally low with respect to
recovery PP, PS, PVC), SB waxes and oils
rubber
High-temperature 650–800 Polyolefins (HDPE, Nitrogen; steam Gas yield is generally high [8, 9, 16, 19, 28, 29,
pyrolysis for LDPE, PP, PVC), High content of olefins 30, 31]
feedstock SB rubber, ABS,
recovery PA, PTFE, . . .
600–800 Mixed polyolefins Liquid-free Generally high yield of gases [9, 10]
(HDPE, LDPE, pyrolysis gas with a high heat-content.
PP, PS) High content of BTX-rich
oils
Catalytic pyrolysis 370–550 PE, PS, PP Nitrogen Product spectrum strongly [18, 25]
depends on the catalyst.
Silica–alumina produces
high yield of liquids from
PE and PP. FCC promotes
high gas yield even for PS
and PE (waxes fraction
decrease from 90 to 1%)
445
446
Table 16.3 Comparison of different gas–solid reactors for plastic pyrolysis
Fixed bed Bubbling fluidized bed Circulating fluidized bed Rotary kiln Melting vessel Extruder
Temperature Large temperature Temperature is Temperature Longitudinal as well Severe temperature Two zones are
profile gradients can almost constant in gradients in as transversal gradients are recommended:
occur. Frequent vertical direction. direction of solid gradient may be difficult to control one at <150◦ C to
presence of hot Limited variation flow can be large and not easy remove the
spots in radial direction limited by high to control volatile fractions
solid flow rate and one at
circulation >250◦ C to
extract HCl gas
Temperature 400–800 500–850 750–850 450–800 300–480 200–520
range
(◦ C)
Heat Inefficient exchange. Very efficient Efficient exchange, Very poor exchange. Poor exchange Degradation occurs
exchange Necessity of large exchange. Large particularly along Then there is often by exposure to
and surface of heat transfer longitudinal the necessity of thermal and
transfer exchanger activated by solids direction long cylinder kilns mechanical work
circulation (shear forces)
Particle size Generally fairly Wide size Fine solids for the No problem for size. Feeding problems The plastics waste
large. Due to the distribution. Mean bed particles Any size can be can arise (air must be shredded
poor temperature particle diameter (generally the treated, from fines lock). The to the size of
control, there is between 0.08 and mean particle to large lumps particle size needs side-plates
risk of sintering 3 mm. Attrition of diameter is to be <1 cm3 and
bed particles and 0.05–0.5 mm). the bulk density
the consequent Plastic waste must >300 kg/m3 .
entrainment may be not larger than Agglomerated
be severe 10 cm polymer
feedstock must
respect severe
specifications
Residence Particles spend Particles pass Very long (1–2 h) Long (20 min)
time substantial time repeatedly trough
(minutes or hours) the circulation
in the bed. Gas loop: residence
residence time time for each
depends on gas circuit is few
velocity that is seconds.
below 2 m/s Gas velocity is
3–15 m/s
Conversion Very high conversion Mixing of solids and High conversion is Conversion can be The conversion Mainly used as a
is possible with gas bypassing can possible high efficiency of the pretreatment
plug flow of gas determine process is over before feedstock

and proper performance 90% recycling
temperature poorer than other processes
control reactors
Process Very limited. Any Excellent. It can be Excellent. The Limited. The Limited Allows highly
flexibility change in process used for low- and reactor can be operating diverse
variables high-temperature operated in either parameters mixed-plastics
(temperature, type pyrolysis, in a co-current (residence time, stockpiles to be
of catalysts, etc.) presence or not of upward flow mode temperature, etc.) homogenized,
needs a new a catalyst. or fast fluidization can be varied in a sterilized,
reactor design Different plastic mode, depending narrow range. compacted,
wastes can be on gas velocity Generally used to chemically
treated and solid produce fuel gas modified and
circulation rate. for energy converted into a
Moreover different recovery form fit for
reactants can be transport
add at different
heights of the riser
447
448
Fixed bed Bubbling fluidized bed Circulating fluidized bed Rotary kiln Melting vessel Extruder
Noncatalytic Unsuitable for Excellent for Excellent for Widely used. Suitable for solids, Not used
pyrolysis continuous continuous continuous Suitable for solids, which may sinter
operation operations, operations which may sinter or melt
yielding a uniform or agglomerate
product
Catalytic Can be used for very Excellent Attrition of catalyst Not used Not used Degradation is
pyrolysis slow or temperature is serious supported by
nondeactivating control allows catalytic effect of
catalyst large-scale added or
operations sprayed-in
chemical agents
(metal oxides) or
by exposure to
reactive gas (air,
oxygen, steam,
hydrogen)
Value of Quality of the oil Can be high, Can be high taking Generally low, since Liquid product The heterogeneous
obtained products is equal particularly in in mind the high the poor yields are commingled
products to that of process for flexibility of the temperature strongly plastics waste is
conventional monomer recovery reactor control leads to a dependent on converted into a
gasoline, kerosene and in wide spectrum of feed type, homogeneous
and diesel oils high-temperature products temperature and liquid or
pyrolysis residence time. granulated at the
The oil products exit of the
require further extruder or heated
purification. The up so much at the
liquid yields and end of the
their quality are extruder
not as high as (>520◦ C) that it
that produced by volatilizes
fluidized-bed
pyrolysis
Scale-up Serious temperature Must be carefully As for BFB Generally not No information The experiments
problems control problems considered. A pilot relevant have been
limit the size of plant is often performed on
the units necessary different sized
equipment (screw
diameter
30–90 mm)
Costs High costs and risk Moderate. The Capital costs higher Moderate cost of A full-scale plant Single-screw
of poisoning/ possibility of that those for investments. Large needs about extruders have
deactivation of small-scale plants BFB. Generally costs of 300 000 t/y of low price and
catalyst makes the convenient for maintenance due plastic waste to operating costs.
investment large-scale plants to moving parts be convenient. Co-rotating twin

alternatives wider. and the fouling Low capital screws are more
Low costs of and erosion of investment, but expensive.
maintenance inner walls processing costs Counter-rotating
that exceed the twin screws
value of the crude occupy an
oil product intermediate
obtained. position
Maintenance
costs can be high
for several
reasons (e.g.
fouling of inner
walls)
449
Freeboard
Elutriation of carbon fines
3 Freeboard 3
Secondary and ternary reactions
of primary products
V F
Comminution
Agglomeration
2 Secondary and ternary reactions 2
of primary products
Bed
Char-sand aggregate formation
Dense bed
V FC Primary cracking of polymer

Melting
1
Polymer-sand aggregate formation
1
Softening
Heating
Figure 16.1 Different steps that a polymer particle undergoes after the injection into a
fluidized-bed pyrolyser. The graph indicates the carbon paths inside the reactor (adapted
from [19]). (Reproduced with permission from Elsevier)
stick on the plastic surface, forming a polymer–sand aggregate that has the external shell
made of sand particles and the internal core made of polymer not yet molten. When the
temperature further increases, the surface of the pellet reaches the melting temperature
and the polymer flows throughout the bed particles of the external shell, so forming a
uniform coating over and between them (steps 2–4). The peculiar features of fluidized
beds [1] make this heating and coating process very fast, so that the beginning of the
pyrolysis, i.e. the cracking of the weak carbon–carbon bonds of the polymer chain, starts
when the polymer has already covered the bed particles. The primary cracking (step 7)
is then not related to the whole molten pellet, but to a layer of polymer, which coats and
adheres on the external surfaces of single sand particles [32, 34, 35]. The thickness of
this coating layer grows with a rate that mainly depends on temperature and degradation
kinetics as well as on polymer feed rate: in any case, measurements under different
operating conditions showed that its value is always of the order of 10 µm, therefore
making the physical resistances negligible (i.e. mass and heat transfer rates related to the
polymer mass) when compared with the chemical kinetics. As a consequence, whatever
the initial size of the plastic pellet, the primary reactions occur on the external surfaces
1
Figure 16.2 Sequence of steps that can occur after the injection of a polymer particle into a fluidized bed pyrolysers (adapted from
[35]). (Reproduced with permission from Elsevier)
451
Coated sand
particle
Polymer molten “drop”
Polymer layer
(a) (b)
Figure 16.3 Molten drop and Coated particle approaches for modelling of primary
cracking of polymers in a fluidized-bed reactor [5]. (Reproduced by permission of Rapra
Technology)
of particles having the same size and shape of the sand particles (Figure 16.3 B and
step 7 in Figure 16.2). This aspect is peculiar to the fluidized-bed pyrolysis and must be
taken into account in the modeling of process as well as in the definition of design and
operating criteria of the reactor. It allows considering a uniform temperature not only in
the fluidized bed, but even throughout the polymer layer, so that the solution of mass loss
rate equation can be strongly simplified [5]. The time for primary cracking as evaluated
by means of this coated particle approach is remarkably different (up to few orders of
magnitude) from that calculated by means of the molten drop approach [36] that considers
the reactions occurring throughout the whole molten polymer drop for which the internal
resistances are not negligible (Figure 16.3).
2.2 THE POLYMER DEGRADATION PROCESS
Just after the heating, melting and coating process the polymer undergoes a radical scission
of the chain that leads to the production of primary products. Depending on the operating
conditions of the reactor (temperature, gas residence time and type of fluidizing gas),
secondary and ternary reactions can become predominant. Figure 16.4 proposes a scheme
of possible reactions that lead to different products: it can help to explain the effect of
the operating parameters on the products of the process, specially with reference to the
different yields and composition of gas, liquids and waxes obtained, for a fixed polymer,
under different conditions (see Table 16.2).
The primary products are involved in a series of successive gas-phase reactions in the
different regions of the reactor. In a bubbling fluidized-bed pyrolyser, it is possible to dis-
tinguish three different regions, dense bed, splashing zone and freeboard, having a relative
extension that depends on the main design and operating variables [1]. Figure 16.5 indi-
cates the zones of the fluidized bed where reactions take place and that are characterized
by different hydrodynamic and thermodynamic conditions (and, as a consequence, by
Polymer Intermediate Gas

wax-like products
Primary
reactions Aromatics
Secondary
reactions
Ternary
reactions Coke
Figure 16.4 Reactions scheme for pyrolysis of polyolefins (adapted from [43]). (Repro-
duced by permission of the American Chemical Society)
Gas output, Qtot = Qfluidizing + Qproducts
Freeboard region.
Splashing zone. Voidage is close to 1.
Bubbles explosion induces mixing. Hydrodynamic regime is close to a plug-flow.
Gases begin to segregate. Segregation of gas is strong.
Secondary and ternary reactions Residence time can be calculated from superficial gas velocity.
proceed with different rates and yields. Heat and mass transfer rates are much lower
than those in the dense bed.
Dense bed: emulsion phase. Secondary and ternary reactions
Bed particles are fluidized at Umf. proceed with different rates and yield.
Heat transfer is favoured by
conduction/convection mechanism.
Mass transfer is favoured by bubbles Dense bed: bubble phase.
rising and by the corresponding Rising bubbles produced by the excess
circulation of bed particles. of gas above that for minimum fluidization (Qbubbles = Qfluidizing − Qmf).
The zone can be assumed as a CSTR. High frequency and rising velocity of bubbles are responsible
Residence time of gas produced in this of the mixing in the emulsion phase.
phase must be calculated by means of Low exchange mass rate between emulsion and bubbles phase
a hydrodynamic model. Reactions inside the bubbles are likely negligible.
Primary reactions occur on the polymer
that coats the bed particles.
Secondary and ternary reactions occur
in the gas inter-particles phase for a time Fluidizing gas, Qfluidizing
that must be calculated as above cited.
Figure 16.5 The different zones of a bubbling fluidized-bed pyrolyser where reactions
take place, with the indication of the specific hydrodynamic and thermodynamic features
different overall rates). These are maximized in the dense bed, due to the high quality of
contact and the good level of mixing; on the contrary, the gas stream segregation in the
freeboard implies a strong reduction of heat transfer and contact efficiency.
3 OPERABILITY RANGE OF FLUIDIZED-BED PYROLYSERS

3.1 THE PHENOMENOLOGY OF BED DEFLUIDIZATION
Stable, long-term operations of fluidized-bed reactors can be compromised by bed material-

to-polymer interactions, which can generate worsening of fluidization quality. Several inves-
tigations carried out with monopolymeric feeds of packaging wastes (PE, PP, PET and PVC)
as well as with mixtures of these wastes showed that, under conditions typical of low-
temperature pyrolysis processes (Table 16.2), there is a considerable risk of worsening in the
bed fluidization quality [32–35] that can eventually lead to the whole bed defluidization. The
phenomenon can occur in different ways, depending on the polymer type, and with different
rates, depending on the reactor temperature and other operating conditions as the polymer
feed rate and the bed amount and type. The sequence of steps that can lead to segregation and
defluidization phenomena is schematically sketched on the right-hand side of Figure 16.2.
For operation with polyolefins waste (such as PE and PP), the bed defluidizes as a conse-
quence of sintering between sand particles (sequence 1-2-3-4-5-9-11 in Figure 16.2). Some
aggregates surely form (step 4) at early instants but, since the polyolefins do not produce a
sticky carbon residue, they crumble rapidly (step 5) so setting several free sand particles.
These are covered by a layer of polymer that, at certain waste feed rates, has no time to
completely devolatilize, so becoming progressively larger. The polymer coating the particle
surface can be seen as a viscous liquid that completely wets the sand particles. When two of
these particles collide, their relative velocity could be too low to overcome the viscous adhe-
sion of the bridge between the surfaces [19, 37]. On the contrary, for operations with PET and
PVC wastes, a large formation of polymer-sand aggregates is observed. These, under a range
of temperatures between 450 and 650◦ C have a lifetime long enough to generate accumula-
tion, as a consequence of the presence of a sticky carbon residue. They take a large fraction
of the bed (up to about 25% at the lowest temperature) and have very high minimum fluidiza-
tion velocities. These aggregates are responsible for the beginning of segregation, with the
consequent worsening of the fluidization quality, and contribute to determine the occurring
of defluidization (sequence 1-2-3-4-6-10-11 in Figure 16.2), as confirmed by the evidence
of experiments carried out in hot and cold models. Some sintering between sand particles
however occur, probably promoted by the reduced momentum of bed material that, in turn,
is determined by the segregation effect [34, 35]. The behavior of plastic waste mixtures, in
particular those substantially made of polyolefins and PET, shows a synergistic interaction
between these two mechanisms: the presence in the mixture of just a small fraction of PET
(or of another polymer having a sticky carbon residue) induces a faster defluidization of the
bed while, when the PET content is gradually increased, the measured defluidization time
becomes substantially equal to that of tests with only PET [35].
Experimental and theoretical studies [32, 33, 35, 37] showed that, for different plastic
waste feeds (PE, PP, PET, their mixtures) and under a fixed reactor temperature, the time
of occurrence of defluidization for a bed of a given material is linearly related to the value
of the ratio between the bed solids hold-up and the polymer feed rate. The latter is a key
parameter of the process. Diagrams in Figure 16.6 summarize all the data obtained in
these experiments under different operating conditions and report the linear relationships
that fit the data very well for the specific temperature and plastic waste feeding.
3.2 PREDICTIVE DEFLUIDIZATION MODELS AND OPERABILITY MAPS
The considerations and the experimental evidence just described suggest that the reactor
design as well as the definition of process conditions need a tool, able to provide reliable
predictions for the on-set of fluidization worsening and bed defluidization. Mastellone and
Arena [37] proposed a predictive defluidization model valid for low-temperature pyrolysis
600
600
PE
550 PP
T = 450°C 550 T = 450°C
500 Ug = 0.22 m/s
500 Ug = 0.22 m/s
silica sand 0.3–0.4 mm
450 silica sand 0.3–0.4 mm
Ug = 0.046 m/s 450 Ug = 0.046 m/s
400 silica sand 0.09–0.2 mm silica sand 0.09–0.2 mm
Defluidization time,s
400
Ug = 0.4 m/s Ug = 0.4 m/s
350 350 silica sand 0.3–0.4 mm
300 tdef = 0.0186*Wbed/QPE Ug = 0.082 m/s
300
250 250 tdef = 0.0163*Wbed/QPP
200 200
150 150
100 100
50 50
0 0
0 2500 5000 7500 10000 12500 15000 17500 20000 0 2500 5000 7500 10000 12500 15000 17500 20000
Wbed/QPE, s Wbed/QPP, s
600 600
PET
550 T = 450°C PE-PP-PET mixture
550 T = 500°C
Ug = 0.22 m/s
500 500 xPET = 10%
450 Ug = 0.046 m/s xPET = 25%
450
silica sand 0.09–0.2 mm xPET = 40%
Defluidization time, s
400 Ug = 0.4 m/s 400

xPET = 100%
350 silica sand 0.3–0.4 mm 350
Ug = 0.082 m/s
300 silica sand 0.09–0.2 mm 300
tdef = 0.0235 * Wbed/QPET
250 250
200 200
150 150
100 100
50 50
0 0
0 2500 5000 7500 10000 12500 15000 17500 20000 0 2500 5000 7500 10000 12500 15000 17500 20000
Wbed/QPET, s Wbed/Qmix, s
Figure 16.6 Experimental defluidization times of different plastic wastes as a function

of ratio between bed amount and polymer feed rate [32, 33, 35]. (Reproduced with
of polyolefins, based on observed defluidization mechanisms and fluidization engineering

principles. It allows construction of an operability map that indicates if, for given reactor
geometry and on the basis of the main operating variables and of physical and chemical
properties of plastic waste, stable or unstable operations will be established inside the
pyrolyser. For the latter case, it is also able to provide the time at which defluidization
will occur, if no actions are managed by the plant operator. Figure 16.7 shows one of
these maps that, for fixed reactor geometry, can be used for PP pyrolysis. Since the
operating conditions (essentially, reactor temperature, plastic waste feed rate, fluidization
velocity, bed amount) cannot be considered as completely ‘free variables’ due to the
constraints that process and throughput requirements could impose, it might be possible
0.14
T = 450°C
0.12 Wbed = 360g
dsand = 350 micron
0.10
0.08
v0, m/s
Stable fluidization zone

0.06
0.04
0.02
0.00
0 10000 20000 30000 40000 50000
Wbed/QPP, s
Figure 16.7 The operability map of PP pyrolysis at 450◦ C, showing the zone of stable
fluidization and that of defluidization. v0 is the particle collisional velocity, which can be
evaluated as reported in [37]. (Reproduced by permission of AICHE)
that a process operation will be localized in the ‘unstable region’ of the map. In this case,
it is however possible to operate without defluidization risk by adopting a specific design
solution, adequately defined by means of a defluidization model. The solution imposes
that a continuous make-up of fresh particles has to be realized, together with simultaneous
withdrawal of a part of the bed. The feed rate of fresh material must be equal to that
of bed drain in order to avoid any increase of bed hold-up [32], and its value must be
determined by the defluidization model in order to avoid an excessive accumulation of
agglomerates in the bed or (for the sintering mechanism) to maintain the thickness of
polymer coating in a range of values limiting the adhesion forces. Defluidization models
have also been recently proposed for other polymers, such as PET and PVC [32, 38].
4 THE EFFECT OF THE MAIN PROCESS VARIABLES ON THE YIELD

AND COMPOSITION OF PYROLYSIS PRODUCTS
Thermal polymer degradation is determined by the chemical structure and length of the
polymer chain, by the presence of unstable structures (such as impurities or additives)
and by the temperature level inside the reactor, which must be high enough to break
the weakest, primary chemical bonds. Madorsky and Straus [39] found that some poly-
mers (such as PMMA and PTFE) mainly revert to their monomers upon heating, while
others (such as PE) yield a great many decomposition products. These two types of
dominant thermal polymer degradation are called end-chain scission and random-chain
scission, respectively. Chain scission, or depolymerization, is the successive release of
monomer units from chain-end or at a weak link, which is essentially the reverse of chain
polymerization; it is often called depropagation or unzipping. Random-chain scission (or
degradation) occurs by chain rupture at random points along the chain, giving a disperse
mixture of fragments which are usually larger than the monomer unit. The two types of
thermal degradation may occur separately or in combination; in the latter case, which is
rather normal, the chain depolymerization is often dominant [40, 41].
The main experimental results recently obtained in the field of fluidized-bed pyrolysis
of different plastic wastes are summarized in Table 16.4. All these studies utilize a bub-
bling bed type as experimental fluidized-bed apparatus, probably due to its easier design
and operating criteria. The information related to circulating fluidized-bed pyrolysers (or
to some other types, like the internally revolving fluidized beds commercialized by Ebara)
is limited and usually covered by industrial secrecy. Moreover, it is difficult to deduce
general considerations about the reactor behavior and the process performance under
different operating conditions since information about reactor geometry, bed material,
hydrodynamic variables as well as that related to procedures for sampling and chemi-
cal analyses is often deficient or sometimes completely missing. This, together with the
already mentioned scale-up difficulties in fluidized-bed reactor engineering, reduces the
relevance of the recalled experimental studies and the possibility of an immediate transfer
to the industrial scale.
Table 16.4 also lists the operating conditions used in the cited experiments, i.e. polymer
type, reactor size, reactor temperature, bed material type and size, fluidizing agent, flu-
idization velocity, as these are reported in the papers. A strong difficulty has been found in
deducing reliable data about gas residence time in the reactor, which is a crucial parameter
to characterize the spectrum of reactions and of possible products. The difficulty comes
from the complete absence of gas residence time data and/or of their calculation proce-
dure, as already complained of by other authors [43]. Due to the complex hydrodynamics
of bubbling fluidized beds (see [1] for the simple two-phase model or Kunii and Leven-
spiel model) is in fact not straightforward the evaluation of an average residence time of
gas: first, it is necessary to take into account the gas fed from the bed bottom and that
produced along the bed as pyrolysis product; then, it could be important to estimate the
gas fraction which is exchanged between the emulsion and bubble phases inside the bed;
finally, it is necessary to distinguish between the time spent along the bed and that along
the freeboard (these usually have different temperature profiles). This lack of information
(that probably means different residence times in different experimental studies), together
with the wide differences in reactor type and geometry, bed and freeboard temperature
profiles, sampling and analytical procedures, make it quite difficult, or often impossible,
to achieve a critical comparison of reported data.
The influence of the applied reaction conditions (temperature, residence time, concen-
trations of reactants and products) on the product spectra obtained from pyrolysis of
different plastic wastes could be estimated under the hypothesis of thermodynamic equi-
librium, as shown by Westerhout et al. [43]. They evaluated the maximum achievable
yield of valuable products during the pyrolysis of PE and PP, with the validation of
experiments carried out under conditions of controlled temperature and residence time. In
large-scale reactors the residence time and temperature control are difficult and certainly
Table 16.4 Main studies on plastic pyrolysis reported in the recent scientific literature 458
Plastic feed; bed material Apparatus Operating conditions Main results Reference
HDPE; sand Bubbling fluidized bed, Batch feeding Gas yield progressively increases [16]
69 mm ID U = 0.036 m/s from 5.7 to 96.5%. Methane,
T = 500, 600,700, 800, benzene, toluene formation is
900◦ C favoured by high residence times.
Gas yield reaches maximum at
800◦ C
Mixed plastics, HDPE; Bubbling fluidized bed, Fluidizing gas: nitrogen; Pyrolysis with steam as fluidizing gas [8]
quartz sand 154 mm ID nitrogen/steam demonstrates that the olefins yield
U = 0.17 m/s is increased due to water–gas
T = 600, 700, 800◦ C reaction.
Q = 1.1–1.4 kg/h Mixed plastics pyrolysis does not
allow optimization of process
temperature since styrene
production from PS requires low
temperatures while olefins
production from PE and PP
requires high temperatures
Mixed plastics; quartz Bubbling fluidized bed, Fluidizing gas: pyrolysis Pyrolysis of mixed plastics lead to [10]
sand 154 mm ID gas aromatics without chlorine yield of
U = 0.2 m/s 48%. Chlorine is present, together
T = 730◦ C with heavy metals, in the solid
fraction
Polyolefins; quartz sand Bubbling fluidized bed, Fluidizing gas: steam With the exception of experiments at [29]
154 mm ID T = 605, 655, 690, 700, 605◦ C, the gas fraction is the main
750, 805◦ C product (58–71%), having a
Q = 1–3 kg/h maximum yield at a temperature of
about 700◦ C. BTX-aromatics
increase from 1.6% at 605◦ C up to
16% at 805◦ C. Distillation residue
is higher at lower temperature (at
which heavier hydrocarbons are
produced) and at the highest (since
more condensed aromatics are
present). Chlorine is present in the

water and in the solids
Mixtures of LDPE, Bubbling fluidized bed, Batch feeding. Fluidizing Liquid and gas phase composition is [27]
HDPE, PP, PS, PVC, 100 mm ID gas: steam given.
PET; silica sand U = 0.072 m/s Gas yield reaches its maximum value
T = 500–700◦ C at 650◦ C
Mixed plastics from Bubbling fluidized bed, Fluidizing gas: nitrogen Two different mixtures of plastics [12]
DSD; quartz sand 154 mm ID T = 685, 710, 716, having different PVC content have
730◦ C been pyrolysed in order to evaluate
Q = 0.4–0.9 kg/h aromatics and light gas yields.
BTX represent the 20% of input,
gases the 44%. Chlorine is absent
in the aromatics compounds due to
reaction with CaCO3

PS, PE; FCC catalyst Bubbling fluidized bed, Fluidizing gas: nitrogen Effect of FCC catalyst on pyrolysis [25]
154 mm ID T = 370–515◦ C of PE and PP is studied. The
Q = 1 kg/h catalyst allows the use of
low-temperature for pyrolysis. The
catalyst induces a strong decrease
in aromatics yield (1–7% styrene
instead of 59–61%) for PS
pyrolysis, and in waxes yield (from
90 to 1%) for PE pyrolysis
HDPE, PP (0.1 mm); Bubbling fluidized bed, Fluidizing gas: nitrogen Two different catalysts were used for [18]
silica-based catalysts 25 mm ID U = 0.4, 0.6 m/s pyrolysis of PE and PP. The SA
(Sio2 :Al2 O3 :Na2 O) T = 400–550◦ C (SiO2 –Al2 O3 ) catalyst increases
the liquids yield
PE/PP/PS, alone and Bubbling fluidized bed, Fluidizing gas: nitrogen Composition of gas, liquids and [26]
mixed; quartz sand 130 mm ID T = 510◦ C waxes obtained with pyrolysis of
Q = 1–3 kg/h PP, PE, PS mixtures are reported.
Composition and yield of gases do
not change for a mixture of the
three polymers
459
460
Plastic feed; bed material Apparatus Operating conditions Main results Reference
HDPE; silica sand Bubbling fluidized bed, Fluidizing gas: The gas yield reaches the maximum [28]
48 mm ID air/nitrogen value at 780◦ C. The oxygen
ER = 0.06–0.07 increases the reactivity of
U = 0.11, 0.18 m/s degradation. Comparison between
T = 640, 700, 730, 780, aromatics yield with the two
850◦ C processes is reported
Filled or not PMMA; Bubbling fluidized bed, Fluidizing gas: nitrogen PMMA with and without filler has [13]
quartz sand 154 mm ID T = 450–480◦ C been pyrolysed at low temperature
Q = 0.3–3 kg/h (lab. (450 and 480◦ C). High monomer
scale) recovery has been obtained (98%).
Q = 30 kg/h (pilot The experiments were carried out
plant) also in a pilot plant 20 times larger
than the lab-scale
SBR (styrene-butadiene- Bubbling fluidized bed, Fluidizing gas: nitrogen, Low temperature pyrolysis [14]
rubber); quartz 154 mm ID steam (500–600◦ C) of tires produces a
sand U = 0.12, 0.28 m/s high carbon black yield (40% at
T = 500, 550, 600◦ C 600◦ C), styrene and butadiene.
Q = 1–3 kg/h Butadiene yield increases if
nitrogen is used instead of
pyrolysis gas due to suppression of
secondary and ternary reactions
Recycled PE; silica sand Bubbling fluidized bed, Fluidizing gas: nitrogen The effect of bed temperature appears [19]
55 mm ID U = 0.15, 0.28 m/s to play a crucial role in defining
yield and composition
T = 550–750◦ C
HDPE; silica sand Bubbling fluidized bed, Fluidizing gas: High yield of waxes and oils found at [30]
48 mm ID air/nitrogen 640 and 700◦ C. The presence of an
ER = 0, 0.06 incharacterized char is highlighted
U = 0.11, 0.17 m/s
T = 640, 700, 730, 780,
850◦ C
Q = 3–4 g/min
Waste tire powders; not Bubbling fluidized bed, Fluidizing gas: Calorific value of gas increases if ER [42]
specified 100 mm ID air/nitrogen decreases. Oil and char content
ER = 0.07–0.41 decreases if ER increases
T = 350–900◦ C
Q = 2–4 kg/h
Recycled PP; quartz sand Bubbling fluidized bed, Fluidizing gas: nitrogen A specific procedure is adopted to [31]
55 mm ID U = 0.13, 0.28 m/s change gas residence time inside
T = 550–750◦ C the bed and along the freeboard.
The bed temperature remarkably
affects the composition of gaseous
products
ER = equivalent ratio; Q = plastic feed rate; T = bed temperature; U = fluidizing velocity

461
far from ideal: this may lead to excessive cracking of the desired intermediate products to
undesired side products [43]. The estimation of the ultimate, maximum achievable, yield
and the influence of different reaction conditions can then be utilized to optimize the
product spectrum in industrial-scale reactors. On the other hand, the differences between
the results of ultimate yields and those of laboratory- or pilot-scale experiments reported
in Table 16.4 can be related to the actual reaction conditions and, in particular, to the
limited residence time, even though the doubtful purity of many polymers may also be
responsible for many of conflicting results reported [41]. In the following, the results of
some of the main experimental studies listed in Table 16.4 are described, by using the
following distinction for the pyrolysis product fractions [26]: gases (up to C4 ); oils (boiling
point <300◦ C, n-C5 – 17 , i-C5 – 20 ); light waxes (bp 300–500◦ C, n-C18 – 37 , i-C21 – 50 ); heavy
waxes (bp >500◦ C, > n-C37 , > i-C50 ); soot, carbon black.
4.1 FLUIDIZED-BED PYROLYSIS OF MONOPOLYMERIC WASTE
Polyethylene (PE). Pyrolysis of PE proceeds via a random degradation mechanism that

initiates by C–C bond scission at the weakest points in the chain and propagates via decom-
position of the macroradicals to produce smaller fragments and, depending on temperature
and residence time, lighter hydrocarbons, aromatics and coke (i.e. aromatic compounds
with two or more benzene rings). Table 16.4 reports related recent papers, which include
interesting observations about the effect of small fraction of oxygen in the fluidizing gas,
that of temperature and residence time and that of catalyst used as bed material. Again,
the differences in the operating conditions do not allow a coherent comparison, but it is
possible to say, accordingly to some fundamental previous papers [8–10], that the gas
and aromatics yield increases with temperature and residence time. An analysis of studies
carried out at temperatures between 450 and 750◦ C [16, 19, 28] shows in fact that: at
450◦ C, the main product is a wax-like fraction (as that shown in Figure 16.8); at 500◦ C,
the solid fraction is substantially negligible and gas and liquid products are obtained;
in the range 650–750◦ C, different studies found the maximum yield of gases (its value
moving from about 40% [16] to 65% [19] until 100% [28]). In order to achieve the same
gas yields at lower temperatures, it is not sufficient to increase the gas residence time
(the typical range for fluidized-bed reactors is about 0.5–5 s) and an intervention on the
dissociation energy is necessary. Mertinkat et al. [25] studied the effect of a catalyst on
PE pyrolysis and indicated that an advantageous product spectrum could be gained by
using a FCC catalysts in a temperature range 370–450◦ C: C3 and C4 gases, together with
BTX and ethylbenzene, can be produced in large quantities with an energy demand much
lower than that of a noncatalytic process.
Polypropylene (PP). Pyrolysis of PP is favored by the branched structure of the poly-
mer: the thermal degradation also proceeds in this case via a random-chain scission, but
the influence of the temperature on the product spectrum is more pronounced than in the
case of PE [43, 31]. At temperatures as low as 515◦ C, Predel and Kaminsky [26] found
that PP pyrolysis leads to the production of 6.8% of gases, 36.7% of oils, 21.6% of light
waxes and 34.6% of heavy waxes. At these low temperatures the main compounds in the
gas fraction are propene and butenes (about 51 and 17% in [26]), but at higher tempera-
tures these products are converted into others [43]. Ponte et al. [31] found a remarkable
Figure 16.8 Scanning electronic microscope pictures of degraded PE as obtained at

450◦ C and U = 0.2 m/s (see [19] for details). (Reproduced with permission from Elsevier)
effect of temperature in the range 500–750◦ C, both on the yield in gaseous products
and on their composition: at higher temperatures the highest values of solid yields and
methane content were measured. This is in agreement with the finding [43] that, at the
equilibrium state (i.e. at very long residence time and/or at very high temperatures), PP
degradation yields methane and coke as the main reaction products. As already observed,
the discrepancy in the cited values of experimental results can be partly justified by con-
sidering the differences in reactor size and geometry, temperature and residence time.
The effect of gas residence time in the different region of the reactor has been recently
investigated, by means of experiments with different bed hold-up (to change the bed
residence time) and with different fluidizing velocity (to change the freeboard residence
time) [31]. Results suggest that a longer residence time inside the bed increases the gas
yield, while a longer residence time along the freeboard does not substantially modify the
gas yield, but affects the gas composition, with increased methane and hydrogen contents
and reduced percentages of heavier hydrocarbons.
Fluidized-bed pyrolysis of virgin or recycled PP has been recently proposed [44] as an
innovative and low-cost production process of carbon nanotubes (CNTs). It is known that
the very high aspect ratio and extraordinary mechanical, electrical and thermal proper-
ties of CNTs can be extremely useful in several fields of application, but the high cost
of production currently limits wider industrial utilization [45]. The new technique uses
fluidized-bed reactors to obtain high heating rates of the injected polymers, high heat and
material exchange coefficients and a reliable control of gas and solids residence time in
the bed and the freeboard [44]. The process, which is still in the development state, has
also been successfully carried out with recycled PE and PET and with their mixtures [46].
It should allow a continuous and low-cost production of CNTs, having a degree of purity
compatible with most of the applications already known for this type of nanostructured
material (Figure 16.9): this could largely extend the potential market of CNTs in a number
of applications as, for instance, those of composite materials.
Polystyrene (PS). The thermal degradation proceeds again by C–C scission, which
is then followed by a complex radical chain reaction. In the early stages of reaction
and at low temperatures (290◦ C), the primary products are styrene, diphenylbutene, and
triphenylhexene. At higher temperature or longer residence times, the final stable products
are toluene, ethylbenzene, cumene, and triphenylbenzene [47]. Fluidized-bed pyrolysis
was applied successfully to pure PS: more than 60% of monomer and 25% of other
aromatics were obtained at a pyrolysis temperature of 515◦ C [25, 26].
Polyethylene terephthalate (PET). At temperatures above 300◦ C PET pyrolysis proceeds
via a random-chain scission of the ester links to yield a mixture of terephthalic acid
monomer and vinyl ester oligomers [47]. The presence in the monomer of oxygen and a
benzene ring implies that the decomposition products contain aromatic and oxygenated
carbon compounds, like CO2 , ketones and aldehydes [27].
4.2 FLUIDIZED-BED PYROLYSIS OF MULTIPOLYMERIC WASTE
In the last decade several studies focused on the pyrolysis of plastic mixture in BFB
reactors, operated under different conditions of temperature, fluidizing gas, bed material,
reactor size and geometry [10, 12, 26, 27, 48]. Particular attention has been devoted to the
effect of PVC presence on the determination of yield of chlorinated aromatics [10, 12, 27].
The effect of temperature, which has been also well studied [12, 27, 48], appears to be
in accordance with that described for single polymer feeding: an increase of temperature
leads to an increase of yields in gas and aromatics and to a decrease of waxes. It is
however noteworthy that the temperature value has to be selected on the basis of mixture
composition, in order to optimize the desired products. In fact, most of polymers produces
aromatics at higher temperatures and residence times (PE, PP) while others (like PS) do
so at lower temperatures.
Figure 16.9 (A) Scanning electronic microscope picture of CNTs as obtained from PP
(B) Transmission electronic microscope picture of CNTs as obtained from PE
The interaction between pyrolysis products coming from different polymers present in
the mixture has been also investigated [26, 43, 48]. The pyrolysis of polymer mixtures
appears to have no significant mixing effect on the product spectrum in comparison with
the spectra obtained from the pyrolysis of pure polymers. This finding is contradictory to
other pyrolysis methods (see, for instance, [49]) and is another indication that predomi-
nantly unimolecular reactions determine the product spectrum since the presence of other
components does not influence it [43]. In particular, Predel and Kaminsky [26] found that
adding 10% PS to either PE or PP or a PE–PP mixture does not change significantly
the distribution of products fractions, apart from additional PS degradation products. The
compositions of the products also remain substantially similar, even though when PS is
added to PP the peak distribution of the waxes changes significantly, although its amount
remains constant.
4.3 FLUIDIZED-BED PYROLYSIS OF OTHER POLYMERIC WASTES
Fluidized-bed pyrolysis of rubber tires has been carried out over a temperature range
from 500 to 740◦ C. A recent study [14] indicates that operation between 500 and 600◦ C
leads to a production of a large amount of solid phase (>60%), made of carbon black
and distillation residue, together with a remarkable amount of distillate (25–30%) and a
limited amount of gases (3–9%). The most valuable fraction is the carbon black: its yield
and quality being an important criterion for the economic evaluation of the process. The
carbon black yield increases from about 30% at 500◦ C to about 40% at 600◦ C. The use of
steam instead of nitrogen as fluidizing gas does not significantly affect yield and quality of
the carbon black nor the yields of the other product fractions. The main product in the gas
fraction is 1,3-butadiene, the monomer of the original rubber. In the steam experiment,
there are also significant yields of CO2 and CO, resulting from the reaction of carbon
black with water to carbon oxides and hydrogen. The latter appears to increase the degree
of oil desulfurization due to the production of H2 S [14].
Waste from electrical and electronic equipment (WEEE) has an absolutely remarkable,
total amount considering that several millions tons are produced only in the European
Union. In a mixed WEEE stream about 75% is made of metals, glass and wood that can
be mechanically recycled while the plastic fraction accounts for 15–20%. This fraction
contains some minor flame retardants additives (such as polybrominated diphenyl ether)
that can form toxic compounds when incinerated. This aspect, together with the presence
of various polymeric materials (both thermoplastic and thermoset), makes pyrolysis a
viable recycling solution. WEEEs are first shredded and then pyrolysed at temperatures in
the range 700–900◦ C, with some interesting advantages. The metals are not oxidized and
thus they can be separated and recovered from further use; the flame retardant additives
are split off in the form of hydrohalogen gas during the process and then removed.
Limited information about technical and economical feasibility of processing of WEEE
by means of thermal processes is available, even though a recent study [50] made a careful
assessment of available processes. Six criteria (energy efficiency, bromine and antimony
recovery, emissions, quality of residues, operational experiences and profit expectations)
were utilized to score all the examined technologies. The composition of plastic fraction
of WEEE has comparable aspects to that of automotive shredder residue (ASR), except for
high metals content. Therefore, in identifying processes for WEEE treatment, operational
experiences with ASR, particularly by means of fluidized-bed reactors [51, 22] give a
good indication of possible performances. Table 16.1 gives information about some of
the processes suitable for pyrolysis of WEEE and ASR (Akzo, Compact-Power, Ebara
TwinRec, Hamburg, Mazda, NKT, PKA, Veba Oel, Takuma, Toshiba, Von Roll): those
carried out by means of fluidized-bed reactors are the well-known Hamburg process and
the Akzo and Ebara TwinRec processes, described in the following paragraph.
5 OPERATING EXPERIENCE WITH INDUSTRIAL FLUIDIZED-BED
PYROLYSERS
Table 16.1 reports an up-to-date list of the main pyrolysis processes that can be utilized
for material and energy recovery from different type of plastic wastes. In the following,
brief descriptions are given of three of them, having a different commercial status, and
involving a bubbling, a circulating and an internally revolving bed, respectively. The
aim is to give an essential summary about the technical process, its environmental and
economic performance and its current commercial status.
5.1 THE BP CHEMICALS POLYMER CRACKING PROCESS
BP Chemicals has led promotion of a fluidized-bed cracking process that could be used to
convert plastic waste into petrochemicals. The Polymer Cracking Process was first tested
on a laboratory scale and then on a continuous pilot scale (having a nominal 400 t/yr
capacity) at BPs Grangemouth site in the UK.
Description of the process. Prepared mixed waste plastics, oxygen free and with a
maximum of 5% of nonpolymeric impurities, are introduced into a bubbling fluidized-bed
reactor, where the low-temperature cracking reaction takes place (Figure 16.10). The bed
is made of sand and is fluidized in an inert atmosphere by nitrogen and/or recycled light
hydrocarbons and heated at about 500◦ C by fired tubes which provide the endothermic
heat of reaction. As the plastics enter the reactor, they quickly melt and coat the sand
particles with a thin layer of polymer. This undergoes thermal cracking and produces
lighter hydrocarbons that leave the bed with the fluidizing gas [21, 32]. The gaseous
products are purified first in a cyclone, which removes the bulk of the entrained fines (made
of a mixture of coke, sand and residual plastic additives) and then in a successive guard
bed, which catches the chloride content coming from PVC destruction by the reaction
of CaO with HCl. The main result is a spent CaO/CaCl2 that has to be landfilled. The
gas exiting the guard bed is purified via cyclones and a collection hopper to remove the
CaO/CaCl2 fines. An intermittent withdrawal of material from both fluidized-bed reactor
Mixed Plastic
Wastes Cyclone Cyclones
Fluidized Venturi Condenser

bed Guard loop Gas
reactor Bed system
Lime
Liquid
Coke, sand, Solid Fines Filter

Nitrogen Wax
residual additives residues
Light hydrocarbons
Figure 16.10 Flowchart for the BP Polymer Cracking process

and guard bed is necessary to purge the bed from accumulated unwanted materials. The
gas resulting from the process is collected in a two-stage process. A Venturi loop system
partially condenses the gas to give a waxy hydrocarbon product. This is condensed first
and filtered to remove remaining fine solid particles: its high degree of purity allows the
mixing with naphtha at levels up to 20% so that the resulting mixture can be directly
utilized in a steam cracker to give classic petrochemical products. The noncondensed
gas stream is compressed, reheated and returned to the cracking reactor as fluidizing
gas: excess gas is continuously removed as a product to keep the process operating at a
pressure of about 4 barg and partially used as fuel for indirect heating of the fluidized
reactor [47, 21, 52].
Process performance and commercial status. The Polymer Cracking Process has an
efficiency of approximately 80% conversion of plastic waste to petrochemical products
with an additional 10–15% utilized as fuel gas in the process itself [21]. The hydrocarbon
feedstock obtained is of high quality while the waxy product can be used as feedstock
material for steam crackers or can be fed into refinery units (such as the FCC unit). It
is not easy to give reliable data about environmental and economic performances since
the process is still in the development stage [53]. However all the emissions should be
very low and should comply with local regulations. Total solid waste products (which
include both feed plastic and the solids used as make-up) are typically up to 0.2 kg/kg of
total solids feed [23]. The overall environmental performance of the process has been also
evaluated and compared with those of alternative options for waste plastics management in
a couple of life-cycle analyses [52, 54]. Both the LCAs highlighted that, in particular with
reference to energy consumption, the BP process has a performance worse than those of
mechanical recycling, monocombustion and of a couple of alternative feedstock recycling
processes. The recent process developments seem to work in the direction of an improved
energy efficiency that could change the results of the above-mentioned comparison [53].
The economic performance of the process will depend on many factors (plant scale,
preparation stages, location, etc.). Some information has been produced by BP Chemicals
and indicated an investment of ¤23–30 million for a 25 000 t/yr plant in Western Europe
(1998 prices), which implies a gate fee of about 260 ¤/t. These figures have an uncertainty
of ±30% and include product values but exclude collection and preparation [23].
5.2 THE AKZO PROCESS
Akzo Nobel is an important producer of chlorine, vinyl chloride and PVC, strongly inter-
ested in a process for feedstock recycling of MPW containing PVC. Since 1994 they have
chosen a fast pyrolysis process in a circulating fluidized-bed reactor, based on the tech-
nique developed by the Battelle Memorial Institute (CO, USA) for biomass gasification.
Description of the process. The process involves the utilization of two separate CFBs,
both operated at ambient pressure (Figure 16.11). The first is a flash pyrolysis reactor in
which waste is converted with the addition of steam, at a temperature between 700 and
900◦ C, into product gas and tar. The reducing atmosphere avoids the dioxins formation.
The product stream, made of fuel gas and HCl in a composition strongly dependent on
feed/steam ratio, is quenched to recover HCl, which is then further purified. The second
CFB is a combustor that provides heat for flash pyrolysis by burning the residual tar: the
Fuel gas
Separation
Quencher
unit
HCl
PVC Flue gas
Nitrogen Sand, inorganic solid
wastes residues, char
Separation
Fluidized unit
bed Fluidized
reactor bed
combustor
Steam or Recirculated
heated sand Natural gas/air/oxigen
nitrogen
Nitrogen
Figure 16.11 Flowchart for the Akzo–Nobel process
heat transfer between the two units occurs by the circulation of heated sand. The choice
of CFB technology allows high PVC waste throughputs [23].
Process performance and commercial status. The Akzo process was investigated on a
pilot scale (30 kg/h) with PVC cable and pipe scrap. Some tests with mixed PVC waste
were carried out on a larger scale (300 kg/h) with the support of the European Council
of Vinyl Manufacturers, giving promising results. At the moment the project is on hold,
even though there is a plan to realize an industrial-scale plant, with a capacity of about
50 000 t/yr. On the other hand, Akzo Nobel has stopped all activities on HCl recycling
from PVC [50]. The process is still at pilot-scale status, so that large uncertainty exists
about its technical, environmental and economic performance.
5.3 THE EBARA TWINREC PROCESS
Ebara Corporation developed the TwinRec process as an innovative combination of two

existing waste-to-energy technologies: the twin internally revolving fluidized bed (IRFB)
combustion technology and the Meltox combined combustion and ash melting technology.
The name TwinRec emphasizes the combined recovery of energy and material from
different wastes, in particular those coming from dismantling and shredding process of
vehicles (ASR). The former license agreement with ALSTOM Power (CH) was terminated
in 2002 and now Ebara provides the technology on their own.
Description of the process. The simplified process flow diagram is shown in Figure 16.12.
The shredder waste (ASR, plastic and electronic waste as well as MSW) is fed in an IRFB,
which operates in a reducing atmosphere and at temperatures as low as 500–600◦ C, allow-
ing easy control of the process. The IRFB reactor separates the combustible portion and the
dust from the inert and metallic particles of the fed waste: the obtained mixture of metallic
and inert particles is sent to a mechanical metal separation while fuel gas and carbonaceous
particles are burnt in a cyclonic combustion chamber for energy production and fine ash
vitrification. Metals such as aluminium, copper and iron can be recycled as valuable prod-
ucts from the bottom off-stream of the IRFB as they are neither oxidized nor sintered with
Shredded Power
wastes Air Air
Lime
Fluidized Cyclonic Heat Flue gas

bed combustion boiler cleaning Flue gas
reactor chamber unit system
Granulated Solid
Ash
slag residues
Separation
unit
Metals Bottom ash
(ferrous/ (glass, stones, etc.)
non-ferrous) Landfill
Figure 16.12 Flowchart for the Ebara TwinRec process
other ash components. After metal recovery, the bottom ashes, which are about the 7–10%
of the waste throughput and have a low carbon and heavy metals content, are sent to land-
fill [51, 20, 22] or can be recycled directly, similar to stocker grate bottom ash, or even be
upgraded by vitrification in the existing ash melting furnace [55]. The combustor operates at
1350–1450◦ C with secondary air addition but without auxiliary fuel. The furnace operates as
a slag tap, with the ash encouraged by the cyclonic action of the air to adhere to the refractory
walls and to flow as a molten slag through the slag tap at the furnace bottom: the molten slag
is then quenched with water and obtained as granulate that can be sold to the construction
industry. The process involves a reduced flue-gas flow rate, which allows for a size reduction
of steam boiler and pollution control units.
Process performance and commercial status. The process can be integrated into existing
recycling schemes by the co-operation with shredding plants, specialized nonferrous sep-
aration plants, the construction industry and the district heat and/or electricity off-taker.
This possibility of integration, together with the avoidance of intermediate pretreatments,
gives attractive environmental and economic performance to the process. In particular,
each recoverable component of the shredder residues has a chance of recovery (metals
are recycled, inert minerals are separated from organics and dusts and recycled, mineral
dusts and metal powders are bound into the glass granulate and recycled) while organic
pollutants are destroyed and the final amount to landfill is reduced. The Ebara process
also shows a wide flexibility on the input wastes, being possible the operation with
ASR and MSW as well as that with plastic waste of electrical and electronic equipment
(WEEE). A TwinRec plant with electrical energy production achieves a net efficiency of
17–25%; if electricity and heat are produced, the net efficiency can be raised to 70%.
As already mentioned, the economic performance depends greatly on the specific project
(plant scale, location, required standards, combinations with existing structures, etc.). As a
rough indication, for ASR the investment cost is between 600 and 1100 ¤/(t/y of installed
capacity) with a gate fee (2004 prices) between 100 and 230 ¤/t [55]. The TwinRec pro-
cess has full commercial operation status. Two pilot plants (1.5 and 5 MWth, respectively)
operated in Japan since 1995, with different wastes, including ASR and WEEE. At the
beginning of 2004, 20 commercial lines were in operation. The Aomori (J) plant has a
capacity of 2 × 10 t/h (about 2 × 40 MW thermal input) and is fed with 70% shredder
residues and 30% mechanically dewatered sewage sludge. Other plants are at Kawaguchi
(3 × 21 MWth), Kurobe (7.4 MWth), Sakata (2 × 12.3 MWth), Ube City (3 × 9.5 MWth)
and Chuno Union (3 × 7.3 MWth). Recently, Ebara received an order from Malaysian
government for a very large plant (1500 t/d) for MSW treatment to be built in Selangor
Province and one more from Tokyo Rinkai Recycle Power Co. for a 550 t/d plant for
treatment of nonhazardous industrial waste to be located on an island in Tokyo Bay.
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17
The Hamburg Fluidized-bed

Pyrolysis Process to Recycle
Polymer Wastes and Tires
WALTER KAMINSKY
Institute for Technical and Macromolecular Chemistry, University of Hamburg,
Bundesstr. 45, 20146 Hamburg, Germany
1 INTRODUCTION
After the first oil crisis in 1975, there was great interest in feedstock recycling of polymers
to recover oil and gas from this hydrocarbon source. Another goal was to protect the
environment from landfilling of plastic materials that decompose very slowly.
The problem for cracking plastics into oil was the low heat transfer, the high heating
energy needed for cracking and the different impurities such as inorganic fillers, food
residues, and paper. Under the leadership of H. Sinn it was decided to build at the
University of Hamburg a process which was able to use filled and dirty plastics in a fast
pyrolysis process [1]. We used an indirectly heated fluidized-bed process to avoid mixtures
of incineration exhaust gases with the pyrolysis products, but with the advantage of an
excellent heat transfer. Up to this time, only a few fluidized-bed had been described
processes for plastics cracking in Japan using air as fluidizing gas and partial incineration
by oxygen to cover the cracking heat.
Polystyrene bottles were pyrolyzed by the Japan Fluid Cracking process (JFC) in a
fluid sand bed reactor of 500 mm diameter and with a capacity of 1 t/day [2]. The oily
products were contaminated by oxidized compounds.
In the years from 1973 to 2005, different size fluidized-bed reactors were built at the
Institute for Technical and Macromolecular Chemistry, continuously working with plastics
throughput of 50 g/h (LWS 1), 500 g/h (LWS 2), 2 kg/H (LWS 3 + 4), 3 kg/h (LWS 5),
a small pilot plant of 10–30 kg/h (TWS1) for plastics, and a pilot plant of 100–200 kg/h
for whole tires (TWS2) [3–5]. All reactors were heated indirectly, the small laboratory
sizes electrically from the outside, and the pilot plants by heating tubes with incineration
476 W. KAMINSKY
of gas (at first propane, later in a run by pyrolysis gas). A flow scheme of a laboratory
plant is shown in Figure 24.1 in a later chapter in this book.
The experiments at the University of Hamburg led to the building of three pilot plants
by companies. The first was built in 1982 in Ebenhausen, Bavaria by DRP/ABB using a
fluidized-bed reactor with a diameter of 1800 mm and a capacity of 800 kg/h of mixed
plastics and whole tires. The second plant was built in Grimma, GDR in 1984 for whole
tires with a capacity of 5000 t/yr. BP also carried out preliminary experiments 1992
at the University of Hamburg and then built a pilot plant in Grangemouth, Scotland
with a capacity of about 5000 t/yr to obtain waxy products from mixed plastics, mainly
polyolefins. These waxy products could be used as feedstock for naphtha-crackers. All
pilot plants ran for only a few years, mainly because economically operation was not
possible due to decreasing crude oil price.
The Hamburg process can be varied by some simple process parameters such as pyrol-
ysis temperature, type of fluidizing gas (nitrogen, steam, cycled pyrolysis gas), residence
time to produce different products from plastic waste (Table 17.1).
The Hamburg process was also used for oil and gas recovery from oil shale, oil sand,
and biomass such as wood (flash pyrolysis), lignin, bark, oil seed, and fat [6–8].
2 PILOT PLANT DESCRIPTION
The scheme of the pilot plant is shown in Figure 17.1. At the heart of the plant is
a fluidized-bed reactor with an inside diameter of 450 mm and a height of 900 mm.
This bed part is followed by a 1075-mm-long freeboard zone in which there is no sand
fluidizing. The height of the sand bed (fluidized bed) is 650 mm. The sand has a particle
size of 0.3–0.7 mm. The reactor is heated by four steel heating tubes which use propane
or the excess gas of the pyrolysis products (Figure 17.2). For feeding, there are three
possibilities: a screw conveyor, a tube for liquid feed from the side, and a lock with two
flap valves for material from the top of the reactor. The feeding system consists of a screw
conveyor nearer to the hooper which controls the amount of the feed and a fast-moving
screw conveyor directly at the reactor which brings the feed into the fluidized bed very
rapidly to avoid the formation of glue and congestion. This screw conveyor is cooled by
a water double jacket. The lock with the two flap valves is used for big pieces of plastics
or for material with a high viscosity. The capacity of the pilot plant is between 10 and
30 kg feed per hour.
Table 17.1 Variation of the Hamburg pyrolysis process feeding polyolefins by different temper-
atures and fluidization gases
Temperature (◦ C) Fluidizing gas Products

400–550 Nitrogen, steam, 70–90% waxy products/oil, 2–9% gas
cycled pyrolysis gas
550–700 steam 60–70% oil and aliphatics, 30–40% gas
700–800 Nitrogen, steam 70–80% gas, mainly ethylene and
propene, 20–30% oil
700–800 Cycled pyrolysis gas 30–50% aromatics, 30–55% gas,
1–10% soot
Cryostat
Lock
Distillation columns
Cyclone Quench Electrostatic

cooler Scrubber Scrubber precipitator Water
Silo
Water
Water
Steam
Reactor Steam
HAMBURG FLUIDIZED-BED PROCESS
Cryostat Oil
Pyrolysis oil
Oil
Overflow
Compressed vesel
air
High
Xylene Toluene Benzene
boiling
Propane fraction fraction fraction
fraction
Sulphur gas Chimney

Exhaust Compressor
Fluidizing gas
gas Flare
Heat Gasometer
exchanger
Pyrolysis gas
Figure 17.1 Scheme of the pilot plant TWS of the Hamburg process for pyrolysis of 30 kg plastics per hour in a fluidized-bed
reactor
477
478 W. KAMINSKY
Figure 17.2 View inside the fluidized-bed reactor from the bottom with four fire tubes
and the hole for feeding
The bottom of the fluidized bed has an incline of about 15◦ and carries the bent gas-
inlet tubes. These tubes are movable vertically so that their distance from the bottom of
the fluidized bed can be varied. With this arrangement, there is a variable settling zone
for small metal pieces and stones which occur as impurities of the plastic waste.
Behind the fluidized bed reactor there follows a cyclone for separation of solids. Then
the product gases pass a washing cooler; in this cooler, xylene is cycled and used as
cooling medium and solvent. It washes the cooler free from waxes and other high-boiling
products. Heat transfer occurs in a tube heat exchanger. After this, the cooled product
gases pass two packed columns in which xylene is used as quenching medium. This
solvent is cooled down to −5◦ C by a cryostat running with ethanol. Before the gas
is compressed, it is cleaned up from fog by an electrostatic precipitator (electrofilter).
Compression is effected by five membrane compressors. Two of them transport the gas
directly into the fluidized bed. The other three press the gas into three steel gasometers.
From this, a part of the gas is used for fluidizing the bed; it can be controlled and is mixed
with the other gases. The correct flow gas rate is the sum of both gases. If a high flow
gas rate is necessary, three membrane compressors can directly pump the gas into the
fluidized bed. The capacity of a compressor is higher if the pressure is less. The excess
gas of the pyrolysis can be burned in the fire tubes or in a flare on top of the building.
HAMBURG FLUIDIZED-BED PROCESS 479
In a separate room (in case of explosion) the distillation and quenching columns are
installed. In the two distillation columns, four distillation boiling cuts can be obtained from
the pyrolysis oil. In the first column with a diameter of 150 mm and a length of 10.5 m,
the fraction with a boiling point of more than 180◦ C is split off from the distillation
residue. In the second column with a diameter of 80 mm and a height of 8 m cuts of
80◦ C, 110◦ C, and 140◦ C (xylene) are obtained. The xylene is used as quenching oil also
in the coolers.
The plant is controlled by a process computer (ABB-Hartmann and Braun) and equipped
with numerous data-collecting instruments. Surveillance is carried out by continuous anal-
ysis of the room air as well as by explosion-limit controls. The pyrolysis gas is analyzed
automatically by a gas chromatograph. All data obtained are registered to enable calcu-
lation of energy and mass balances. Some basic components are continuously monitored
by infrared spectroscopy, i.e. ethylene in the pyrolysis gas, sulphur dioxide and oxygen
in the exhaust gas.
The heating of the fluidized bed by fire tubes was necessary to up-scale the plant. The
Ebenhausen plant and the Grimma plant used fire tubes, for heating. A scheme of the fire
tube is shown in Figure 17.3.
The fire tube consists of two tubes. The outer tube is closed in front, while the inner
tube is open. The flame is started at the burner lead and the exhaust gases passes between
the inner and outer tubes. They are collected outside the reactor and go through a heat
exchanger in which the incoming gas for fluidizing is heated up. There is no mixing of
exhaust and product gas. The whole reactor is shown in Figure 17.4, isolated by rock
wool.
In one run, 200–500 kg of plastic materials are pyrolyzed and 50–150 L of oil and
20–290 kg gas are obtained. The products are analyzed by GC and GC-MS with four
different separation columns.
1 2 3 4 5 6 7
Figure 17.3 Fire tube for heating of the fluidized bed. 1 closed outer tube; 2 open inner
tube; 3 ignition; 4 reactor wall; 5 outlet for exhaust gas; 6 inlet for air; 7 inlet for propane
or gas; 8 spark plug; 9 burner head
480 W. KAMINSKY
Figure 17.4 Isolated fluidized-bed reactor with the outside fire tubes (middle), the screw
conveyor for feeding (right) and the drump for inorganic fillers from the overflow (left)
2.1 PYROLYSIS OF WHOLE TIRES
Fluidized sand beds are surprisingly insensitive to the unit size of the feed material.
Pieces of scrap tires up to a weight of 2.7 kg each were fed and quantitatively pyrolyzed.
These results offer the perspective for a pyrolysis process for scrap tyres without prior size
reduction. Most pyrolysis processes use feed crushed to a 200–20 mm size which involves
considerable expense [9]. Successful pyrolysis experiments in an indirectly heated rotary
kiln have been conducted by Kobe Steel [3].
In cooperation with the Hamburg company C.R. Eckelmann, a pilot plant fluid-bed reac-
tor (TWS 2) for a 1.5–2.5 t/day throughput of scrap tires has been built at the University
of Hamburg (Figure 17.5). Its particular construction shows horizontal, fluidizing-gas inlet
7
2
9
3
10
Figure 17.5 Scheme of the pilot plant for the pyrolysis of whole scrap tires. 1 steel wall
with fireproof walling; 2 fluidized bed; 3 tiltable grate; 4 radiation fire tubes, two layers,
third layer inlet tubes for fluidizing gas; 5 nozzles to remove sand and metal; 6,8, and 9
flanges for observation and repairs; 7 gas-tight lock; 10 shaft for steel cord
tubes. The fluidized-bed reactor has a square inner size of 900 × 900 mm and a height of
3200 mm [10].
The pyrolysis zone itself, i.e. the fluidized sand bed, indirectly heated by seven fire
tubes in two layers, has a fireproof wall. The whole tires roll through a gas-tight lock into
the reactor. A tiltable grate is extended into the fluidized sand to remove the steel cord
482 W. KAMINSKY
from the pyrolyzed tires. On top of the tiltable grate, the fluidized bed extends to a size
of 1000 × 1000 mm to form a freeboard and to provide sedimentation of the sand.
The pyrolysis products, together with the fluidizing gas (i.e. the noncondensable pyrol-
ysis gases), leave the reactor via a cyclone, where dry carbon soot and filler materials
are precipitated. A cooling system and an electrostatic precipitator condense the liquid
fraction of the pyrolysis products. The waste heat is used to heat up the fluidizing gas.
A stream of pyrolysis products is branched off the main product cycle and refined in the
rectification unit described for the smaller test plant.
The investigations up to now suggest that this fluidizing technique allows the formation
of a stable fluid bed with a minimum of coagulations, independent of the size of the feed,
which, of course, causes a significant viscosity change inside the bed. In addition, this
construction allows the use of the inclined bottom of the reactor as a settling zone for the
metal pieces.
The throughput of the plant is definitely limited by the capacity of heat radiation of the
commercial fire tubes. The prototype reactor allowed a space-time yield of 1.3 t/m3 fluid
bed per hour. The heating value of the pyrolysis gas produced was sufficient to balance
the heat demand of the process.
3 PYROLYSIS PRODUCT COMPOSITION
Tables 17.2–17.5 show some detailed product composition of different plastic feeds,
pyrolyzed in a laboratory or pilot plant [11, 12].
It can be seen that under these conditions high amounts of aromatics are produced. The
benzene content is 12.2 wt% at a pyrolysis temperature of 740◦ C and 24.75 at 780◦ C.
Other main components of the PE pyrolysis (780◦ C) are methane, ethylene, and propene
as gas and toluene, naphthalene as aromatics. The amount of carbon soot is low. Tire
pyrolysis produces mainly carbon black (filler), gas, and aromatics. Steel cord is one of
the other main products if whole tires are fed.
The pyrolysis of polypropylene gives similar results to the pyrolysis of polyethylene
(Table 17.3). The amount of methane and oil is slightly higher, the amount of aliphatics
is lower. The feedstock recycling of polyolefins is easy. Up to 50 wt% can be obtained
as aromatics if the pyrolysis gas is cycled and used as fluidizing gas. The other 50% are
gas components. Benzene and toluene reach 25 wt%.
A real plastic waste collected by the German Dual System (DSD) from municipal
packaging waste was pyrolyzed in the laboratory plant as well as in the pilot plant. The
composition of the mixed plastic wastes is shown in Table 17.4.
Beside polyolefins it contains polystyrene, polyesters, and PVC up to 4% and others.
Table 17.5 gives a detailed composition of the obtained pyrolysis products.
The results are similar to those with polyolefins as feedstock, but the amount of styrene
is higher because of the high amount of polystyrene in the feed. The HCl coming out from
PVC was quantitatively absorped by calcium oxide which was added in 5% weight to the
feed. The CaCl2 formed was separated in the cyclone after the fluidized-bed reactor.
No chlorine was found in the gas fraction. The oil (run at 728◦ C) contains 15 ppm
chloroorganic compounds, mainly chlorobenzene, the soot separated by the cyclone con-
tains 18.4 wt% CaCl2 . There were no chlorinated dibenzodioxines (TCDD) or furane
(TCDF) found in the oil (detection limit 0.01 ng/g).
Table 17.2 Pyrolysis of polyethylene (PE), used syringes, and tires by the Hamburg Pyrolysis
process in a fluidized-bed using pyrolysis gas as fluidizing gas. Products in wt%
Reactor LWS TWS1 TWS1 TWS1 TWS2

Feed Material PE PE Used syringes Tire pieces Whole tires
Temperature (◦ C) 740 780 720 750 700
Hydrogen 0.5 0.17 0.49 1.30 0.42
Methane 16.1 20.27 19.09 15.13 6.06
Ethane 5.3 4.33 6.64 2,95 2.34
Ethylene 25.4 16.89 15.44 3.99 1.65
Propane + 0.80 0.12 0.29 0.43
Propene 9.03 5.35 9.93 2.50 1.53
Butene 0.5 0.08 3.03 1.31 1.41
Butadiene 2.8 1.28 1.38 0.92 0.25
Isoprene + 0.09 0.31 0.34 0.35
Cyclopentadiene 1.0 2.63 2.08 0.39 0.25
Other aliphatic
compounds 13.3 0.69 3.13 0.36 1.07
Benzene 12.2 24.75 13.62 4.75 2.42
Toluene 3.6 5.94 4.20 3.62 2.65
Xylene 1.1 + + + +
Styrene 1.1 1.46 0.45 0.17 0.35
Indan, Indene 0.3 1.27 0.46 0.31 0.48
Naphthalene 0.7 3.73 2,48 0.85 0.42
Methylnaphthalene 0.15 0.84 0.92 0.83 0.67
Diphenyl 0.02 0.34 0.33 0.49 0.39
Fluorene 0.01 0.29 0.15 0.15 +
Phenanthrene 0.02 0.59 0.47 0.29 0.19
Pyrene + 0.22 + 0.21 0.06
Other aromatic
compounds 5.1 5.40 8.24 8.50 13.67
Carbon monoxide 3.80 1.48
Carbon dioxide 1.95 1.74
Water 0.10 5.11
Hydrogen sulfide 0.23 0.02
Thiophene 0.15 0.25
Carbon soot,
fillers 0.9 1.50 5.80 40.59 40
Steel cord 1.62 11.30
LWS laboratory-scale reactor; TWS1 pilot plant; TWS2 pilot plant for whole tires; + trace detection
To recover a maximum of olefins and butadiene from recycling polyolefins, it is nec-

essary to have a short residence time of the product gases in the fluidized bed zone to
avoid no secondary reactions. The pyrolysis gas should not be circulated and used as
fluidizing gas. For the experiments, steam was used as fluidizing gas [13, 14]. An easy
separation of the hydrocarbon products is possible by condensation to water in a cooler.
The results are shown in Table 17.6. As feedstock a light plastic fraction from household
waste separation was used which contains 95.8% of PE and PP, 3% of PS, and 0.2% of
PVC.
In all experiments, the pyrolysis products are rich in olefins. The highest yields are
produced at 690 and 700◦ C. The yield of ethylene is 29–31 wt%, of propene 14–18
484 W. KAMINSKY
Table 17.3 Pyrolysis of polypropylene (PP) and mixtures of PP and PE in the pilot plant (TWS1)
using pyrolysis gas as fluidized gas. Products in wt%
Temperature (◦ C) 740 760 710 720

Feed PP PP PP:PE(1:1) PE:PP(5:1)
Throughput (kg) 435 330 355 325
Hydrogen 0.63 0.74 0.28 0.46
Methane 20.60 28.21 17.17 15.25
Ethylene 13.32 13.90 15.36 18.31
Ethane 4.43 4.01 5.91 7.85
Propane 0.16 0.09 0.08 0.19
Propene 7.09 3.69 9.71 8.01
1-Butene 2.32 0.17 1.06 0.62
2-Butene 0.11 0.21 1.29 0.22
1,3-Butadiene 0.96 0.41 1.90 1.75
Pentene 0.28 0.10 0.69 0.35
Isoprene 0.08 0.21 0.53 0.04
Pentadiene 0.05 0.11 0.36 0.26
Cyclopentene 0.11 0.15 0.55 0.36
Cyclopentadiene 0.50 0.23 1.11 1.11
Dicyclopentadiene 0.96 0.62 1.01 1.50
Hexene 0.02 0.15 0.09
Hexadiene 0.03 0.03 0.08
Methylcyclopentane 0.02 0.01 0.05 0.05
Methylcyclopentene 0.05 0.002 0.02
Cyclohexene 0.01 0.19 0.11
Cyclohexadiene 0.04 0.01 0.08 0.09
Other aliphatics 0.08 0.05 0.23 +
Benzene 18.12 18.23 15.28 19.31
Toluene 6.67 6.64 6.08 4.93
Styrene 0.08 0.99 0.79 0.71
Vinylbenzene 0.11 0.11 0.12 0.12
α-Methylstyrene 0.11 0.13 0.08 0.01
Indane 0.19 0.20 0.22 0.31
Indene 0.62 0.82 0.52 0.83
Methylindane 0.11 0.06 0.14 +
Methylindene 0.36 0.30 0.32 0.45
Naphthaline 3.15 3.48 2.52 3.22
Dimethylindene 0.04 0.02 0.02
2-Methylnaphthaline 0.60 0.56 0.47 0.46
1-Methylnaphthaline 0.42 0.35 0.32 0.35
Diphenyl 0.38 0.35 0.29 0.56
Ethylnaphthaline 0.12 0.08 0.07 0.04
Dimethylnaphthaline 0.10 0.09 0.04 0.06
Acenaphthylene 0.22 0.23 0.14 0.16
Acenaphthene 0.02 0.04 0.03 0.04
Fluorene 0.25 0.30 0.16 0.22
Methylfluorene 0.12 0.07 0.07 0.11
Phenanthrene/anthracene 0.60 0.68 0.43 0.44
1-Phenylnaphthaline 0.01 0.01 0.02 0.01
2-Phenylnaphthaline 0.01 0.02 0.02 0.01
Methylphenanthrene 0.10 0.12 0.10 0.05
Fluoranthene + 0.04 0.03 0.01
Pyrene 0.09 0.22 0.09 0.08
Other aromatics 13.61 10.73 12.48 9.62
Carbon soot, fillers 1.61 1.70 1.41 1.85
Total gas (H2 , C1 –C4 ) 46.62 51.43 52.76 52.66
Total oil > C4 46.94 45.87 44.68 44.92
Total aromatics 44.52 44.27 39.49 40.86
Table 17.4 Different compositions (A and B) of the mixed
plastic wastes used in wt% collected by the DSD system
Fraction (feed) A B
Polyolefins 65 65
Polystyrene 14 25
PVC 3.8 1.2
Polyester/paper 7.2 1.5
Other plastics 2.0 1.3
Water 4.0 4.1
Fillers, metals 4.0 1.9
Table 17.5 Mass balance of the pyrolysis of mixed plastics (different fractions A and B see
Table 17.4) in a fluidized bed with different feedstocks and plants using pyrolysis gas for fluidization
Plant LWS5 LWS5 LWS5 LWS5 TWS1

Throughput (g) 1185 1165 1230 2800 212 kg
Feed A A A B B
Temperature (◦ C) 685 710 716 738 730
Gases (total) 41 44 43 38 35
Hydrogen 0.4 0.5 0.6 0.7 0.4
Carbon monoxide 4.6 5.5 6.0 1.3 1.3
Carbon dioxide 2.0 2.5 1.7 0.6 0.4
Methane 10.9 12.3 16.2 20.5 11.9
Ethylene 8.6 8.9 10.1 10.3 8.9
Ethane 4.0 3.9 3.3 2.2 3.9
Propene 6.3 6.0 3.2 1.0 5.0
Propane 0.5 0.6 0.2 0.1 0.6
n,i-Butane 0.08 0.08 0.05 0.19 0.03
n,i-Butene 2.1 2.3 0.7 0.1 1.6
Butadiene 0.8 0.9 0.7 0.5 0.7
trans-2-Butene 0.2 0.2 0.1 0.1 0.2
cis-2-Butene 0.2 0.2 0.1 0.1 0.1
Other gases 0.1 0.1 0.1 0.3 0.1
Oils (total) 48 44 45 50 51.8
Paraffins C5 –C6 5.7 4.9 2.2 0.7 3.1
Paraffins C7 –C9 2.3 1.6 0.5 0.2 0.5
Benzene 9.5 10.8 14. 17.4 9.1
Toluene 6.7 6.1 4.8 3.9 7.6
Xylene 0.6 0.6 0.5 0.2 0.8
Ethylbenzene 0.9 1.0 0.9 0.2 2.5
Styrene 9.0 7.9 6.8 8.7 10.8
C3 -Benzene 0.6 0.5 0.5 0.5 1.2
Methylstyrene 1.4 1.1 1.5 0.2 1.6
C4 -Benzene 0.1 0.1 0.1 0.3 1.1
Indene 0.6 0.8 2.1 2.5 1.2
Methylindene 0.4 0.3 0.5 0.3 0.7
Naphthalene 0.8 1.2 4.2 7.2 2.3
Methylnaphthalene 0.3 0.4 0.5 0.1 1.0
Diphenyl 0.1 0.1 0.2 0.1 0.4
Fluorene 0.04 0.07 0.05 0.18 0.1
Phenanthrene/anthracene 0.01 0.02 0.04 0.63 0.2
Other aromatics 0.7 0.6 0.6 0.5 2.5
Oxygen compounds 0.1 0.3 0.01 0.01 0.01
Nitrogen compounds 0.02 0.1 0.01 0.01 0.01
Other compounds 8.1 5.8 5.0 6.2 5.1
Distillation residue 5.8 5.6 6.3 6.5 11.0
Soot/fillers 5.2 6.4 5.7 5.5 2.2
486 W. KAMINSKY
Table 17.6 Feedstock recycling of polyolefin mixtures to high amounts of olefins using steam as
fluidizing gas by different pyrolysis temperatures
Temperature (◦ C) 655 690 700 700 750 805

Residence time reactor (s) 2.7 1.8 2.3 3.2 2.9 3.1
Products (wt%):
Gases 68 75 72 72 69 58
Hydrogen 0.4 0.6 0.6 0.6 0.9 1.3
Carbon monoxide 1.3 1.3 1.0 1.4 0.8 1.4
Carbon dioxide 0.6 0.9 1.4 1.3 1.6 2.2
Methane 5.4 8.9 11 8.8 13 13
Ethylene 24 29 31 30 36 30
Ethyne 0.08 0.3 0.3 0.4 0.8 1.3
Ethane 2.9 3.3 3.4 2.8 0.8 1.7
Propene 18 18 14 15 8.4 3.2
Propane 0.6 0.7 0.5 0.5 0.2 0.07
n/i-Butene 6.7 4.7 2.2 3l0 0.6 0.2
cis/trans-2-Butene 0.7 0.9 0.6 0.7 0.3 0.08
Butadiene 7.1 6.9 5.4 6.4 4.0 2.2
Aliphatics 9.8 7.2 3.7 4.5 1.5 0.7
C5 -Hydrocarbons 6.9 4.6 2.8 3.4 1.5 0.7
C6 -Hydrocarbons 2.4 1.2 0.5 0.6 0.03 0.01
BTX-aromatics 5.9 9.8 13 9.9 14 16
Benzene 3.9 6.8 9.4 7.4 11 13
Toluene 1.9 2.7 3.2 2.4 2.8 2.4
Other aromatics 2.6 4.6 6.0 4.6 7.7 7.7
Styrene 1.0 1.6 1.8 1.4 2.1 2.1
Indene 0.2 0.5 0.7 0.6 1.0 1.1
Naphthalene 0.2 0.7 1.4 0.8 2.7 2.9
Total oil 18 22 23 19 24 24
Distillation residue 13 3.4 4.7 8.5 6.4 18
Soot 0.6 0.4 0.6 0.9 0.8 0.7
wt%, of butanes 2–5 wt%, and of butadiene 5–7 wt%, a total of more than 59 wt%. This
is even higher than naphtha crackers produce (55%). The other components produced are
pyrolysis benzene 24–26 wt%, methane 9–11 wt%, and styrene 1.4–1.8 wt% because of
the small amount of PS in the plastic feed. Similar results can be obtained if nitrogen is
used instead of steam as the fluidizing gas. Steam reduces the formation of soot.
As shown, it is possible to recover directly high amounts of olefins similar to that of a
naphtha crackers from polyolefin wastes. For selling, the olefins have to be cleaned up in
distillation plants. To avoid problems with HCl from unexpected PVC fractions, it is safer
to produce from polyolefins a waxy material which can be analyzed and, if free from HCl
and chloroorganic compounds, mixed with naphtha and used as cracker feed. This was
the concept of BP Chemicals. The test runs were made in our Hamburg laboratory plant
(LWS3) [15]. Detailed material balances for experiments are provided in Table 17.7
To obtain low amounts of gas and aromatics, the pyrolysis temperature was mild and
varied from 450 to 530◦ C. Only 1–8 wt% of gas is produced. With a heat of combustion
of some 47 MJ/kg, it can be used for the indirect heating of the fluidized bed. The waxes
Table 17.7 Pyrolysis of polyolefins in a fluidized bed (LWS3) using nitrogen as fluidizing gas at
low temperatures to recover oily and waxy products; products in wt%
Temperature (◦ C) 530 510 510 510 510 450

Material HDPE HDPE LLDPE PP Mix LLDPE
Input (kg) 1.6 2.7 5.5 4.9 4.6 1.8
Throughput (kg/h) 0.9 0.9 1.1 1.0 0.9 1.0
Methane 0.8 0.3 0.4 0.6 0.4 0.1
Ethylene 2.0 0.6 0.8 0.5 0.6 0.2
Ethane 0.8 0.3 0.6 1.0 0.5 0.2
Propene 1.8 0.7 0.8 3.0 1.5 0.2
Propane 0.7 0.3 0.3 0.4 0.3 0.2
Butenes 1.1 0.3 0.5 0.7 1.0 0.2
Total gas 7.6 2.6 3.4 6.3 4.7 1.1
Pentenes 0.1 0.2 0.3 0.5 1.0 0.1
Pentanes 0.03 0.1 0.1 1.2 1.7 0.1
Pentadienes 0.1 0.1 0.1 0.1 0.2 0.04
Hexenes 0.9 1.0 1.0 1.7 2.3 0.4
Hexanes 0.2 0.2 0.2 0.2 0.4 0.1
Hexadienes 0.1 0.1 0.1 0.5 0.4 0.03
Heptenes 0.8 0.6 0.6 0.6 1.0 0.3
Heptanes 0.3 0.4 0.3 + 0.3 0.2
Heptadienes 0.01 + + 0.5 0.2 0.01
Octenes 0.6 0.4 0.5 0.3 0.4 0.3
Octanes 0.2 0.2 0.2 0.3 0.4 0.2
Octadienes 0.03 0.01 0.02 0.2 0.01 0.01
Nonenes 0.7 0.4 0.4 7.8 4.2 0.2
Nonanes 0.2 0.2 0.2 0.3 0.4 0.2
Nonadienes 0.1 0.1 0.04 0.1 0.1 0.02
Decenes 1.0 0.7 0.7 0.8 0.8 0.4
Decanes 0.2 0.2 0.2 + 0.1 0.2
Decadienes 0.1 0.1 0.1 + 0.03 0.04
Total C5 –C10 6.9 5.2 5.6 15 14 3.4
Total C11 –C20 9.9 6.9 6.7 13 5.7 6.1
Total > C20 34 24 24 35 37 18
Total BTX-aromatics 0.3 0.05 0.05 0.02 0.1 0.03
Total waxes bp < 500◦ C 51 36 37 64 57 28
Total waxes bp > 500◦ C 42 61 60 30 38 71
Mix PP/LLDPE/HDPE: 40/15/45, wt%; + detected, but not quantified
are made of hydrocarbon groups forming a homologous series when pure polyethylene
is used as feedstock. The alkenes, alkanes, and alkadienes of each group are their main
components. The total amount of waxes reaches 93–99 wt%, while the total amount of
aromatics is less than 0.5 wt%.
Beside the polyolefins described polystyrene (PS), polymethylmethacrylate (PMMA),
polytetrafluoroethylene (PTFE) (see Chapter 24) and polyester (PET) [16], polyamide
(PA) [17], polyurethane (PUR) [17], and polyepoxides [18] were used as feedstock for
the Hamburg process. The fluidized-bed process is very flexible for different feeds and
process parameters.
488 W. KAMINSKY
3.1 INDUSTRIAL PILOT PLANTS
The first industrial pilot plant using the Hamburg pyrolysis process was built in 1983
at Ebenhausen/Ingolstadt by Deutsche Reifen und Kunststoff-Pyrolyse (DRP) and later
operated by Asea Braun Bovery (ABB). The plant contains two fluidized-bed reactors,
each with a diameter of 1800 mm. A scheme is shown in Figure 17.6 [19]. The heating
tubes are in contact from the top of the reactor to the fluidizing sand bed (Figure 17.7).
Impurities such as metal particles and stones, glass and sand can be removed at the bottom
by a water cup to avoid the loss of gases.
One reactor was used for the feedstock recycling of plastics and the other for tires. The
feedstock passes a lock and then is transported by a screw conveyor into the fluidized
bed. Exhaust gases from the heating tubes are used to render the feedstock inert.
The product gas is cleaned up from solids by hot-working cyclones, and then cooled
down. In the first step, high-boiling oil is obtained. After compression and cooling, low-
boiling oil is separated. The oil-free gas is used as heating gas for the heating tubes and for
fluidization. The capacity of the plant was 800 kg plastics per hour in one reactor. In this
time, scrap material from cable dismantling (cross-linked polyethylene), polypropylene
carpet wastes, and mixed plastics from household waste separation were used as feed-
stock. The most valuable light-oil fraction reached 40 wt%. The composition is shown in
Table 17.8.
The necessary electrical power for 1 ton of plastic operation was measured to be
between 200 and 280 kW. The heating tubes consumed 19 wt% of the plastic products as
P K F Q K DW
KM
HS LS
WT
Gas
Figure 17.6 Scheme of the industrial pilot plant for the pyrolysis of 5000 t/yr plastics
or tires. Z cyclone; Q quench cooler; K cooler; DW high-pressure quench cooler; KM
compressor; WT heat exchanger; F flare; G excess gas; R carbon black; P plastic feed; K:
calcium oxide, LS low-boiling oil; HS high-boiling oil
Figure 17.7 View of the top of the fluidized-bed reactor, DRP plant with the inlet of the
12 fire tubes
Table 17.8 Composition of pyrolysis light oil obtained at the DRP plant in Ebenhausen, compared
with pyrolysis benzene (PBC) from a cracker
Feedstock PBC CPE CPP MPW

Benzene 40 43.7 18.6 17.5
Toluene 20 15.9 14.6 12.5
Xylene 8 2.9 12.2 9.0
Styrene 8.1 16.3 15.0
BTX + styrene 68 70.6 71.7 54.0
Others 32 29.4 28.3 46.0
Fluidized bed temperature 700◦ C. CPE cross-linked polyethylene; CPP: carpet polypropylene waste, MPW:
mixed plastic waste
gas. There is more gas produced (40–50 wt%) than needed for the heating and electrical
power. The composition of the gas can be seen in Table 17.9.
The heating value of the gas varies between 10.3 to 13.5 kW h/m3 . The plant ran for
two years from 1984 to 1985. It was then closed because the crude oil price decreased
and this small plant of about 5000 ton plastics per year and 5000 ton tires per year was
uneconomic.
The industrial pilot plant built up in Grimma, Germany for the pyrolysis of 5000 whole
tires per year has a similar structure to that of the university plant, shown in Figure 17.5.
There was only one reactor with a size of 2000 × 3600 mm. A picture of the plant is
shown in Figure 17.8. The plant ran until the reunification of Germany in late 1989 and
490 W. KAMINSKY
Table 17.9 Composition of the pyrolysis gas in the DPR plant in Ebenhausen, obtained from
different feedstocks (see Table 8) at 700◦ C in volume%
Feedstock CPE CPP MPW

Hydrogen 18.8 14.4 30.0
CO2 1.9 1.4
CO 5.7 2.1 7.2
Methane 58.2 45.5 51.8
Ethylene 10.2 13.2 5.7
Ethane 3.0 7.7 1.2
Propene 1.2 7.7 0.1
Others 1.0 9.4 2.6
Figure 17.8 View of the Grimma plant for feedstock recycling of whole tires, in front
two cyclones to separate the carbon black
was then closed down. The plant required too many workers for recycling only 5000 tons
of tires a year. The most valuable compound was carbon black which was reused again
for tire production.
REFERENCES
1. H. Sinn, Recycling of plastics, Chem. Ing. Techn., 46, 579–589 (1974).

2. Prospect material from Japan Gasoline Co., Fluid Cracking Process, 1974.
3. W. Kaminsky, J. Menzel and H. Sinn, Recycling of plastics, Conservation Recy-
cling, 1, 91–110 (1976).
4. H. Sinn, W. Kaminsky and J. Janning, Plastic waste and scrap tires into chemical
raw materials, especially by pyrolysis, Angew. Chem. Int. Ed. Engl., 15, 660–672
(1976).
5. W. Kaminsky and H. Sinn, Pyrolysis of plastic waste and scrap tires using a fluidized
bed process, ACS Symposium Series, 130, 423–439 (1980).
6. W. Kaminsky, W. Schweers and H. Schwesinger, Properties and Decomposition of
Lignins, Decomposition by Pyrolysis in a Fluidized Bed, Holzforschung, 34, 73–76
(1980).
7. W. Kaminsky and A. B. Kummer, Fluidized bed pyrolysis of digested sewage sludge,
J. Anal. Appl. Pyrolysis, 16, 27–35 (1989).
8. M. Predel and W. Kaminsky, Pyrolysis of rape-seed in a fluidized bed reactor, Biore-
source Technology, 66, 113–117 (1998).
9. H. W. Schnecko, Pyrolysis of used tires, Chem. Ing. Techn., 48, 443–447 (1976).
10. W. Kaminsky, Pyrolysis of plastic waste and scrap tyres in a fluid bed reactor,
Resource Recovery Conserv., 5, 205–216 (1980).
11. W. Kaminsky, Thermal recycling of polymers, J. Anal. Appl. Pyrolysis, 8, 439–448
(1985).
12. W. Kaminsky and J. -S. Kim, Pyrolysis of mixed plastics into aromatics, J. Anal.
Appl. Pyrolysis, 51, 127–134 (1999).
13. W. Kaminsky and F. Hartmann, New pathways in plastics recycling, Angew. Chem.
Int. Ed., 39, 331–333 (2000).
14. C. M. Simon, W. Kaminsky and B. Schlesselmann, Pyrolysis of polyolefins with
steam to yield olefins, J. Anal. Appl. Pyrolysis, 38, 75–87 (1996).
15. H. Kastner and W. Kaminsky, Recycle plastics into feedstocks, Hydrocarbon Pro-
cessing, May 1995, 109–112.
16. G. Grause, W. Kaminsky and G. Fahrbach, Hydrolysis of poly(ethylene)terephthalate
in a fluidized bed reactor, Polym. Degrad. Stab., 85, 571–575 (2004).
ysis in a fluidized bed, Polym. Degrad. Stab., 85, 1045–1050 (2004).
18. N. Grittner, W. Kaminsky and G. Obst, Fluid bed pyrolysis of anhydride-hardened
epoxy resins and polyether-polyurethane by the Hamburg Process, J. Anal. Appl.
Pyrolysis, 25, 293–299 (1993).
19. H. Timmann, DRP Process, In: Pyrolyse von Abfällen, K. J. Thomé Kozmiensky,
(ed) EF Verlag Berlin, pp. 195–208, 1985.
18
Liquefaction of PVC Mixed Plastics

THALLADA BHASKAR AND YUSAKU SAKATA
Department of Applied Chemistry, Faculty of Engineering, Okayama University,
Okayama 700–8530, Japan
1 INTRODUCTION
In today’s modern world, plastics make a fundamental contribution to all activities such
as agriculture, the automobile industry, electricity and electronics, building materials,
packing and so on. Recently, plastics have shown rapid and visible growth compared
with other materials. This is primarily because of substitution of other materials with
plastics as well as their applications in new areas, and material’s durability and versatility.
Plastics are low-cost materials and widely used, they can be easily processed into light
but durable materials with low thermal and electrical conductivity. The rapid growth in
plastics consumption is increasing and subsequently plastic waste is accumulated, and
poses serious problems to the environment due to their non-biodegradable nature. The
world’s annual consumption of plastic materials has increased around 5 million tons in
the 1950s to nearly 150 million tons today. Due to the world’s limited reserve of coal,
crude oil and natural gas, it becomes very urgent to preserve the existing non-renewable
materials. Various recycling methods have been developed and being used now. However,
reduction or minimizing the consumption of raw materials through the novel design of
products may allow the reduction of wastes generated.
Recovery can be classified as material recycling and energy recovery. Material recy-
cling can be performed using two approaches such as mechanical recycling and feedstock
recycling. In general, recycling must be applied only when the amount of energy con-
sumed in the recycling process is lower than the energy required for the production of new
materials. Mechanical recycling is performed in the following manner. The waste plastics
are collected, sorted, washed to remove contaminants, baled, shredded into flakes and
then placed into an extruder by heat and reprocessing into new plastic goods. This tech-
nique is limited to thermoplastics and not applicable to thermosets; compatibility between
the different types of polymers also poses problems. Another difficulty with mechanical
recycling is the presence of plastic waste products made of the same resin, but with
494 T. BHASKAR AND Y. SAKATA
different colors, which usually impart an undesirable grey color to the recycled plastic.
Finally, the recycled polymers usually exhibit lower properties and performance than the
virgin material, and are useful only for undemanding applications. Mechanical recycling
can be performed solely on single-polymer plastic waste because a market can be found
only if the recycled products match the original products as closely as possible in quality.
Feedstock recycling is the process for conversion of waste plastics into chemicals and
fuels. The detailed discussion on feedstock recycling will be provided in the following
sections.
If neither secondary market nor feedstock recycling is possible, incineration can be
applied to produce energy from the waste plastics combustion. Plastic wastes greatly
contribute to the energy production in incineration plants, as plastics are materials of high
calorific value. They can be used in cement kilns, industrial furnaces or power plants.
However, there are problems with the halogen-, i.e. chlorine- and bromine-containing
plastics due to the possible formation of dioxins during the incineration. Incineration of
plastic waste to produce heat may be a possibility, but its organic content would totally
be destroyed and converted into CO2 and H2 O. The nonavailability of proper landfill sites
and opposition from the public can make landfilling difficult.
On the other hand, plastic waste has a high content of organic materials and energy
that is totally lost by disposal or is recovered only in a very small amount by incineration.
Due to the world’s limited reserve of coal, crude oil and natural gases it becomes very
urgent to preserve the existing non-renewable materials and to find other carbon sources
as feedstock materials or as fuels. Pyrolysis is one of the best methods to recover the
material and energy from polymer waste, as only about 10% of the energy content of
the waste plastic is used to convert the scrap into valuable hydrocarbon products. This is
obtained by breaking down polymers at high temperatures into petrochemical feedstock
components from which they originate while the additives in the polymer materials (e.g.
metals, inorganic fillers and supports) remain in the pyrolysis residue. New pathways
in plastic recycling and status of plastics recycling have been recently highlighted by
Kaminsky and Hartmann [1]. The development of different viable recycling technologies
for plastic waste materials is becoming increasingly important. There is growing interest
in thermolysis and catalytic polymer degradation as methods of producing various fuel
fractions from polymer wastes. Pyrolysis is one of the best methods for preserving valuable
petroleum resources in addition to protecting the environment by limiting the volume of
nondegradable waste. Pyrolysis of waste plastics is favored because of the high rates of
conversion into oil. The gaseous products coming from the pyrolysis process with high
caloric value may be used as fuel in the process. Recycling by pyrolysis has high potential
for heterogeneous waste materials, which cannot be economically separated.
There has been a plethora of research work published on the pyrolysis of waste plastics
into fuel. Pyrolysis involves the thermal degradation of organic matter in an oxygen free
environment. Kastner and Kaminsky [2] studied the thermal cracking of PE in a fixed-bed
reactor over the temperature range 500–600◦ C. At temperatures below 550◦ C, high yields
of useful products with low yields of gas and aromatics were obtained. Ding et al. [3, 4]
have studied hydrocracking of PE using HZSM-5 and metal-loaded hybrid catalysts pre-
pared from HZSM-5 and silica–alumina. HZSM-5 produced more aromatic hydrocarbons,
whereas hybrid catalysts (especially Ni-loaded) showed higher hydroisomerization ability.
An interesting result was that the liquid products obtained over hybrid catalysts were
LIQUEFACTION OF PVC MIXED PLASTICS 495
clean and white or light yellow with a gasoline-like smell, while the liquids produced
from thermal cracking and over HZSM-5 were brown red with a strong unpleasant smell.
Aguado et al. [5] investigated the effect of β-zeolite on the degradation of PP, LDPE and
HDPE at 400◦ C in a batch reactor. It was observed that degradation of HDPE affords
a high selectivity of C5 –C12 products (70 wt%) whereas in the cracking of LDPE and
PP, selectivity to gasoline is reduced (64 wt%) and higher proportions of lighter products
C1 –C4 are obtained. Dehydrochlorination of plastic mixtures was studied by Bockhorn
et al. [6–7]. They explained how stepwise low-temperature pyrolysis mixtures of PVC,
polystyrene and polyethylene have been separated into hydrogen chloride, the monomer
of polystyrene and aliphatic compounds from polyethylene decomposition. The degree of
conversion of chlorine from PVC into hydrogen chloride in the low temperature (330◦ C)
is about 99.6% [7]. Sen and Pifer reported the chemical recycling of plastics to useful
organic compounds by oxidative degradation [8]. The new procedure for the oxidative
degradation of polythene to valuable α,ω-diacids under fairly mild conditions [9].
Pyrolysis of plastic wastes and the effect of plastic waste composition on product
yield [10], and the effect of catalyst on product yield have been discussed in detail [11].
The liquefaction of waste plastics into fuels have been studied by various researchers
using the model mixed plastics and real waste plastics. Novel tertiary plastics recycling
method for the production of fuel over microporous catalysts were reported by Gobin
and Manos [12a]. They reported that the US-Y is the most active catalyst, but produced
the highest amount of coke, due to its strong acidity. Whereas, the presence of ZSM-
5 increased the yield to gaseous products and decreased the coke content, due to their
small pores (shape-selective catalysts). Pyrolysis of individual plastics and plastic mix-
tures in a fixed-bed reactor was performed by Williams and Williams [13]. Production
of harmful compounds such as PAHs were produced during the pyrolysis of polyvinyl
chloride, polyvinyl benzyl chloride or polychloro styrene [14]. Hydrogen chloride formed
by elimination from PVC depresses the formation of PAHs more effectively in the pres-
ence of iron. Chlorine from polyvinyl benzyl chloride increased the production of PAHs
in the presence of copper. The effect of carbon black on the thermal decomposition of
vinyl polymers were studied by Jakab and Blazso [15]. In our earlier studies [16–18],
we have reported on the catalytic degradation of PP and PE by silica–alumina catalyst
in a semi-batch reactor and showed that silica–alumina was effective in increasing the
degradation rate and yield of oil products. The studies [18–21] on the effect of catalyst
type on polymer degradation indicated that the catalysts with strong acid sites such as
zeolite accelerated the degradation of PP and PE into gases, which resulted in low liquid
yields.
Pyrolysis of non-halogenated polymers such as polyethylene, polypropylene, and
polystyrene is simple and the liquid products obtained by thermal degradation can be used
as fuel oil or as a feedstock. However, municipal waste plastics or commingled waste
plastics from packaging and other sectors contain chlorine plastics such as polyvinyl
chloride or polyvinylidene chloride. The pyrolysis of PVC-containing mixed plastics
produce corrosive mineral acid (HCl) and chlorinated organic compounds in the liquid
products. The presence of such chlorine compounds in the liquid products is not desirable
to use as a fuel or feedstock. The key technology for the utilization of valuable organic
content from PVC-containing mixed plastics is the dehalogenation of liquid products.
Compared with studies, on non-halogenated plastics pyrolysis halogen-containing plastics
pyrolysis and dehalogenation studies are few in the literature. The thermal and catalytic
degradation of individual PE/PVC, PP/PVC, and PS/PVC by silica–alumina catalysts and
dechlorination by iron oxides (FeOOH and Fe3 O4 sorbents) has been studied [20–22].
The halogen-free liquid products can be produced in two stages, i.e. degradation and
dehalogenation or simultaneous degradation and dehalogenation (single stage) of PVC-
containing plastics. The following sections will address the detailed information on the
development of various catalysts, sorbents for dechlorination, dechlorination of plastic-
derived oil with chlorine compounds (plastic-derived oil obtained in first step of a
two-stage process), simultaneous degradation and dehalogenation of various commingled
plastics, and finally application of this process to the real municipal waste plastics.
2 EXPERIMENTAL AND ANALYTICAL METHODS

2.1 PREPARATION OF IRON AND CALCIUM COMPOSITES
Calcium carbonate, iron oxide carbon composites were cooperatively prepared with Toda
Kogyo Corporation, Hiroshima, Japan. Briefly, about 90 wt% of calcium carbonate is
mixed with 10 wt% phenol resin by mechanical kneading, during the kneading process
20% of water is added to the mixture and pellet formation is achieved by extrusion.
The prepared sorbent was calcined at 500◦ C for 1 h in a nitrogen atmosphere and in the
calcination process the phenol resin was converted into carbon. The addition of phenol
resin and calcination gave good mechanical strength and loss of hygroscopic nature of the
sorbent, which are important parameters for the successful use in pilot plant. The finished
sorbent designated as Ca-C [calcium carbonate carbon composite]. In a similar way with
the same weight ratios of active component to the carbon material, the iron oxide carbon
composite sorbent with α-FeOOH was prepared. The physical properties such as surface
area (BET), and pore volume were obtained from nitrogen adsorption analysis and they
are as follows:
Sorbent BET surface area (m2 /g) Pore volume, (mL/g)
Ca-C (CaCO3 ) 40 0.11
Fe-C (Fe3 O4 ) 83 0.44
2.2 EXPERIMENTAL PROCEDURE
A schematic diagram of the experimental set-up is shown in Figure 18.1. Pyrolysis of

PP/PE/PS mixed with PVC was carried out in a glass reactor (length 350 mm; id 30 mm)
under atmospheric pressure by batch operation with identical experimental conditions
and temperature program. Briefly, 10 g of mixed plastics (weight ratio: PVC/PP/PE/PS =
1/3/3/3) was loaded into the reactor for degradation in vapor phase contact with Ca-C.
The fresh PP/PE/PS and PVC grains were well mixed and used for degradation. The
Ca-C (1 mm average diameter) was loaded into another reactor (dechlorination reactor)
and the sorbent bed temperature was kept at 350◦ C. In a typical run, after setting the
reactor, the reactor was purged with nitrogen gas at a flow rate of 10 mL/min and held at
120◦ C for 60 min to remove the physically adsorbed water from the sorbent and plastic
sample. The reactor temperature was increased to the degradation temperature (430◦ C)
N2 Gas (10 mL/min)
Dechlorination
reactor
i.d.:30 mm Condenser
Glass reactor L:480 mm
i.d.:30 mm
L:350 mm Water out
Furnace
(350°C)
Furnace
(430°C)
Cold
water in
Plastic sample
Sorbent/
Thermocouple catalyst
Thermocouple
Teflon bag
Graduated cylinder
for liquid products
NaOH trap
Figure 18.1 Schematic experimental set-up for pyrolysis of plastics and dehalogenation
process. (Reproduced with permission from the American Chemical Society)
at a heating rate of 3◦ C/min (degradation reactor temperature program: room tempera-

ture, rate 3◦ C/min → 120◦ C, rate 3◦ C/min; hold 60 min → 430◦ C). The dechlorination
reactor temperature (350◦ C) was increased linearly at a heating rate of 5◦ C/min (dechlo-
rination reactor temperature program: room temperature → 350◦ C, rate 5◦ C/min). In a
similar way, the thermal degradation of plastics was carried out in the absence of sorbent.
The waste plastic bed temperature was taken as the temperature of the degradation and
the sorbent bed temperature was taken for the dechlorination process (Figure 18.1). The
gaseous products were condensed (using a cold water condenser, Figure 18.1) into liquid
products and trapped in a measuring jar. 80 mL of 1 M NaOH was used for NaOH trap
(container capacity 100 mL). The weight of a reactor including the mixed plastics was
measured before and after the degradation process. The weight difference before and
after degradation was taken as a measure of liquid and gas yields. The residue (plastic
feed, 10 g −) was the difference between plastic feed and liquid and gas yields. There
is very small amount of liquid products on the reactor walls and on side arm. In a similar
way, other combinations of mixed plastic samples pyrolysis were performed.
2.3 ANALYSIS PROCEDURE
The quantitative analysis of the liquid products (collected once at the end of the experi-
ment) was performed using a gas chromatograph equipped with a flame ionization detector
(FID; YANACO G6800; column, 100% methyl silicone; 50 m × 0.25 mm × 0.25 µm;
temperature program, 40◦ C, hold 15 min → 280◦ C, rate 5◦ C/min; hold 37 min) to obtain
the quantity of hydrocarbons and carbon number distribution of the liquid products. The
distribution of chlorine compounds and the halogen content (organic) in liquid products
were analyzed by a gas chromatograph equipped with an atomic emission detector (AED;
HP G2350A; column, HP-1; cross-linked methyl siloxane; 25 m × 0.32 mm × 0.17 µm).
1,2,4-Trichlorobenzene was used as the internal standard for the quantitative determina-
tion chlorine content using the GC-AED analysis. The amount of Cl content in NaOH
trap (Figure 18.1) was analyzed using an ion chromatograph (DIONEX, DX-120).
The main liquid products were also analyzed by a gas chromatograph with a mass-
selective detector (GC-MSD; HP 5973; column, HP-1; cross-linked methyl siloxane,
25 m × 0.32 mm × 0.17 µm; temperature program, 40◦ C, hold 10 min → 300◦ C, rate
5◦ C/min, hold 10 min) for the identification of various chlorinated hydrocarbons in liquid
products. The composition of the liquid products was characterized using C-NP gram
[23] (C stands for carbon and NP from normal paraffin) and Cl-NP gram (Cl stands for
chlorine). The curves were obtained by plotting the weight percent of Cl, which was
in the liquid products against the carbon number of the normal paraffin determined by
comparing the retention times from GC analysis using a nonpolar column. The analysis
of various degradation products are given in Figure 18.2.
2.4 HCl ADSORPTION CAPACITY
Reaction of hydrogen chloride with various composite sorbents was carried out using
a fixed-bed microreactor (diameter 8 mm, length 470 mm). About 2 g of sorbent was
loaded into the reactor in between two quartz wool plugs and reactor temperature was
increased linearly (5◦ C/min) to 350◦ C in a nitrogen atmosphere (50 mL/min) and kept
for an hour for the pretreatment (removal of moisture content) of sorbent. For low-
temperature hydrogen chloride reaction process, the sorbent was pretreated at 350◦ C in N2
atmosphere for an hour and cooled to the required adsorption temperature (100, 200, and
270◦ C). A high-temperature (400◦ C) reaction was carried out by pretreating the sorbent
at 400◦ C for an hour in N2 atmosphere followed by hydrogen chloride sorption. A known
concentration of hydrogen chloride gas mixed with nitrogen gas was fed to the reactor and
the outlet of reactor gases (not adsorbed HCl gas) was trapped using ion-exchanged water
(600 mL). The ion-exchanged water trap was changed with a 1-h interval during all the
sorption experiments. The quantity of inlet HCl concentration fed into the reactor over 1 h
was determined in a separate experiment. The quantitative analysis of hydrogen chloride
evolved from the reactor and trapped in ion exchanged water trap was carried out by an
ion chromatograph (DIONEX: DX-120). The isothermal adsorption break through curves
were plotted against reaction time (h) on the x-axis and the quantitatively estimated outlet
HCl concentration (ion chromatograph) on the y-axis. The cylinder containing 2% (v/v)
hydrogen chloride balance nitrogen was used.
3 FUNDAMENTAL STUDIES ON THE DECOMPOSITION OF PVC

3.1 PRODUCT DISTRIBUTION AND MECHANISM OF PVC DECOMPOSITION
Poly (vinyl chloride) (PVC) is essentially a linear polymer with a head-to-tail configura-
tion. Theoretical calculations and model compound studies predicted that PVC of ideal
Liquid (Oil) GC-FID, GC-AED,
GC-MSD
Catalyst/Sorbent
Cl or Br
Degradation
plastics Gas Ion Chromatograph (HCl and HBr),
Products
mixture TCD
LIQUEFACTION OF PVC MIXED PLASTICS
Residue Combustion flask
XRD,
SE M/EDX, TGA
Ion Chromatograph
Figure 18.2 Analysis of degradation products and catalyst/sorbent

499
structure should be thermally stable. Nevertheless, pristine PVC has very low thermal and
photo-oxidative stability. Thermoplastic processing requires elevated temperatures; how-
ever, PVC undergoes thermal degradation, oxidation and mechanochemical chain scission
already above 100◦ C. In spite of the low thermal stability, PVC has become one of the
most widely used plastics because the stabilization technology has developed greatly
over the last 40 years and PVC is compatible with various plastic additives (stabilizers,
plasticizers, fillers, etc.) [24].
The combustion of PVC leads to the formation of harmful polychlorinated dibenzodiox-
ins, dibenzofurans and diphenyls; therefore, other recycling methods are necessary for the
elimination and utilization of PVC-containing plastic wastes. The thermal decomposition
of PVC begins with dehydrochlorination of the polymer chains. Long-term heat-treatment
leads to HCl release already above 100◦ C. When PVC is heated at a 10◦ C/min heating
rate in a helium atmosphere, the decomposition commences above 220◦ C. The DTG curve
reveals three maxima. In earlier studies, the first two maxima were not well separated or
were considered as one decomposition stage [25–27], while later studies identified three
decomposition stages [28, 29]. The dehydrochlorination is a two-stage process. In the first
step, benzene is evolved in addition to HCl at about 300◦ C. The second decomposition
step is dominated by the release of HCl, which can be attributed to the dehydrochlori-
nation of the irregular structures. From the irregular structures (branching, etc.), HCl can
be eliminated at some what higher temperatures than from the regular polymer segments,
and benzene formation is restricted. The third decomposition step takes place between
400 and 500◦ C and is dominated by the release of toluene, and other alkyl substituted
aromatics. Methane was also detected by TG/MS, indicating the occurrence of charring
reactions. In helium, 5% char is produced after the decomposition of PVC. The char yield
strongly depends on the experimental conditions (e.g. atmosphere, sample size, heating
rate) and can even reach 15% by analytical techniques.
The detailed product distribution of PVC pyrolysis can be studied by pyrolysis-gas
chromatography/mass spectrometry (Py-GC/MS), where the samples are heated at a high
heating rate in helium atmosphere. At a lower temperature (400◦ C), unsubstituted aro-
matic compounds (benzene, naphthalene, anthracene and diphenyl) are detected in addition
to HCl. However, the formation of benzene is dominant among the aromatic products.
At higher pyrolysis temperature (550◦ C), the formation of substituted aromatic products
(toluene, styrene, methyl indene, methylnaphthalene, etc.) and indene becomes significant
besides the formation of low-temperature products. Alkenes, alkadienes and cyclic dienes
are also formed during the third stage of degradation [30].
The formation of the major products can be described by the following mechanisms
(Scheme 18.1). After initiation, HCl elimination takes place from the adjacent monomer
units and conjugated double bonds are formed in the polymer chains. The average polyene
sequence length is about ten double bonds. The formation of more extensive polyene chain
segments is prevented by the defect sites in the polymer chains or by the subsequent
degradation pathways. The polyene segments undergo cyclization accompanied by chain
cleavages [31] resulting in the evolution of benzene and smaller amount of condensed
aromatic compounds (naphthalene, anthracene, etc).
At low temperatures, PVC pyrolysis yields only traces of volatile chlorinated hydro-
carbons. The main chlorine-containing hydrocarbons reported are methyl chloride, vinyl
chloride, ethyl chloride and chlorobenzene. Heating PVC at 10◦ C/min up to 500◦ C in
+ condensed aromatics
cyclization
−HCl
Cl Cl Cl Cl Cl Cl
crosslinking
alkyl aromatics + char
Scheme 18.1 Major routes of the thermal decomposition of PVC
vacuum results in the evolution of several chlorinated organic compounds. Chlorinated

alkenes, alkanes and alicyclic hydrocarbons as well as chlorobenzene and alkyl chloroben-
zenes have been detected by McNeill et al. [27] The chlorinated compounds detected
account for 0.14 wt% of the polymer and 1.75 wt% of the liquid fraction. Lattimer and
Kroenke[12b] established that most chlorine-containing compounds are formed by sec-
ondary reactions of HCl with the products or polyenic segments of PVC as well as
with the compounding ingredients of PVC. Direct scission of the PVC chains to form
chlorine-containing products is a very minor degradation pathway.
3.2 DEGRADATION OF PVC – POLYMER MIXTURES
Recently the pyrolysis of polymer mixtures has become a focus of interest due to the
increasing role of plastics recycling. Many researchers have investigated the thermal
decomposition of various polymers in the presence of PVC. Knümann and Bockhorn
[25] have studied the decomposition of common polymers and concluded that a sepa-
ration of plastic mixtures by temperature-controlled pyrolysis in recycling processes is
possible. Czégény et al. [31] observed that the dehydrochlorination of PVC is promoted
by the presence of polyamides and polyacrylonitrile; however, other vinyl polymers or
polyolefins have no effect on the dehydrochlorination. PVC generally affects the decom-
position of other polymers due to the catalytic effect of HCl released. Even a few per
cent PVC has an effect on the decomposition of polyethylene (PE) [32], HCl appears to
promote the initial chain scission of PE. Day et al. [33] reported that PVC can influence
the extent of degradation and the pyrolysis product distribution of plastics used in the
electronics industry (acrylonitrile–butadiene–styrene polymer, polycarbonate, and poly-
oxymethylene). PVC promotes the hydrolytic decomposition routes of polyamides and the
product distribution is changed significantly in the presence of PVC [34, 35]. Macropyrol-
ysis of PVC and poly(ethylene terephthalate) (PET) mixtures results in the formation of
a series of chloroorganic compounds including chloroesters of terephthalic and benzoic
acids [36]. It was concluded that PET will reduce the efficiency of dehydrochlorina-
tion during the pyrolytic recycling process in an autoclave. The yield of liquid products
decreased with increasing reaction pressure during the PVC degradation, whereas the
yield of residue increased, reaching maxima at 9.8 MPa (400◦ C) and 22.4 MPa (440◦ C)
[37]. The pressure dependences of the product distribution and atomic ratio of hydrogen
to carbon (H/C) imply that some of the liquid products were polycondensed with the
dehydrochlorinated PVC and were retained in the residue under high pressure. Some of
the polyene chains underwent hydrogenation to form linear paraffins under high pres-
sure [37]. The decomposition of polyvinyl chloride using supercritical water was also
performed by Sato et al. [38].
4 LIQUEFACTION WITH COMMINGLED PLASTICS

AND DECHLORINATION
4.1 PYROLYSIS OF PE, PP OR PS WITH PVC
Degradation of plastic samples can be performed in two different catalyst contact modes
(Figure 18.3): (i) the catalyst is mixed with the plastic samples (catalyst with liquid
phase contact); (ii) the catalyst is kept away from the plastic samples and the gas/vapors
produced during the heat treatment contact the catalyst (catalyst with vapor phase con-
tact). There has been extensive research work on the degradation of PVC mixed waste
plastics into plastic-derived oil and dechlorination of plastic-derived oil by various cat-
alysts/sorbents by Lingaiah et al. [39–42]. In the later stages, it was found that the
simultaneous degradation and dehalogenation was found to be effective and can be per-
formed successfully. The degradation of PE (8 g)/PVC (2 g) at 430◦ C, PP (8 g)/PVC (2 g)
at 380◦ C and PS (8 g)/PVC (2 g) at 360◦ C into fuel oil was performed in a glass reactor
(Figure 18.1) under atmospheric pressure by batch operation without any catalysts (ther-
mal degradation). Table 18.1 shows the yield of products obtained from the degradation
of PVC mixed plastics, and Table 18.2 shows the distribution of chlorine in products and
chlorine content (both organic and inorganic) of oil. Liquid yield was highest (73 wt%)
for PP/PVC and lowest (60 wt%) for PS/PVC degradation. The residue, which consists of
both carbonaceous materials and heavier hydrocarbons, was highest in the case of PS/PVC
degradation. From chlorine balance, 91–96 wt% of the chlorine content of the sample
was evolved as gaseous HCl, 3–12 wt% as liquid, and less than 0.5 wt% as residues.
The organic chlorine content of the oil from PP/PVC degradation was 12 700 ppm, which
was the highest among the PVC mixed plastics. The oil obtained from PE/PVC mixed
plastics degradation contained 2800 ppm.
Figure 18.4 shows the composition of the liquid product: (a) for hydrocarbons and
(b) for organic chlorine compounds. The liquid products from both PE/PVC and PP/PVC
are distributed broadly in the range C5 –C25 , and the distribution of products from PS/PVC
had a sharp peak at C9 , which is mainly due to styrene monomer. The organic chlorine
catalyst
catalyst
Catalyst/sorbent with Non-catalytic Catalyst/sorbent with

liquid phase contact thermal vapour phase contact
Figure 18.3 Schematic diagram of catalyst/sorbent contact mode during the liquefaction
of plastics. (Reproduced with permission from the American Chemical Society)
Table 18.1 Yields of the products obtained from the degradation of (PE or PP or
PS)/PVCa into fuel oil. (Reproduced with permission from the American Chemical Society)
Degradation Product yield (wt%) dc Cnpd

temperature (g/mL) (−)
(◦ C) Liquid Gas Residue
(L) (G)b (R)
PE/PVC 430 67.9 17.5 14.6 0.76 13.4
PP/PVC 380 73.2 12.8 14.0 0.78 13.0
PS/PVC 360 60.4 12.3 27.3 0.89 9.2
a
Cl content of PVC polymer is 56.8 wt%;
b
G = 100 − (L + R);
c
liquid density;
d
average carbon number of liquid
Table 18.2 Distribution of Cl in the products obtained from the degradation of (PE or PP or
PS)/PVC into fuel oil. (Reproduced with permission from the American Chemical Society)
Degradation Cl distribution (wt %)

temperature (◦ C)
Liquid Gas Residue Cl content in
oil (ppm)
Organic Inorganic Inorganic Organic Inorganic Total Organic Total
PE/PVC 430 1.8 1.1 96.6 0.1 0.1 99.7 2800 4500
PP/PVC 380 8.8 3.4 89.4 0.1 0.0 101.7 12700 17600
PS/PVC 360 4.2 1.8 91.8 0.5 0.0 98.3 7400 10500
compounds were distributed in the boiling point range 36–174◦ C (equivalent to the boiling
points of n-C6 to n-C10 ) for PE/PVC and PP/PVC and 174–195◦ C for PS/PVC. The
main chlorine compounds from PE/PVC and PP/PVC liquid products were identified as
2-chloro-2-methylpropane and 2-chloro-2-methylpentane, and from PS/PVC degradation
were α-chloroethylbenzene and 2-chloro2-phenyl propane. Ivan et al. [43] have reviewed
60 CH2 CH C–NP–gram
CH3 CH3 CH3

CH2 C CH2 CH CH CH2
(Propylene trimer)
Weight percent /%
40
Propylene tetramer
Propylene pentamer
PE/PVC 430˚C
20
PP/PVC 380˚C
PS/PVC 360˚C
0
5 10 15 20 25
Carbon number
0.8
CH3 Cl-NP-gram
CH3 C CH3
Cl CH3
Org. Cl content in oil/wt%
0.6 CH3 CH2 CH2 C CH3

Cl
Cl
0.4 CH3 CH Cl CH3 C CH3
0.2 PE/PVC 430˚C

PP/PVC 380˚C
PS/PVC 360˚C
0.0
5 10 15 20 25
Carbon number
Figure 18.4 (a) C-NP gram of liquid products from thermal degradation of (PE or PP or
PS)/PVC (8/2) mixture (10 g); (b) Cl-NP gram of liquid products from thermal degradation
of (PE or PP or PS)/PVC (8/2) mixture (10 g). (Reproduced with permission from the
the mechanism of dehydrochloriantion of PVC. The degradation of PP/PVC mixture

was carried out at 380◦ C in the presence of a silica–alumina (SA1) catalyst, which is
known as an effective catalyst for the degradation of hydrocarbons. Figure 18.5 shows
the C-NP gram of liquid products obtained from the PP/PVC at 380◦ C in the presence
and absence of SA1 catalyst. The initial slope of the cumulative volume curve represents
the initial recovery rate of oil. As can be seen, by the use of solid acid catalyst, the rate
of oil recovery is increased and the weight fraction of heavier hydrocarbons decreased.
Therefore, the solid acid catalyst accelerated the rate of oil recovery and lowered the
boiling point distribution of products.
20
Thermal
Weight percent/%
SA1
10
0
5 10 15 20 25
Carbon number
Figure 18.5 C-NP gram of liquid products from thermal and catalytic (SA1) degradation
of PP/PVC (8/2) mixture (10 g) at 380◦ C. (Reproduced with permission from the American
Chemical Society)
4.2 THERMAL DEGRADATION OF PP/PVC BY SOLID ACID CATALYSTS

AND DECHLORINATION WITH IRON OXIDES
The effect of iron oxides such as FeOOH, Fe2 O3 , and Fe3 O4 as chlorine sorbents were
examined for the degradation of PP/PVC at 380◦ C. Table 18.3 shows the product yield and
chlorine content of oil obtained from the thermal degradation of PP/PVC. As mentioned
earlier, the oil from the thermal degradation of PP/PVC contained 12 700 ppm of organic
chlorine compounds. When only the solid acid catalyst SA1 was used in both liquid
(No. 2) and vapor phase contact (No. 3), the chlorine content of oil decreased slightly;
however, when FeOOH was used in both liquid (No. 4) and vapor phase contact (No. 5),
the chlorine content of oil decreased significantly (3000–4000 ppm). The best result, i.e.
the lowest content of chlorine (1100 ppm) in oil was obtained when both FeOOH and
SA1 were in the vapor phase (No. 7).
Figure 18.6 shows the C-NP gram of the liquid products obtained from PP/PVC with
different catalysts and mode of contact and Figure 18.7 shows the Cl-NP gram of the
liquid products obtained from PP/PVC. It is evident that when SA1 was used in liq-
uid phase contact the amount of higher molecular-weight products decreased and the
lower-molecular-weight products increased. FeOOH had no effect on the nature of the
degradation products. When FeOOH was used as chlorine sorbent, the organic chlorine
compounds identified in the products were the same as the thermal degradation, but the
amount decreased significantly.
The effect of type of iron oxides on the removal of chlorine from the PP/PVC-derived oil
was investigated using Fe2 O3 , Fe3 O4 , and FeOOH in vapor phase contact. The distribution
of chlorine in the gases (inorganic only), liquids, residues, catalysts and sorbents of the
products are shown in Figure 18.8. As can be seen, the distribution of chlorine in FeOOH
and Fe3 O4 was more than 90%, which indicates that these iron oxides are very effective
for fixing chlorine in their structural framework. However, in the case of Fe2 O3 , the
506
Table 18.3 Degradation of PP/PVC = 82 (10 g) into fuel oil at 380◦ C. (Reproduced with permission from the American Chemical Society)
No. Contact mode Catalyst Degradation yield (wt %) d c (g/mL) Cnpd (−) Cl content in oil (ppm)
Liquid (L) Gas (G)a (HCb /HCl ratio) Residue (r) Organic Total
1 Thermal 73.2 12.8 (24.1/75.9) 14.0 0.78 13.0 12700 17600
2 Liquid phase SAl 59.2 21.0 (52.4/47.6) 19.8 0.71 8.6 7000 8600
4 Liquid phase FeOOH 73.4 9.7 (81.2/18.8) 16.9 0.78 12.9 4100 5400
6 Liquid phase FeOOH, SAl 60.6 17.0 (88.5/11.5) 22.4 0.73 8.7 18100 23100
3 Vapor phase SAl 68.4 14.5 (35.5/64.5) 17.1 0.74 10.1 11400 13900
5 Vapor phase FeOOH 62.6 8.9 (92.4/7.6) 28.5 0.75 10.9 3200 4100
7 Vapor phase FeOOH, SAl 63.9 16.4 (98.4/1.6) 19.7 0.73 9.8 1100 1700
Vapor phase FeOOH
8 60.5 13.6 (97.8/2.2) 25.9 0.72 8.8 5600 14900
Liquid phase SAl

Vapor phase SAl
9 63.1 17.5 (92.2/7.8) 19.4 0.77 10.4 4900 6200
Liquid phase FeOOH
a
G = 100 − (L + R);
b
gaseous hydrocarbon;
c
liquid density;
d
average carbon number of liquid
T. BHASKAR AND Y. SAKATA
30
Propylene trimer Thermal and catalytic
degradation
Propylene tetramer
Weight percent / %
20
Propylene pentamer
1 Thermal
2 SA1 LP
10 3 SA1 VP
4 FeOOH LP
5 FeOOH VP
0
5 10 15 20 25
Carbon number
Figure 18.6 C-NP gram of liquid products from thermal and catalytic degradation
of PP/PVC (8/2) at 380◦ C. (Reproduced with permission from the American Chemical
Society)
CH3
0.6 CH3 C CH3 Cl NP gram
Cl
Org. Cl content in oil/wt%
CH3
0.4 CH3 CH2 CH2 C CH3
Cl
1 Thermal
CH3 2 SA1 LP
0.2 CH3 CH2 C CH3 3 SA1 VP
Cl 4 FeOOH LP
5 FeOOH VP
0.0
5 10 15 20
Carbon number
Figure 18.7 Cl-NP gram of liquid products from thermal and catalytic degradation
of PP/PVC (8/2) at 380◦ C. (Reproduced with permission from the American Chemical
Society)
distribution of chlorine in the sorbent was less than 50%, and gaseous products were
about 40%. Furthermore, the chlorine content in oil (Figure 18.8) was almost the same
as the thermal degradation. This indicates that Fe2 O3 is not as effective as FeOOH and
Fe3 O4 . The crystalline structure of used iron oxides was determined using an X-ray
diffractometer. The crystalline structure of both FeOOH and Fe3 O4 was Fe3 O4 after use
in the PP/PVC degradation. However, no crystalline phase of iron chloride was observed.
The formed FeCl2 can be present as a monolayer on iron (II) oxides, and no crystalline
peaks of FeCl2 are observed under these conditions [44]. Although the data on chlorine
removal from PE/PVC and PS/PVC degradation using solid sorbents are not shown, they
Org. Cl content in oil Gas Sorbent

Org. + Inorg. Cl content in oil Liquid Residue
100
Distribution of Cl in products/wt%
20000
80
Cl content in oil/ppm
15000
60
40 10000
20 5000
0 0
Thermal FeOOH TR-96103 Fe2O3 Fe3O4
Figure 18.8 Distribution of chlorine in products and sorbents from thermal and catalytic
degradation of PP/PVC (8/2) at 380◦ C. (Reproduced with permission from the American
Chemical Society)
showed similar effects to those in PP/PVC, i.e. the content of chlorine in the oil products
was decreased by the use of chlorine sorbents. Detailed discussion on the effect of various
other iron oxides is given elsewhere [21].
4.3 THERMAL DEGRADATION OF PE MIXED WITH PET
The thermal degradation of PE mixed with polyethylene terephthalate (PET) and PE only
degradation were compared. The presence of small amounts of PET is quite possible
with the mixture of PE, PP, and PS, which is generally considered as municipal waste
plastics. The yields of product gases, liquids and residues from the degradation of PET
and the mixtures of PET and PE in ratios of 1:9 and 2:8 are shown in Table 18.4. Unlike
PE or PVC, no liquid products could be obtained from the degradation of PET. The
decomposition of PET proceeds with the production of a large amount of pale yellow
Table 18.4 Product yields for thermal degradation of PET and mixtures of PE and PET at 430◦ C.
Samples PE/PET Product yielda Average density of liquid

(wt ratio) Liquid (L) Gas Residue (R) product (g/cm2 )
(wt%) (wt%) (wt%)
PE(10 g) 10:0 69.2 8.5 22.3 0.76
PET(1 g) + PE(9 g) 1:9 52.2 11.2 36.6 0.77
PET(2 g) + PE(8 g) 2:8 32.7 15.3 52.0 0.76
PET(10 g) 0:10 33.4 66.6
a
G = 100 − (L + R).
20
PE 10g
PET : 1g + PE 9g
15 PET : 2g + PE 8g
Weight percent/%
10
0
5 10 15 20 25
Carbon number
Figure 18.9 C-NP gram of the liquid products from degradation of mixtures of PE and
PET at 430◦ C. (Reproduced with permission from Elsevier)
particles, most probably consisting of benzoic acid and terephthalic acid, which eventu-
ally blocked the outlet of the reactor. Carbonaceous residues were also obtained inside
the reactor. Total yield of residues (both carbonaceous compound and yellow particles)
was 66.6 wt% and the yield of gaseous products was 33.4 wt%. The gaseous products
were mainly carbon monoxide and small amount of hydrocarbons (C1 –C3 ). As was the
case with the mixture of PE and PVC, the addition of PET to PE affected the product
yields of gaseous product and residues increased compared with the product yields of PE
degradation.
Figure 18.9 shows the NP grams of liquid products obtained from the degradation of
the mixture of PE and PET, and is compared with the NP gram of liquid products from
PE. Due to the addition of 10% PET to PE,, the weight fraction of higher-molecular-
weight components decreased in the liquid products and those of low-molecular-weight
components increased compared with the degradation products (liquid) of PE. Addition
of 20% PET further enhanced the degradation of PE into low-molecular-weight products.
These results suggest that the presence of the residues from PET decomposition may
promote the degradation of PE. Visual inspection of the inside of the reactor during the
thermal degradation of plastics such as PE, PVC and mixtures of PE with PVC, and PE
with PET have been discussed in detail [45].
4.4 LABORATORY EVALUATION OF VARIOUS CARBON COMPOSITES

AS HCl SORBENTS
Calcium-, iron- and potassium-based carbon composites were evaluated for the HCl sorption
capacity for use in the dehalogenation process with PVC mixed plastics degradation. It is
2000
Inlet HCI
1800
Ca-C
1600 K2CO3-C
1400
Outlet HCI, ppm
1200 Fe-C
1000
800
600 Ca-C
400 Fe-C
K2CO3-C
200
0
0 2 4 6 8 10 12 14 16 18 20
Reaction time, h
Figure 18.10 HCl reaction profiles with Ca-C, Fe-C and K2 CO3 -C sorbents at identical
reaction conditions. (Reproduced with permission from the American Chemical Society)
well known that the presence of chlorine-containing plastics in the degradation process
produces more than 95% of chlorine (depending on degradation conditions it may vary) in
the form of hydrogen chloride and the remaining chlorine as some chlorinated hydrocarbons
and some part in the residue. An effective sorbent should have high hydrogen chloride
sorption capacity, be economical and should be recycled easily. A schematic experimental
set-up for the reaction of hydrogen chloride with various sorbents, experimental and analysis
conditions have been given in detail elsewhere [46].
The reaction of hydrogen chloride with calcium carbonate (CaCO3 )-, iron oxide
(Fe3 O4 )-, and potassium carbonate (K2 CO3 )-based carbon composite sorbents and the
results are presented in Figure 18.10. Figure 18.10 shows that the Ca-C sorbent completely
captured the hydrogen chloride (1820 ppm) for a period of 7 h, Fe-C and K2 CO3 -C did
not effectively adsorb the HCl gas. K2 CO3 -C reacted completely with the HCl gas for
1 h, but from the second hour onwards leakage from the reactor (sorbent) was observed
and within a short reaction time of 3 h, the inlet and outlet HCl concentrations were same,
indicating that there is no reaction with the sorbent after the third hour. The Fe-C sorbent
released HCl from the first hour onwards. However, adsorbed HCl at a steady rate of
45% of inlet HCl concentration from third hour onwards. It indicates that the Fe-C reacts
with HCl, but the reaction rate is slow compared with Ca-C.
The theoretical sorption capacities of three sorbents calculated based on stoichiometric
equations and experimental sorption capacities calculated taking the HCl sorbed before
breakthrough are presented in Table 18.5. Theoretical adsorption capacities of Ca-C, Fe-C,
and K2 CO3 -C were 0.73 g/g, 0.95 g/g, 0.53 g HCl/g sorbent respectively. Observed sorp-
tion capacities of three sorbents (Table 18.5) until steady state level shows that the Ca-C
(0.48) has higher sorption capacity per gram of sorbent than Fe-C (0.23) and K2 CO3 -C
(0.17 g/g). Table 18.5 shows that the sorption capacity of Ca-C until the breakthrough
Table 18.5 Theoretical sorption capacities, consumed theoretical capacities during HCl reaction,
and adsorption time consumed until steady state time for various sorbentsa . (Reproduced with
permission from the American Chemical Society)
Sorbent (A) theoretical (B) amount of HCl Theoretical Observed adsorption Adsorption time
adsorption capacity adsorbed before the consumed capacity capacity until continued until
b
[HCl(g)]/[ads(g)] breakthrough (B)/(A)100 [%] steady state steady state, h
[HCl(g)]/[ads(g)] [HCl(g)]/[ads(g)]
Ca–C 0.73 0.31 (7 h) 43 0.48 16
Fe–C 0.95 0.00 0.23 10
K2 CO3 –C 0.53 0.04 (1 h) 8 0.17 6
a ◦
Parameters: temperature 350 C; weight of sorbent 2 g; total gas flow 535 mL/min; linear gas velocity 0.18 m/s; particle size
(average diameter): 1 mm;
b
breakthrough point was taken when the HCl leakage observed at the outlet of the reactor
point (43% of theoretical adsorption capacity) was much higher than K2 CO3 -C (8%) and
Fe-C. Experimental (observed) sorption capacities were calculated based on the quantity
of reacted HCl before breakthrough (leakage of HCl from reactor). The sorption of HCl
with different sorbents carried out for different times, as the steady state level of sorbent
with the HCl was reached at different time for various sorbents.
The reaction of various metal oxides with hydrogen chloride and the reverse reac-
tions have been extensively studied [47] the reaction behavior of hydrogen chloride with
various bivalent and trivalent metal oxides has been reported. Sakata et al. reported the
spontaneous degradation of municipal waste plastics at low temperature [48] and also
the dechlorination of chlorine compounds from PVC mixed plastics-derived oil using
solid sorbents [22]. Courtemanche and Levendis [49] reported the control of HCl emis-
sion from the combustion of PVC by in-furnace injection of calcium–magnesium-based
sorbents at gas temperatures of 850 and 1050◦ C. In the present study, the adsorption tem-
perature 350◦ C was found to be optimum for the complete removal of hydrogen chloride
at moderate concentrations (1820 ppm).
Some important parameters affecting the chlorinating process are sorbent size, HCl
concentration, adsorption temperature, porosity, total surface area, and residence time.
For effective heterogeneous reactions, the sorbent should be small in size, porous, and
well dispersed in the combustion effluent gases. Superior intraparticle transport enhanced
the reactivity of sorbent cenospheres, and increased calcium utilization were reported
by Steciak et al. [22]. Small pores are prone to plugging by chlorination or sulfation
products. These results suggest that calcium-based sorbents can be used for the complete
removal of hydrogen chloride. The following paragraphs provide the optimized physical
parameters for the HCl adsorption reaction parameters for a calcium-based sorbent.
The effect of temperature on HCl sorption capacity of Ca-C was studied using sorbent
weight (2 g), average particle diameter (1 mm), total gas flow (530 mL/min), inlet HCl
concentration (1820 ppm) and varied temperatures 100 200, 270, 350, and 400◦ C and the
reaction profiles are presented in Figure 18.11. It can be clearly seen from the sorption
profile at 100 and 200◦ C that the amount of reacted HCl is very small and that leakage
from the reactor was observed from the first hour. The sorption profile obtained for
270◦ C showed that until 4 h (breakthrough point) the HCl is completely captured by
Ca-C; leakage is observed from 4 h onwards and it reaches a steady state level after
13 h. Sorption profile obtained for 400◦ C shows that HCl leakage started from 5 h and
2000
Inlet HCl
1800
100
1600 200
1400
400
Outlet HCl, ppm
1200
1000 270
800
600
100 C
200 C
400 270 C
350
350 C
200 400 C
0
0 2 4 6 8 10 12 14 16 18 20
Reaction time, h
Figure 18.11 Effect of temperature on reaction profiles of HCl for Ca-C sorbent. (Repro-
duced with permission from the American Chemical Society)
after 10 h, it reached a steady state. It can be concluded that low temperatures and high
temperatures are not favorable for the adsorption HCl gas without leakage and high
breakthrough time. The sorption profile obtained at 350◦ C shows the complete capture of
HCl up to 7 h (breakthrough point), reaching a steady state level around 14 h. From these
results, the 350◦ C were found to be optimum temperature for the adsorption of HCl gas
on Ca-C with higher breakthrough point. In a similar way Levendis et al. [50] reported
the relative utilization of calcium-based sorbents for the capture of HCl gas using HCl
gas diluted with nitrogen, and found that the chlorination of the sorbents occurred in
the hot zone of the furnace at gas residence times ∼1 s. They observed that the calcium
carbonate reached a relative utilization of 54% in the mid-temperature range, while the
calcium oxide reached an 80% relative utilization at the lowest temperature examined
(600◦ C) [50]. The contact times during the present study were also less than 1 s and
detailed studies on effect of gas flow rates were presented in the following sections.
Weinell et al. [51] found that the reaction of calcium-based compounds with HCl ceases
at a certain extent without complete conversion of the sorbent. This was defined as the
maximum conversion, and was found to increase with the temperature. They also found
that increasing particle diameter in the range of 0.2–2 mm and HCl concentration in the
range 1.3–4 vol% led to a smaller conversion of CaCO3 to CaCl2 . The progress of the
reaction was reported to be influenced by pore blocking and at higher temperatures by
a molten phase of CaCO3 to CaCl2 . They reported that the conversion from CaCO3 to
CaCl2 depends not only on particle size and HCl concentration, but also on the relative
humidity of the gas.
The effect of inlet HCl concentration was studied with 1090, 1800, and 3900 ppm
as inlet HCl concentration. The other reaction parameters such as sorbent weight (2 g),
average sorbent particle diameter (1 mm), total gas flow (535 mL/min), linear gas veloc-
ity (0.18 m/s), and temperature of adsorption (350◦ C) was kept constant. The results
showed that the sorption capacity with 1090 ppm was 37% and the sorption capacity
value increased to 43% for 1820 ppm. At higher HCl concentration (3900) the adsorption
capacity was decreased to 35%. The HCl adsorption capacity (43%) with 1820 ppm was
more than 1090 and 3900 ppm, even though the observed HCl adsorption until saturation
was less (1820 rather than 1090 on 3900 ppm). The adsorption capacity of Ca-C sorbent
was more (43%) with 1820 ppm inlet HCl with 7 h breakthrough time. In similar condi-
tions, the effect of total gas flow rate was studied using 250, 535 and 900 mL/min. The
total gas flow was varied keeping the inlet HCl concentration as 1820 ppm. The results
showed that the increase of flow rates decreased the breakthrough point and the sorption
capacity of sorbent due to less contact time. The breakthrough of HCl for 250, 535 and
900 mL/min was 16, 7 and 3 h respectively. It is clear from these studies that the sorption
capacities of Ca-C were found to decrease from 45 to 31% with the increase of flow rate
from 250 mL to 900 mL/min.
The effect of particle size on the HCl sorption capacity of Ca-C was studied varying
the particle sizes i.e. 0.25, 1.0, and 2.0 mm. The other reaction parameters such as sor-
bent weight (2 g), total gas flow (535 mL/min), linear gas velocity (0.18 m/s), inlet HCl
concentration (1820 ppm), and temperature of adsorption (350◦ C) were kept constant.
Figure 18.12 shows that with increase of sorbent particle size the breakthrough of HCl
was found to increase from 11 h (0.25 mm) to 2 h (2 mm). The results calculated from
the adsorption isotherms, such as amount of HCl adsorbed before breakthrough, observed
HCl adsorption until steady state level and adsorption time until steady state are presented
in Table 18.6. The adsorption capacity of Ca-C was 63% with particle size 0.25 mm. The
increase of particle size from 0.25 to 2 mm decreased the theoretical consumed capacity
from 63 to 11%. These studies clearly indicated that calcium-based sorbents are effective
for the dechlorination of PVC mixed waste plastics pyrolysis process.
2000
Inlet HCl
1800
1600
1400
Outlet HCl, ppm
1200
1.0
1000 2.0
0.25
800
0.25 mm
600
1.0 mm
400
2.0 mm
200
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
Reaction time, h
Figure 18.12 Effect of particle size on HCl reaction profiles for Ca-C sorbent. (Repro-
duced with permission from the American Chemical Society)
Table 18.6 Effect of particle size on consumption of theoretical capacity of Ca-C. (Reproduced
with permission from the American Chemical Society)
Particle size of (B) amount of HCl Theoretical Observed adsorption

sorbent (mm) adsorbed before consumed capacity amount until
average diameter the breakthroughb (B)/(Ac )100 [%] steady state
[HCl(g)]/[ads(g)] [HCl(g)]/[ads(g)]
0.25 0.46 (11 h) 63 0.58 (22 h)
1.0 0.31 (7 h) 43 0.48 (16 h)
2.0 0.09 (2 h) 11 0.21 (7 h)
a
Parameters: temperature 350◦ C; weight of sorbent 2 g total gas flow 535 mL/min;
b
breakthrough point was taken when the HCl leakage observed at the outlet of the reaction;
c
(A) theoretical adsorption capacity [HCl(g)]/[ads(g)] = 0.73
Table 18.7 Product yields and properties of liquid product from PVC mixed PP/PE/PS plastic
degradation using Ca-C (6 consecutive runs) and thermal degradation. (Reproduced with permission
from the American Chemical Society)
Degradation and run Yield of degradation products Liquid products

number using Ca–C (wt %)
Liquid Gas Residue Cnpc Density
(L) (G)b (R) (g/cm3 )
Thermal 63 24 13 10.4 0.79
1 67 23 10 10.8 0.80
2 65 22 13 10.7 0.79
3 67 21 12 10.7 0.79
4 69 21 10 10.9 0.80
5 75 15 10 10.8 0.81
6 70 20 10 10.6 0.80
a
Weight ratio: PVC:PP:PE:PS = 1:3:3:3; weight of Ca–C: 4 g; degradation temperature 430◦ C; dechlorination
temperature 350◦ C;
b
G = 100 − (L + R);
c
Cnp = average carbon number of liquid products based on C–NP gram
4.5 LIQUEFACTION OF PVC MIXED PLASTICS AND DECHLORINATION

WITH Ca-C
The pyrolysis of mixed plastics containing PVC (PVC/PP/PE/PS) was performed under
atmospheric pressure in a batch process using Ca-C sorbent and thermal degradation (no
sorbent). Table 18.7 shows the yield of products (gas, liquid, and residues) and average
carbon number (Cnp), density of liquid products obtained during thermal degradation
and using Ca-C sorbent. The thermal degradation (PVC/PP/PE/PS at 430◦ C) produced
liquid products (63 wt%), with average carbon number of 10.4 and density 0.79 g mL−1 .
The liquid product obtained during the degradation with Ca-C sorbent was about 67
(run 1) and 75 wt% (run 5). There is no appreciable change in the Cnp, and density of
liquid products obtained during both in thermal degradation and degradation using Ca-C
sorbent (Table 18.7). The gaseous products obtained during the thermal degradation were
approximately the same as for degradation using sorbent. There is no appreciable change
Table 18.8 Chlorine content in PVC mixed PP/PE/PS plastic degra-
dation liquid products using Ca-C and theoretical consumed sorbent
capacity for each runa . (Reproduced with permission from the Amer-
ican Chemical Society)
Degradation and Chlorine content Consumed theoretical

run number in liquid products capacity of CaCO3
using Ca–C (ppm) (%)
Thermal 360
1 0 18
2 0 35
3 0 53
4 0 71
5 150 89
6 3000 106
a
Weight ratio PVC:PP:PE:PS = 1:3:3:3; weight of Ca–C 4 g; degradation
temperature 430◦ C; dechlorination temperature 350◦ C
in amount of residue for the thermal degradation and degradation using sorbent from
run 1 to run 4. Roy et al. [52] reported on the vacuum pyrolysis of commingled plastics
(HDPE/LDPE/PP/PS) containing PVC at a final temperature of 500◦ C and under a total
pressure of 2 kPa. During their vacuum pyrolysis studies, the pyrolysis oil contained
12 ppm Cl on a pyrolysis oil basis. Pyrolysis under vacuum reduces the incidence of
secondary reactions in comparison with slow pyrolysis at atmospheric pressure [52].
The total chlorine content in liquid products obtained during thermal degradation, using
Ca-C sorbent and theoretical consumed capacity of Ca-C sorbent during each run of mixed
plastic degradation is presented in Table 18.8. As can be seen from the table, 360 ppm of
chlorine content is found in liquid products obtained during thermal degradation. However,
the chlorine content is zero (not detected) from run 1 to run 4 when using Ca-C sorbent
(4 g), indicating that the chlorine compounds (inorganic and organic) were completely
removed from the liquid products. The theoretical consumed capacity of CaCO3 was
calculated as follows. In the present study 1 g of PVC (for each batch 1 g of PVC) and
4 g of CaCO3 (the same sorbent repeatedly used for run 1 to run 6) sorbent used for the
experimental investigation. 1 g of PVC contains 0.524 g of Cl and 4 g of CaCO3 can
consume 2.92 g of Cl (1 g CaCO3 can react with 0.73 g Cl). Table 18.8 shows that Ca-C
sorbent consumed all the chlorine for run 1, indicating that about 18% (0.524/2.92 × 100)
of theoretical sorbent capacity was utilized. In a similar way, the theoretical consumed
sorbent capacity was calculated for run 2 to run 6.
The chlorine content in aqueous NaOH trap was analyzed by an ion chromatograph.
During thermal degradation about 92 wt% of HCl (gaseous) was found in NaOH trap,
about 3 wt% chlorine was observed in residue. The degradation using Ca-C sorbent
showed that there is no chlorine in oil from run 1 to run 4. However, there is a small
amount of chlorine in the NaOH trap during run 3 (0.33 wt%) and run 4 (1.21 wt%). The
degradation for run 5 and run 6 showed the presence of chlorine in the oil (Table 18.8)
and in the NaOH trap (run 5 = 1.68 and run 6 = 55.3 wt%).
Meszaros [53] reported the pyrolysis of municipal plastic waste (MPW) containing 3%
of PVC in an auger kiln reactor (Conrad recycling process). Lime was used in order
to trap the HCl evolved, which resulted in liquid products with 25 ppm of chlorine. In
the present process, the inorganic chlorine (HCl) was captured by Ca-C sorbent and the
chlorinated hydrocarbons produced during the PVC mixed plastic pyrolysis process were
dehydrohalogenated by Ca-C. About 71% of theoretical HCl sorption capacity of Ca-C
was utilized for the four batches of PVC mixed PP/PE/PS plastic pyrolysis process. The
chlorine content 150 ppm was observed during run 5 of degradation and the chlorine
content increased from 150 ppm to 3000 ppm (run 6), which is higher than the thermal
degradation. This clearly indicates that the sorbent cannot be used in the process after
71% of theoretical capacity (Table 18.8). The presence of a higher content of chlorinated
hydrocarbons during run 6 (3000 ppm) than for thermal degradation (360 ppm) might be
due to the hydrocarbons produced during the pyrolysis process reacting with the calcium
chloride (CaCO3 converted to CaCl2 during process) and forming the chlorinated hydro-
carbons in the liquid products. This is an additional process than forming the chlorinated
hydrocarbons by reaction of free hydrogen chloride with hydrocarbons produced during
the thermal degradation [54]. In the preset study; we were able to utilize about 71% of its
theoretical capacity (up to 4 batch processes) without chlorine compounds in the liquid
products. Bockhorn et al. [7] studied the pyrolysis of a PVC/PS/PE (1:6:3 by weight) mix-
ture in three circulated-sphere reactors arranged in a cascade and they detected 44 ppm
of chlorine in oil from the third reactor, which mainly contained aliphatic compounds.
However, the chlorine content in the oil from the second reactor was still high at 210 ppm.
The C-NP diagram of liquid products showed that the hydrocarbons (C6 –C11 ) dur-
ing the thermal degradation and degradation using Ca-C sorbent was 47 wt%. As with
the C-NP diagram, the carbon number distribution of chlorinated hydrocarbons (wt% of
chlorinated hydrocarbons = g(Cl)/g(Oil) × 100 wt%) in the liquid product was prepared
from the gas chromatogram obtained using a gas chromatograph with an atomic emission
detector (GC-AED). The wt% of chlorinated hydrocarbons is shown in a Cl-NP diagram
in Figure 18.13. The hydrocarbons containing the chlorine were distributed in the range
0.15
Thermal (360 ppm Cl)

1st run (0 ppm Cl)
Weight percent of chlorine
2nd run (0 ppm Cl)

0.1
3rd run (0 ppm Cl)
4th run (0 ppm Cl)
5th run (150 ppm Cl)
6th run (3000 ppm Cl)
0.05
0
5 10 15 20 25
Carbon number
Figure 18.13 Cl-NP gram of liquid products obtained during PP/PE/PS mixed with PVC
thermal degradation and degradation using Ca-C sorbent. (Reproduced with permission
of C6 –C11 . The liquid products were analyzed by GC-MS to identify the compounds.
Both the chlorine content and concentration of chlorine-containing organic compounds in
liquid products were determined by gas chromatography with an atomic emission detector
(GC-AED), which provides selective detection of Cl in the liquid products.
The selective chlorine compounds analyzed by GC-AED chromatograms are presented
in Figure 18.14. The presence of chlorinated compounds during the thermal degradation
and degradation with sorbent (run 5 to run 6) was observed. 2-Chloro-2-phenyl propane
was the major chlorine compound observed during thermal degradation (Figure 18.14a)
and also during run 6 (Figure 18.14d). 2-Chloro-2-methyl propane, 2-chloro-2-methyl
pentane, and α-chloro ethyl benzene was also identified during runs 5 and 6 (Figure 18.14c
and 18.14d). The formation of chlorinated hydrocarbons might be due to either of the
following reactions: Cl radicals produced by the thermal degradation of PVC reacting with
cracked hydrocarbon species, or free hydrogen chloride reacting with cracked hydrocarbon
species. We suggest the latter, i.e. that organic compounds are produced by the reaction
between hydrogen chloride originating from PVC and the hydrocarbons obtained from
the degradation of PE, PP and PS [22]. The chlorinated hydrocarbons formed during the
pyrolysis of commingled plastics were different from those obtained during the thermal
Counts
40
20 (d) Run 6
0
0 10 20 30 40 50 60 min
Counts
40
(c) Run 5
20
0
0 10 20 30 40 50 60 min
Counts
40 (b) Run 1 to 4
20
0
0 10 20 30 40 50 60 min
Counts
40 (a) Thermal
20
0
0 10 20 30 40 50 60 min
Retention time, min
Figure 18.14 GC-AED chromatograms of chlorine compounds for PP/PE/PS mixed with
PVC thermal degradation and degradation using Ca-C. (Reproduced with permission
Internal standard for chlorine (1,2,4-trichloro benzene)
2-chloro-2-phenyl propane
α-chloro ethyl benzene
2-chloro-2-methyl pentane
2-chloro-2-methyl propane
(b) After degradation

(peaks due to CaCl2,nH2O)
where n = 2, 4
Intensity(a.u.)
(a) Before degradation

(peaks due to CaCO3)
5 25 45 65
2 Theta
Figure 18.15 X-ray diffraction patterns of Ca-C sorbent before and after the pyrolysis:
(a) before degradation (peaks due to CaCO3 ); (b) after degradation (peaks due to CaCl2
nH2 O), n = 2, 4. (Reproduced with permission from the American Chemical Society)
decomposition of pure PVC. However, the hydrocarbons produced in the oil fraction were
similar to those identified during the pyrolysis of single plastics [52].
Representative X-ray diffraction patterns of the Ca-C before and after the degradation
experiment are shown in Figure 18.15. The X-ray diffraction pattern before degradation
indicates the presence of a CaCO3 phase (Figure 18.15a) but after degradation peaks due
to CaCl2 .nH2 O (where n = 2, 4) phase (Figure 18.15b) were observed, indicating the
sorption of chlorine by CaCO3 . It was demonstrated that the pyrolysis of PVC-containing
PP/PE/PS mixed plastics (degradation at 430◦ C) using Ca-C sorbent gave halogen-free
liquid products (dechlorination at 350◦ C). The Ca-C sorbent was used successfully for the
consecutive 6 batch processes and obtained halogen-free liquid products up to 4 run by
utilizing 71% of sorbent theoretical HCl sorption capacity. The use of the same sorbent
beyond its experimental sorption capacity produced more chlorinated compounds than the
thermal degradation. In order to see the debromination effect of Ca-C sorbent, the Ca-C
has been used during the pyrolysis of brominated flame retardant containing high-impact
polystyrene (HIPS-Br), PVC and PE, PP, PS mixed plastics.
4.6 LIQUEFACTION OF PP/PE/PS/PVC WITH HIPS-Br

AND DEHALOGENATION WITH Ca-C
The thermal degradation of mixed plastics (weight ratio PP/PE/PS/PVC/HIPS-Br =
3:3:2:1:1) was carried out under atmospheric pressure in a batch process at 430◦ C and
Table 18.9 Product yields and properties of liquid products from PP/PE/PS/PVC/HIPS-Br degra-
dation at 430◦ C in the absence and presence of Ca-C sorbent (weight ratio PP:PE:PS:PVC:
HIPS-Br = 3:3:2:1:1). (Reproduced with permission from The Royal Society of Chemistry)
Degradation Yield of degradation Liquid products

method products (wt%)
Liquid Gas Residue Cap b Density
(L) (G)a (R) (g cm−3 )
Thermal 71 17 12 13.7 0.82
Ca–C (2 g) 62 26 12 11.9 0.81
Ca–C (4 g) 66 25 9 12.4 0.81
a
G = 100 − (L + R);
b
Cap = average carbon number of liquid products based on C-NP gram
degradation also carried out with Ca-C. Table 18.9 shows the yield of products such as
gas, liquid, residue, average carbon number, and density of liquid products obtained during
thermal degradation and also degradation using Ca-C. The thermal degradation yielded
liquid products (71 wt%) with the average carbon number 13.7 and density 0.82 g cc−1 .
The use of Ca-C sorbent in the degradation process decreased the liquid products from
71 to 62 wt% (Ca-C 2 g) and 66 wt% (Ca-C 4 g). The amount of residue observed with
thermal degradation and Ca-C (2 g) was 12 wt%. However, the residue in the degradation
process with Ca-C 4 g was about 9 wt% (Table 18.9). The density of liquid products did
not change in the presence or in the absence of Ca-C sorbent. The gaseous products,
which are not condensed as liquid products, were passed through a high-temperature fur-
nace (900◦ C) with aspirator. During this, the gaseous halogenated organic compounds (if
any) were converted into inorganic halogen compounds, which were then passed through
a water trap to capture HBr or HCl.
It is noteworthy that the AED-GC can detect the chlorinated and brominated com-
pounds selectively. The quantitative analysis of chlorine and bromine in the liquid prod-
ucts was carried out by GC-AED and the results are presented in Figure 18.16. As
can be seen from Figure 18.16 that the thermal degradation of mixed plastics (weight
ratio PP/PE/PS/PVC/HIPS-Br = 3:3:2:1:1) produced liquid products with 7300 ppm of
bromine and 1120 ppm of chlorine. However, the use of 2 g Ca-C in the degradation
process drastically decreased the halogen content, the bromine content to 320 ppm and
chlorine to 115 ppm. With the increase of sorbent from 2 to 4 g in the degradation process,
the halogen content was completely removed from the liquid products.
The liquid products were analyzed by GC-MS to identify the compounds. In
our present study, the major hydrocarbons during (thermal and Ca-C) degradation
were aromatic hydrocarbons such as benzene, toluene, ethylbenzene, propylbenzene,
styrene, 1-methylethylbenzene, butylbenzene, α-methylstyrene, etc. In addition to
these compounds, anthracene, naphthalene and substituted derivatives of anthracene,
naphthalene were also observed during the thermal degradation. The presence of
chlorinated and brominated compounds during both the thermal degradation and
degradation using 2 g Ca-C was observed. The chlorinated hydrocarbons found during
the thermal degradation were 2-chloro-2-phenyl propane, 2-chloro-2-methyl propane,
2-chloro-2-methyl pentane, and α-chloro ethyl benzene and brominated hydrocarbons
8000
7300
7000 Cl
6000 Br
Halogen content in oil, ppm
5000
4000
3000
2000
1120
1000 320
115
0
Thermal Ca-C [2 g] Ca-C [4 g]
Degradation method
Figure 18.16 The effect of Ca-C sorbent for dehalogenation (Cl and Br) during PP/PE/PS/
PVC + HPS-Br degradation at 430◦ C. (Reproduced with permission from The Royal
Society of Chemistry)
were bromocyclohexane, and 1-(bromoethyl) benzene, etc. The formation of SbBr3 is

observed in earlier studies on thermal degradation of polyester flame-retarded with
antimony oxide/brominated polycarbonate [55]. However, we have not observed any such
compounds in the liquid products obtained during HIPS-Br mixed with PVC/PP/PE/PS
at 430◦ C.
Striebich et al. [56] reported that the high-temperature degradation of polybrominated
flame-retardant materials produced Br-benzenes, Br-phenols, polybrominated dibenzodi-
oxins (PBDD) and polybrominated dibenzofurans (PBDFs). However, they were sub-
sequently destroyed at high temperature (800◦ C). Dioxin formation (PHDD) and furan
formation (PHDF) in the thermal treatment of plastics containing polybrominated diphenyl
ether with several flame retardants and the diantimony trioxide and decabromodiphenylene
ethers (heating of HIPS for 20 min) produced the dioxins at 275◦ . Former test campaigns
by the Forschungszentrum Karlsruhe and the Association of Plastic Manufacturers in
Europe, at the Karlsruhe TAMARA test facility for waste combustion, focused on the
existence, partitioning, and destruction of bromine and its influence on the formation of
bromine containing dibenzo-p-dioxins and dibenzofurans. In the present study, we have
not found any such compounds, and the gases (which are not condensed) were passed
through the furnace at 900◦ C for complete destruction of compounds [57].
The average carbon number (Cnp) of the liquid product decreased due to the cracking
of higher-molecular-weight compounds in the presence of Ca-C sorbent (Table 18.9 and
30
Thermal
g(c)/g(oil) X 100 (wt%)

20
Ca-C [2g]
Ca-C [4g]
10
0
5 10 15 20 25
Carbon number
Figure 18.17 C-NP gram of liquid products obtained during PP/PE/PS/PVC + HIPS-Br
thermal degradation and degradation using Ca-C sorbent. (Reproduced with permission
from The Royal Society of Chemistry)
Figure 18.17). Figure 18.17 shows the C-NP diagram of the liquid products obtained by
analyzing their gas chromatogram. The carbon numbers in the abscissa of the NP diagram
are equivalent to retention values of the corresponding normal paraffin and the ordinate
shows the weight percent of the corresponding hydrocarbons. The higher hydrocarbons
decreased in the presence of Ca-C at 430◦ C. The hydrocarbons in the C6 -C10 range
during the thermal degradation was 20 wt%, and in the presence of Ca-C [2 and 4 g]
degradation produced approximately 30 wt%. However, the hydrocarbons in the range
C16 –C20 were decreased in the presence of Ca-C sorbent (Figure 18.17). In contrast to
the PVC, there has been various problems with the brominated flame-retardant plastics, as
they contain synergists and also other additives. The effect of antimony trioxide (Sb2 O3 ) on
the degradation products and their composition were well discussed elsewhere [58]. The
degradation of PVC and HIPS-Br and dehalogenation by iron oxide–carbon composites,
effect of PET on the mixed plastics with HIPS-Br and HIPS-Br with PET have been
extensively studied by Bhaskar et al. [59–62].
4.7 LIQUEFACTION OF REAL MUNICIPAL WASTE PLASTICS
The thermal degradation of MWP, 3P/PVC and 3P/PVC/PET was performed under
atmospheric pressure at 430◦ C,where 3P = PP/PE/PS. Table 18.10 shows the yield of
degradation products and average carbon number (Cnp), density of liquid products. The
liquid products (59 wt%) produced with the MWP (20 g) were higher than 3P/PVC/PET
and lower than 3P/PVC liquid products (Table 18.10). It is clear from Table 18.10 that
the presence of PET has predominant effect on the formation of liquid products. The
degradation residue during the MWP thermal degradation was higher than that of model
plastics, due to the presence of various additives in the MWP. There is no appreciable
change in the Cnp, and density of liquid products obtained from PET containing samples
such as 3P/PVC/PET and MWP.
Table 18.10 Products yield and properties of liquid product from 3P/PVC, 3P/PVC/PET and
MWP (20 g) thermal degradation at 430◦ C. (Reproduced with permission from Elsevier)
Plastic sample Yield of degradation products (wt%) Liquid products

Liquid (L) Gas (G)a Residue (R) Cnpb Density (g cc−1 )
3P/PVC 70 25 5 12.1 0.80
3P/PVC/PET 53 34 13 11.6 0.82
MWP 59 25 16 11.9 0.84
Weight of plastic samples PE (6 g) + PP (6 g) + PS (6 g) + PVC (2 g); PE (6 g) + PP (6 g) + PS (6 g)

+ PVC (2 g) + PET (2 g); MWP (20 g)
a
G = 100 − (L + R)
b
Cnp, average carbon number of liquid products based on C–NP gram
Table 18.11 The distribution of chlorine content in various thermal degradation products of
3P/PVC, 3P/PVC/PET and MWP (20 g) at 430◦ C. (Reproduced with permission from Elsevier)
Plastic sample Chlorine in degradation products (mg) Total (mg)

Liquid (L) Gas (G) Residue (R)
Organic Inorganic
3P/PVC 17 0.3 870 2.7 890
3P/PVC/PET 28 3.2 760 21 812
MWP 52 57 53 162
Weight of plastic samples PE (6 g) + PP (6 g) + PS (6 g) + PVC (2 g); PE (6 g) + PP (6 g) + PS (6 g)

+ PVC (2 g) + PET (2 g); MWP (20 g)
The liquid products were analyzed by a gas chromatograph equipped with an atomic
emission detector for the quantitative estimation of chlorine content in liquid products.
As can be seen from the Table 18.11, that the presence of chlorine content in liquid
products is higher with 3P/PVC/PET (28 mg) than 3P/PVC (17 mg). Furthermore, the
chlorine content in liquid products is almost doubled in the MWP (52 mg) pyrolysis. It is
interesting to note that the presence of PET in model and MWP decreased the formation of
inorganic chlorine content (Table 18.11). The inorganic chlorine content during 3P/PVC
(870 mg) was higher than 3P/PVC/PET (760 mg) and MWP (57 mg). The presence of
chlorine content in degradation residue is higher in MWP than the mixed model plastics
3P/PVC and 3P/PVC/PET. Meszaros [53] reported the pyrolysis of municipal plastic
waste (MWP) containing 3% of PVC in an auger kiln reactor (Conrad recycling process).
Lime was used in order to trap the HCl evolved, which resulted in liquid products with
25 ppm of chlorine.
Figure 18.18 illustrates the C-NP diagram of the liquid products obtained by analyzing
their gas chromatogram. The carbon numbers in the abscissa of the NP diagram are equiv-
alent to retention values of the corresponding normal paraffin and the ordinate shows the
weight percent of the corresponding hydrocarbons (g(Cn)X100/g(Oil), wt%). The hydro-
carbons in the range C7 –C10 were very high and about 10 wt% of liquid products are
in the ranges C13 –C15 and C17 –C19 . The hydrocarbons containing chlorine were dis-
tributed in the range of C5 –C9, C10 –C12 , C14 and C21 range in both the model mixed and
50
MWP
40
g(Cn) X 100/g(oil), wt% 3P + PVC
3P + PVC + PET
30
20
10
0
5 7 9 11 13 15 17 19 21 23 25
Carbon number
Figure 18.18 C-NP gram of liquid products obtained during real MWP and model
mixed plastics (3P/PVC and 3P/PVC/PET) thermal degradation at 430◦ C. (Reproduced
with permission from Elsevier)
MWP. However, the quantity of chlorinated hydrocarbons during MWP degradation was
higher than 3P/PVC/PET and 3P/PVC degradation liquid products. Gas chromatography
equipped with an atomic emission detector (GC-AED), was used for selective detection
of Cl in the liquid products. As can be seen from Figure 18.19, the presence of PET
produced the additional chlorinated hydrocarbons than 3P/PVC. The liquid products were
analyzed by GC-MS to identify the compounds. The presence of chlorinated compounds
with model and MWP were observed as 2-chloro-2-phenyl propane, 2-chloro-2-methyl
propane, 2-chloro-2-methyl pentane, and α-chloro ethyl benzene.
In addition, the presence additional chlorinated compounds in the PET mixed plastics
such as 3P/PVC/PET and MWP were found to be chlorine derivatives of benzoic acids.
Kulesza and German [36] reported the influence of poly(vinyl chloride) on poly(ethylene
terephthalate) pyrolysis. They reported that the chloroesters of terephthalic and benzoic
acids were found with PVC and PET mixtures (1:1). In our present investigation, the
PVC/PET ratio was 1:1 and contains the other plastics such as PE, PP and PS. The ratio
of mixed plastics PP: PE: PS: PVC: PET was 3:3:3:1:1 and this composition was prepared
are similar to the real municipal waste from Sapporo, Japan. 2-Methyl benzoylchloride
was identified as one of the additional chlorinated hydrocarbons observed in 3P/PVC/PET
and MWP degradation than 3P/PVC degradation chlorinated hydrocarbons. The other
chlorinated hydrocarbons could not be identified in 3P/PVC/PET and MWP degradation.
It is evident from the studies that the new chlorine compounds obtained due to the presence
of PET in plastic samples in either model mixed on MWP.
5 PILOT PLANT SCALE STUDIES FOR THE LIQUEFACTION OF PVC

MIXED PLASTICS
Based on the laboratory-scale study, the degradation of both model waste plastics (3P
[150]/PVC [3], 153 kg) and MWP (50 kg) was carried out in a large-scale pilot plant
0.16
MWP
0.12
g(Cl) X 100 /g(oil), wt%
3P + PVC
3P + PVC + PET
0.08
0.04
0
5 7 9 11 13 15 17 19 21 23 25
Carbon number
Figure 18.19 Cl-NP gram of liquid products obtained during real MWP and model
mixed plastics (3P/PVC and 3P/PVC/PET) thermal degradation at 430◦ C. (Reproduced
Table 18.12 Raw materials plastics used by operation in pilot plant, and product yields and Cl
concentration in products for thermal and catalytic degradation of 3P/PVCa mixture and municipal
waste plasticsb
No. Raw materials plastics Sorbent Product yield (wt%) Cl content

(kg) (kg) (ppm)
PP PS PE PVC MWP Total Ca–C: Liquid Gas Residue Oil Water
8 mm φ (L) (G)c (R) trap
1 50 50 50 3 150 69 28 3 530 2940
2 50 50 50 3 153 20 82 16 2 NDd 6
3 50 50 20 53 39 6 100 7
a
Cl content of PVC polymer 52.4 wt%;
b
MWP = municipal waste plastics were supplied by Sapporo city, Japan
c
G = 100 − (L + R);
d
ND = not detected (less than the detection limit of instruments)
set-up (250 kg/batch) using calcium-based carbon composite and thermal degradation.
Mixed model plastics and MWP used in pilot plant operation and the distribution of
products, chlorine content are shown in Table 18.12. Municipal waste plastics were sup-
plied by Sapporo City, Japan, and may contain 5–7% of PVC. Table 18.12 shows the
yield of products such as liquid, gas and residue and chlorine content. The thermal degra-
dation of 3P/PVC mixture was carried out and the liquid products contained 530 ppm
of chlorine (organic) and the water trap contained 2940 ppm of HCl. However, degrada-
tion with Ca-C removed all organic chlorine compounds and the concentration of HCl
decreased to 6 ppm (water contained 5–7 ppm HCl). In the case of the degradation of
MWP, the derived oil contains 100 ppm of organic and the water trap contains 7 ppm.
The halogen-free plastic-derived oil obtained during the pilot plant studies was tested in
diesel power generation engines in a 1:3 mixture with commercial fuel oils (kerosene)
and the test was successful.
6 CONCLUSIONS
Studies on the liquefaction of mixed plastics containing PVC at laboratory scale and
pilot plant scale suggest that it can successfully produce chlorine-free plastic-derived oil.
Removal of a major portion of chlorine in PVC as HCl is an important step to avoid
the formation of high-chlorine-content organic compounds in the liquid products. Opti-
mization of liquefaction conditions and selection of dehalogenation catalyst/sorbent are
essential for the successful production of halogen-free liquid products. Iron oxide carbon
composites worked as dechlorination catalysts and calcium carbonate carbon composites
worked as chlorine sorbents. However, the waste plastic stream should not mix with other
condensation polymers such as poly(ethylene terephthalate) etc. The presence of PET pro-
duces high amounts of organic chlorine that is difficult to remove by low-cost, iron and
calcium-based catalyst/sorbents. In a similar way, the brominated plastics were also used
for the liquefaction and completely removed the bromine content from the liquid products
using the iron- and calcium-based composites. Protection of the environment and recov-
ery of valuable organic content from halogenated waste plastics (PVC and HIPS-Br) by
liquefaction are important aspects.
The Japan Energy Corporation(JEC) has agreed and accepting the Waste Plastics Deri-
ved Oil(PDO) into the existing refinery plant as a feedstock from 2002.The PDO was
produced by waste plastics liquefaction plants in Japan with advanced dechlorination
technology, which is a key technology for the feedstock recycling of halogenated mixed
waste plastics.
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19
Liquid Fuel from Plastic Wastes

Using Extrusion–Rotary Kiln
Reactors
SAM BEHZADI AND MOHAMMED FARID
Department of Chemical and Materials Engineering, The University of Auckland, Private
Bag 92019, Auckland, New Zealand
1 INTRODUCTION
This chapter examines the production of liquid fuels from waste plastics by pyrolysis
using rotary kiln reactors. Due to increased environmental awareness and depletion of
natural oil deposits, many industries are looking for alternative fuel sources to drive their
processes. One area that has gained notable attention and popularity in recent years is
the production of fuels from waste organic materials. These materials range from waste
plastics to waste biomaterials (e.g. used cooking grease, beef fat and vegetable oils).
Pyrolysis can be one solution [1–6].
There is strong evidence that we have limited time before our natural resources of crude
oil and gas run out. Currently, many of the large oil companies such as BP and Mobil
are investing in alternative energy sources such as wind and solar energies.
The industrial revolution provided us with the phenomenal power to create energy,
advanced materials and processes, which improved our everyday lives. In a sense, we
attribute most of our daily comforts to the industrial revolution. However, we have learned
that nothing in this world is free and every thing comes with a cost. Until present day
crude oil has been the major source of energy. This is because crude oil has always
been cheap and plentiful, but this is no longer the case. As indicated by many monitoring
organizations, we have limited supply of oil, coal and gas. Thus, there is a need to use our
most valuable asset wisely or other wise we could be faced with serious repercussions.
In modern day engineering, plastics and plastic-derived materials are the most com-
monly used products. In most cases these materials are obtained from chemical alteration
of crude oil. Compared with steel and other metallic products, most of these plastics have
532 S. BEHZADI AND M. FARID
much greater life expectancy. At present plastics provide a fundamental contribution to all
activities such as agriculture, the automobile industry, electricity and electronics, building
materials, packaging and so on.
Not only do we have a shortage of energy resources, but also an increasing amount of
nondegradable waste materials. These waste materials are generated as a result of many
industries and domestic processes. At present most of these waste materials are landfilled.
In the United States alone, up to 20 million tonnes of waste plastics and 45 million tonnes
of hydrocarbon waste were generated in 2001 [1]. At the present time, we have very few
remedial processes that can reduce these wastes and harness their energy. Thus, processes
that can reuse these wastes and generate energy are highly beneficial.
One option is to reuse or incorporate the waste in new products. This can occur only
if the waste plastic has the correct specification required by product design. Incineration
of plastic waste to produce heat may also be a possibility, but its organic content would
be destroyed and converted into CO2 and H2 O. In addition, depending on its nature,
combustion may produce pollutants such as light hydrocarbons, nitrous and sulphur oxides,
dusts, dioxins and other toxins that have a highly negative impact on the environment.
Pyrolysis is one of the best methods for preserving valuable petroleum resources, in
addition to protecting the environment, by limiting the volume of nondegradable waste [2].
More importantly, due to global instability, the price and availability of crude oil can
vary considerably from day to day. Waste fuels can help to solve some of the problems
relating to environmental and economic issues which may lead to the shortage of safe
fuel. Renewable or recycled fuels can help with:
• decreasing toxic air emissions;
• diminishing imports of crude oil and also increasing energy security;
• increasing local employment and income and stimulating economic development.
In summary, pyrolysis is a tertiary recycling process that is used to break down large
polymer molecules. In this process, the polymer samples are heated in an inert atmosphere,
which causes the carbon–carbon bonds to break along the polymer backbone. This depoly-
merization step results in monomers (short-chained compounds) being formed. Generally,
three types of products are formed from pyrolysis reactions: gas, oil and char. All three
have the potential to be used as a fuel or chemical feedstock. Depending on the feed poly-
mer and the reaction conditions, different products can be obtained. The pyrolysis oil can
either be used directly or can be used as a raw material for the petroleum industry [1–5].
At present several pyrolysis plants have been built based on different processes such
as: the BASF pyrolysis process, the BP University of Hamburg fluidized-bed pyrolysis
process, the VEBA hydrogenation process, and several more are under way [4, 5].
2 PYROLYSIS
As discussed in the previous sections, plastic waste is a major issue. Pyrolysis is one
method of reducing waste plastics and other hydrocarbon waste. If applied correctly,
it should allow the recycling of some of the stored energy within the waste plastics
(Figure 19.1).
General advantages of pyrolysis include [5]:
EXTRUSION–ROTARY KILN REACTORS 533
Pyrolysis
oil
Extraction
Upgrading
Boiler Engine Turbine
Gasoline
Chemicals
& diesel
Electricity
Figure 19.1 Application of pyrolysis oil [6]. (Reproduced with permission from Elsevier)
• very low energy consumption;

• it can handle plastic wastes, which cannot be efficiently recycled by other recycling
process;
• it operates without the need of air and at low pressures;
• the HCl produced from pyrolysis of PVC plastics can be recovered and utilized as a
raw material;
• since pyrolysis is conducted in a closed system, there are no pollutants.
Table 19.1 lists the calorific values of some common polymers and compares them with
some conventional fuels. As illustrated in the table, the calorific values of these plastics
are very similar to those of liquid fuels. Thus, there is a potential for recycling of these
waste plastics as liquid fuels.
2.1 INDUSTRIAL-SCALE PYROLYSIS PROCESSES
This section examines some of the established extrusion–rotary kiln pyrolysis processes
currently operating. As illustrated in the previous sections of this book, pyrolysis is a
Table 19.1 The calorific value of some major

plastics and common fuels [7]. (Reproduced by
permission of John Wiley & Sons, Ltd)
Sample Calorific value (MJ kg−1 )

Polyethylene 46.50
Polypropylene 46.50
Polystyrene 41.90
Kerosene 46.50
Gas oil 45.20
Heavy oil 42.50
process that uses high temperatures to break polymer structures into smaller hydrocarbon
molecules. These molecules can be reused either directly, or as a feedstock material for
the petroleum process. Thus, pyrolysis can be considered as a multi-step plastic recycling
process [5]. The industrial rotary kiln processes that are examined in this section are: the
VEBA hydrogenation process and Conrad recycling process.
Rotary kiln processes are continuous processes that use a rotary kiln reactor to depoly-
merize plastic [4, 5]. They have a lower capital cost compared with fluidized-bed processes
and their liquid product resembles crude oil. The following are some general characteris-
tics of kiln processes:
• the liquid yield depends on feed, reaction temperature and reaction time (i.e. residence
time);
• heteroatom capture is a problem. Heteroatoms such as chlorine and oxygen generated
from PVC and PET are not trapped and pass through the process, thus, requiring
further cleaning steps to purify the oil products;
• fouling on the reactor wall occurs due to carbon deposits.
• lower capital cost;
• lower processing rate;
• feedstock feeding can be a problem (air lock).
2.1.1 Veba Pyrolysis Process

The Veba Oel pyrolysis processes was originally designed for the upgrading of heavy oil
hydrogenation residues (such as coal and petroleum residues). The pyrolysis process uses
a rotary kiln reactor with spheres and crossform bodies to prevent coke deposition. The
kilns used in this process were operational until 1964. However, it was found that these
kilns had three disadvantages [8]:
• spheres were abrasive;
• the rotary kilns had poor sealing;
• low specific throughput of the kiln.
Based on these disadvantages Veba Oel Technologies constructed a new pilot plant for
the pyrolysis of refinery and hydrogenation residues using indirectly heated rotary kilns
(Figure 19.2 shows the process flow diagram).
As described by Wenning [8] the solid waste is fed into the rotary kiln by a screw
conveyor. The kiln used in this process has an inner diameter of 0.8 m and a length
of 7 m. Gas burners at a slight over pressure (∼10 mbar) are used to generate the heat
required for pyrolysis. The process is carried out in an oxygen-free atmosphere and
operated at above 650◦ C. The reactor used in this process is built from high-temperature-
resistant steel, which allows the reactor to be operated at temperatures of 850◦ C. The
residence time of the materials is varied by changing the inclination and the rotating
speed of the kiln.
As a result of the thermal cracking, solid coke and pyrolytic vapours are produced.
The coke is removed from the reactor and utilized further, while the vapour products are
passed into a two-step condensation system. Wenning [8] states that, in order to prevent
Waste Material
liquid solid Flue gas
Pyrolysis gas
Blower
CW
Condenser II Condenser I Heating gas + air

CW Pyrolysis kiln
Container
Pyrolysis coke
Separator
Pyrolysis oil
(>350 °C)
Pyrolysis oil
(<350 °C)
Waste water
Figure 19.2 Veba Oel pilot plant flow diagram [8]. (Reproduced with permission from
Elsevier)
partial condensation of high-boiling pyrolysis oils in the coke discharge outlet of the kiln,
part of the pyrolysis gas is reheated using the flue gas and is recycled back into the coke
discharge area. In the first stage of condensation the vapours are cooled to 300◦ C, allow-
ing the high-boiling-point oils to be separated out. This is carried out by direct quenching
using the condensed pyrolysis oil. The second condenser cools the remaining vapours
down to 35◦ C to condense out the light hydrocarbons. The noncondensable gases are
separated and purified to remove harmful substances. These gases are also used as fuel
to heat the pyrolysis reactor [5, 8].
According to Wenning [8] the pilot plant processed a total of 1600 tonnes of residues
by mid-1989. The pilot was operated for a total time of 7800 h. At the conclusion of these
experiments Veba Oel Technologies examined the use of different feed material such as
plastic waste. Wenning [8] described a proposed design of a mixed plastic waste pyroly-
sis plant (Figure 19.3) that has a throughput of 12.5 t/h (100 000 t/a) (Table 19.2 shows
the feed composition of mixed plastic waste). Since the mixed plastic waste contains
PVC they suggested that the feed be initially treated in a PVC decomposition process
and then pyrolysed to produce liquid oil, coke and gas free of chlorine contaminate.
They suggested that the dechlorination process should be carried out by melting the
plastic waste in an extruder at a temperature of about 350◦ C. At this temperature HCl
536
Waste heat Flue gas

boiler
Steam
11.5 t/h
Plastic waste Grinding PVC-De Coke Pyrolysis coke

Pyrolysis
12.5 t/h (<20 mm) composition cooling 1.1 t/h
Air
(>350°C)
Pyrolysis oil
Pyrolysis vapours
Pyrolysis gas
HCl-Yield Condensation Scrubber
61 MWh/h
Waste water
1 m3/h
(<350°C)
Pyrolysis oil
Hydrogen Syncrude
Hydrotreating
800 m3/h 5.2 t/h
Hydrochloric acid
2.4 t/h
Figure 19.3 Flow diagram of a mixed waste plastic pyrolysis plant [8]. (Reproduced with permission from Elsevier)
S. BEHZADI AND M. FARID
Table 19.2 Feed composition of mixed plastic waste [8].
Feed material Composition (wt%)

Polyethylene (PE) 60
Polypropylene (PP) 5
Polyvinyl chloride (PVC) 10
Polystyrene (PS) 15
Polyamide (PA) 5
Polyethylene terephathalate (PET) 5
gas is produced which then can be removed from the process. The chlorine-free feed-
stock is then passed through a rotary kiln reactor where the pyrolysis reaction would
take place. The pyrolysis gases are condensed into light and heavy fractions and the
noncondensable gases are recycled back into the system for process heating. These
oils can then be reprocessed using the hydrogenation process to produces synthetic
crude oil.
2.1.2 Conrad Recycling Process

The other industrial kiln reactor that is examined in this chapter is the Conrad recycling
process. This process uses an auger kiln reactor to transform plastic and/or tyres in the
absence of oxygen into liquid petroleum, solid carbonaceous material and noncondensable
gases at high temperatures. Conrad currently has two facilities in operation. They have
a 200 lb/h pilot unit and a 2000 lb/h commercial scale unit at Chehalis research facility
(Figure 19.4 shows the process diagram) [9].
The Conrad reaction process is well described by US Patent 4412889 [10]. Initially
the feed material (14) from storage tank (16) is fed through a rotary feed valve air
lock (18) down into an infeed screw conveyor. The conveyor (20) conveys the feed
material up into the top end of the vertical inlet conduit (22) of the reactor. The feed
material is then fed into the reactor (10) were it is depolymerized into gases, liquids
and solids. Note that the feed material initially travels through an inlet region (24)
slightly cooler than the reactor to stop feed material from vaporizing before enter-
ing the reactor. This area is cooled by a stainless steel cooling jacket (56) around
the inlet conduit (22) using cold water. Typically the reaction chamber is heated to
1400◦ F (760◦ C). The reaction chamber in this process uses an impeller shaft (36) and
impeller blades (38) to convey the feed material through the reactor (Figure 19.5 shows
the reactor design). The Conrad pilot plant uses a single-pass auger kiln reactor 6 ft
in length. The relatively short length of the reactor makes the determination of the opti-
mum reaction temperature and feed rate very difficult. However, commercial-scale Conrad
units consist usually of two larger reactors in series that allow for a longer residence
time [9].
The solid products are removed from the reaction chamber through an outlet conduit
(40) into an outfeed screw conveyor (42) and into a storage container (44).The gas and
liquid product are removed from the reaction chamber through an outlet conduit (32) into
a recovery system (70). The recovery system includes a water spray system to separate
14 86
16
18 70
20
84
22 32
PUMP 56
10
38
24 36
38
26
40
42
Figure 19.4 Process diagram of a Conrad pyrolysis plant [10]. (Reproduced by permis-
sion of the US Copyright Office)
82
10
38
32 36 24 114
40
38 30°
26
Figure 19.5 Reactor design of Conrad pyrolysis plant [10]. (Reproduced by permission
of the US Copyright Office)
out liquid vapour from noncondensable gas. The recovery system could also contain a
gas-filter and a cyclone separator to separate out solid particles from the pyrolysis gas.
The system uses a portion of the noncondensable pyrolysis gas to heat the reactor up.
Heat is supplied by combustion of pyrolysis gas and natural gas is used only during start-
up (26). The combustion gases produced by the burner flow co-current with the flow of
feed materials through the reaction chamber and escape out from the reactor through an
exhaust (86). However, before the gases are released into the atmosphere they go through
a heat exchanger (84) cooled using air. The heated air from the heat exchanger is then
recycled into the burner for combustion.
According to Meszaros [9], the feed preparation is simplified in comparison to other
processes, which require size reduction, washing and removal of nonplastic contaminants.
Furthermore the inorganic contaminants in the plastic feed do not disrupt the process and
exit the unit with unreacted material and carbonaceous products.
Researchers at the Chehalis facility carried out 18-months of parametric study to assess
the Conrad recycling process [9]. Their objective was to identify process bottlenecks,
develop operating parameters and begin to assess product value and markets. For the initial
experiments a base feed mixture of 60:20:20 high-density polyethylene, polypropylene and
polystyrene (HDPE: PP: PS) was used as representative of the major constituents found
in post-consumer plastic streams.
The initial results obtained by the pilot plant illustrate that the final yield depends on
feed rate, auger rotation speed and reaction temperatures (Tables 19.3–19.5). It was found
that by reducing the feed rate and the auger rotation the formation of liquid product was
increased and the wax formation was reduced.
In order to improve the understanding of the process capabilities and product yields, fur-
ther studies were carried out by Meszaros [9], using base feed enriched with LDPE, PS and
PET. The results obtained showed that the LDPE-rich feed containing 20:48:16:16 LDPE:
HDPE: PP: PS behaved similar to that of the base feed. However, slightly higher yields
of C12 –C15 aliphatics were produced. A PS-rich feed containing 48:16:36 HDPE: PP: PS
also produced similar yield to that of base feed mixture. However, in the liquid product
higher yields of styrene were observed. Also slightly lower yields of higher molecular
weight (>C12 ) were obtained. The PET-rich feed mixture containing 20:48:16:16 PET:
Table 19.3 Product yield from base feed at different reaction temperatures [9]. (Reproduced by
permission of the American Chemical Society)
Oven temperature Liquid yield Gas yield Solid yield

(◦ F)a (wt%)b (wt%) (wt%)
1450 (788◦ C) 28 64 8
1300 (704◦ C) 48 51 1
1200 (649◦ C) 73 27
1100 (593◦ C) 79 21
a
Retort temperatures are about 200◦ less than oven
b
Combination of liquids and paraffin waxes from solids collection drum
Table 19.4 GC analysis of products from pyrolysis of base mixture [9]. (Reproduced by permis-
sion of the American Chemical Society)
Oven temperature (◦ F) 1300 1200 1100

Auger temperature (◦ F) 1095 980 895
Partial oil analysis (wt%)
Benzene 7.0 2.3 1.1
Toulene 20.0 11.0 9.1
Ethylbenzene 9.0 5.7 4.8
Styrene 20.0 17.0 14.7
C10 10.0 9.4 6.8
C11 –C15 14.5 16.6 13.1
C16 –C20 8.6 9.9 14.5
C21 –C25 3.0 3.5 6.4
C26 –C30 1.7 1.7 4.5
C31 –C40 1.1 1.5 4.2
Partial Gas Analysis (vol%)
H2 4.0 2.6 2.2
Methane 18.0 13.6 10.5
Ethylene 19.4 18.1 13.8
Propylene 21.4 21.8 21.0
Isobutylene 5.0 6.1 6.8
Table 19.5 Physical analysis of oil

product [9]. (Reproduced by permission
Specific gravity 0.8860

RVP (psi) 4.1
Pour Point (◦ F) 20
Viscosity@75 ◦ F (cst) 3.5
Viscosity@122 ◦ F (cst) 1.5
HDPE: PP: PS behaved differently from the base mixture and produced more solids at
lower temperatures (Table 19.6). The products from these runs were analysed using gas
chromatography.
In the second phase of the parametric study the removal of halogens from the reac-
tion products was examined. Two different halogen removal methods were studied. The
first method used a calcium oxide fixed bed placed between the reactor and condenser
to remove organochloride vapours. However, it was found that the calcium oxide bed
would plug up very rapidly if PET was present in the feed mixture and would become
ineffective. This is because the PET would depolymerize into terephthalic acid and CO2
and would react with calcium oxide and cause it to plug up. The second method that
was used for removal of chlorine was to add calcium oxide or hydroxide directly into the
reactor with the plastic feed. It was found that this approach is far more effective than
the previous method. Through trial and error it was found that calcium hydroxide feed of
10 wt% would remove the highest amount of chlorine (Table 19.7) [9].
Table 19.6 GC analysis of products from pyrolysis of base mixture [9]. (Reproduced by permis-
sion of the American Chemical Society)
Feed Base + LDPE Base + PS Base + PET

◦
Oven temperature ( F) 1300 1200 1100 1300 1200 1100 1450 1300 1200
Auger temperature (◦ F) 1100 1010 925 1100 1000 910 1180 980 870
Yields (wt%)
Liquids 41 45 50 36 45 50 32 55 59
Solids 3 8 32 3 8 28 1 7 21
Gas 56 47 18 60 47 22 67 38 20
Aliphatics 30.5 43.1 50.8 23.5 30.9 46.5 16.7 46.3 8.5
<C25 saturated 6.2 7.7 10.8 5.5 5.5 5.57 3.8 6.8 10.9
<C25 unsaturated
1 unsaturation 13.9 23.9 27.5 9.7 16.8 25.8 5.9 25.7 32.9
2 unsaturations 6.8 7.7 6.1 6.1 4.7 7.1 4.5 8.1 8.7
C25 +aliphatics 1.7 1.7 5.4 0.8 2.7 4.9 1.7 3.4 5.0
Aliphatics by carbon number
<C10 20.1 27.5 21.2 14.4 16.6 23.2 5.0 28.2 21.3
C11 –C15 4.6 8.5 12.6 4.1 7.7 9.4 3.0 9.2 17.6
C16 –C20 2.8 3.8 7.2 3.1 2.3 5.9 5.0 2.9 9.9
C21 –C25 1.4 1.6 4.1 1.1 1.5 2.9 2.0 2.5 4.7
C26 –C30 0.6 0.7 1.8 0.4 0.9 1.9 0.7 1.7 2.2
C31 –C35 0.4 0.4 1.2 0.2 0.7 1.2 0.4 0.7 1.2
C36 –C40 0.2 0.2 0.8 0.0 0.5 0.7 0.2 0.3 0.6
C40 + 0.2 0.2 0.8 0.0 0.4 0.8 0.1 0.2 0.4
Aromatics 63.5 49.3 39.8 71.5 62.4 42.4 76.1 40.4 29.2
Benzene 7.0 3.2 1.0 6.3 1.9 1.4 19.6 3.0 1.4
Toulene 15.7 10.8 8.0 16.2 10.5 7.3 16.5 7.2 3.8
Ethylbenzene 7.6 5.5 4.6 8.6 7.9 5.5 3.14 3.7 2.6
Xylenes 2.1 1.3 0.5 2.2 1.1 0.7 2.0 1.4 1.1
Styrene 16.7 16.6 14.6 20.6 27.1 17.0 12.0 8.9 8.2
C3−benzenes 6.8 5.4 4.9 7.4 7.4 4.7 5.7 3.8 3.9
C4+benzenes 2.8 3.4 4.2 3.0 3.7 3.9 4.1 5.8 4.5
Napthalenes 4.7 3.2 2.0 7.0 2.8 2.1 13.1 6.8 3.7
Unidentified compounds 6.8 7.5 9.4 5.0 6.7 11.1 7.3 13.3 12.3
Table 19.7 Chlorine removal step [9]. (Reproduced by permission of the American Chemical
Society)
Run PVC (%) PET (%)a Feed rate (lb/h) Temperature (◦ F) Cl (ppm)
Feed Ca(OH)2
25 3.0 0.0 80 0 1215 2500–3500
34 0.5 0.0 134 10 925 4–19
35 1.0 0.5 120 12 950 4–12
36 1.0 10.0 120 12 975 6–13
41a 3.0 0.0 120 9 900 90–140b
41b 3.0 0.0 20 9 900 120c
41b 3.0 0.0 120 9 900 80d
41c 3.0 0.0 120 12 900 60–70
a
Percent PVC/PET in base mixture
b
Average from run
c
Individual sample from run, analysed unwashed
d
Same sample as 41b, but washed with water to remove inorganic chlorides
Note, these experiments were carried out using a laboratory-scale process
2.1.3 Screw Kiln Reactor

Serrano et al. [11] studied the use of a laboratory-scale screw kiln reactor to transform
low-density polyethylene (LDPE) into petrochemical feedstock. In this process, pyrolysis
was carried out at reaction temperatures of 400–550◦ C and screw speeds of 3–20 rpm
(Figure 19.6). In this process the plastic feed is initially heated in a feed hopper until
the feed is melted. The melted plastic is then fed into the screw conveyor where it is
depolymerized into gas, liquid and solid. The hopper is equipped with a stirrer to mix the
feed plastic. Nitrogen is also used to provide an inert medium for pyrolysis.
The hopper and the reactor are heated using five separate electric furnaces (FA , FB , FC ,
FD and FE ). The hopper is heated to 300◦ C using FA and FB while the reactor can be heated
up to 550◦ C using furnace FD and FE . Furnace FC is used to keep the feed material in
the molten state while FD and FE are adjustable and used to vary the reaction temperature
(T1 and T2 ). The reaction zone consists of a screw conveyor inside a 52-cm-long stainless
steel tube. The screw speed can be adjusted in the range of 0.5–25 rpm.
In order to determine the performance of the screw kiln reactor Serrano et al. [11] car-
ried out several experiments looking at the effect of screw speed and reaction temperature.
The output was calculated as the sum of the gaseous, liquid and solid products exiting
from the reactor (Table 19.8).
The results obtained by Serrano et al. [11] illustrated that at higher reaction temper-
atures a higher product yield can be obtained (i.e. higher conversion of larger carbon
molecules to smaller hydrocarbon molecules). This was achieved at reaction temperatures
of 450–550◦ C. Table 19.9 gives details of product distribution.
The main products derived from the thermal degradation of LDPE in the screw reactor
at the set operating conditions were gasoline and middle distillates. Serrano et al. [11]
showed that the flow in the screw kiln is sufficient to avoid overcracking of heavy fractions
into smaller hydrocarbons such as gas which commonly occurs in batch processes.
Product variation was observed when the screw speed was increased from 0.7 to 11 rpm
(i.e. decreasing the residence time). The results illustrated that at longer residence times
higher amount of gas is produced since a greater amount of thermal cracking takes place
(Figure 19.7 and Table 19.10). However, the exception to this rule is at screw speeds of
FA
FE FD
FB
T1 T2 FC
Figure 19.6 Screw kiln reactor [11]. (Reproduced with permission from Elsevier)
Table 19.8 Effect of temperature and screw speed on product [11]. (Reproduced with permission
from Elsevier)
Experiment Reaction temperature (◦ C) Screw speed (rpm) Output∗ (g/h)

◦
T1 , FD T2 ( C), FE
1 400 400 11 85.2
2 400 450 11 84.5
3 400 500 11 99.4
4 450 500 11 92.0
5 450 550 11 90.2
6 450 550 0.7 13.2
7 450 550 3.0 38.0
8 450 550 8.5 76.6
9 450 550 15.0 35.8
10 450 550 20.0 35.9
Output*: Total sum of the products exiting the reactor
Table 19.9 Effect of temperature on LDPE degradation (screw speed of 11 rpm) [11]. (Repro-
Reaction temperatures (◦ C) Product selectivity (wt%) Olefin/paraffin

T1 T2 C1 –C4 C5 –C12 C13 –C33 C34 –C55 C2 –C20
400 500 1.0 25.4 59.2 14.4 1.06
450 500 4.3 26.2 55.6 13.9 1.22
450 550 7.1 25.4 53.9 13.6 1.61
7%
Screw speed 0.7 rpm
6%
5%
4%
3%
2%
1%
0%
C1 C5 C9 C13 C17 C21 C25 C29 C33 C37 C41 C45 C49 C53
(a)
7%
Screw speed 11rpm
6%
5%
4%
3%
2%
1%
0%
C1 C5 C9 C13 C17 C21 C25 C29 C33 C37 C41 C45 C49 C53
(b)
Figure 19.7 Effect of screw speed (450/550◦ C) on product yield (wt%): (a) screw speed
0.7 rpm; (b) screw speed 11 rpm [11]. (Reproduced with permission from Elsevier)
Table 19.10 Effect of screw speed on LDPE degradation (reaction temperature 450/550◦ C) [11].
Screw speed (r.p.m.) Product selectivity (wt%) Olefin/paraffin

C1 –C4 C5 –C12 C13 –C33 C34 –C55 C2 –C20
0.7 16.4 31.3 48.4 3.9 1.45
3 9.6 28.9 51.2 10.3 1.30
8.5 6.8 27.6 53.2 12.4 1.48
11 7.1 25.4 53.9 13.6 1.61
15 10.1 29.2 51.1 9.6 1.68
20 10.2 29.8 51.4 8.6 1.71
15 and 20 rpm. The results obtained at these speed were very similar to that of 3 rpm.
This is because at higher screw speeds less plastic is fed through the reactor.
2.2 EFFECT OF CATALYST ON THE PYROLYSIS REACTION
To improve the reaction yield or to change the properties of the liquid products some
processes have examined the use of catalysts. These catalysts range from acid to nonacidic
solid catalysts. However, the common catalysts that are used are zeolite (ZSM-5) and
silca–alumina [5, 11–14].
Aguado et al. [12] studied the effect of catalyst on the conversion of low-density
polyethylene using a continuous screw kiln reactor (see Figure 19.6). In this study, meso-
porous Al-MCM-41 was used as the catalyst. Initially the plastic feed and the catalyst
were mixed together in the hopper at 300◦ C before being fed into the screw kiln reactor
for pyrolysis. The feed mixture consisted of 250 g LDPE and 5 g of catalyst (50:1 w/w
plastic: catalyst ratio). The results obtained showed that the catalytic cracking over AL-
MCM-41 generates more hydrocarbon products within the gasoline range with up to 80%
selectivity (Table 19.11). This is highly favourable since thermal cracking generates a
broad range of products and in most cases the products need further refining before they
can have any industrial value.
Serrano et al. [11] also studied the effect of catalyst on the conversion of LDPE using
a continuous screw kiln reactor. The same experimental method was used as Aguado
et al. [12]. They also noticed that when using mesoporous MCM-41 aluminosilicate cat-
alyst a higher yield of gasoline fraction can be obtained (Table 19.12). They believe
that the cause of this is secondary reactions that take place inside the reactor between the
smaller volatile groups as they travel through the kiln. This occurrence is greatly improved
in the catalytic cracking since the catalyst strongly promotes secondary reactions (i.e.
oligomerization) between volatiles.
2.3 EFFECT OF TEMPERATURE
Temperature is one of the most important parameters in pyrolysis reactions. Reaction

temperature has direct correlation with product yield. For example, from an economic
prospective solid product produced by pyrolysis is the least desired product. This is
Table 19.11 Catalytic and thermal cracking of LDPE [12]. (Reproduced with permission from
Elsevier)
Experiment Screw speed T1 /T2 Output Conversion TOF Selectivity

(rpm) (◦ C) (g/h) (wt.%) (s−1 ) (wt%)
C1 –C4 C5 –C12 C13 –C23 C24 –C55
ST 3.0 450/550 38.0 100 – 9.4 28.9 35.7 26.0
SC1 3.0 400/450 19.6 69.1 0.291 21.4 66.4 4.6 7.6
SC2 6.0 400/450 26.9 64.9 0.374 18.1 69.3 9.7 2.9
SC3 15.0 400/450 41.2 51.4 0.454 18.3 77.7 2.0 2.0
ST, SC: thermal and catalytic cracking

TOF: turnover frequency. Values calculated as mass of converted LDPE/mass of Al in the catalysts, but this
will not give S−1 unit
Note, the catalytic cracking of LDPE was performed at T1 /T2 400/450 at screw speeds of 3–15 rpm. The results
were compared with a previous thermal cracking experiment carried out by Serrano et al. [11] using screw
speed of 3 rpm and reaction temperature of 450/550◦ C.
Table 19.12 Catalytic cracking of LDPE at screw speed of 8.5 rpm [11]. (Reproduced with
T1 /T2 (◦ C) Conversion (wt.%) Productivity (wt%)

C1 –C4 C5 –C12 C13 –C33 C34 –C55
400/400 24.8 16.1 76.5 7.1 0.3
400/450 60.8 9.0 81.0 10.0 0.0
450/450 87.9 5.1 80.3 13.1 1.5
450/500 100 12.6 74.2 11.9 1.3
because the solid product has very little use. However, Williams and Besler [15] showed
that the solid product could be reduced if higher reaction temperatures were used. They
found that at 720◦ C the final product contained less solid. This is because at the higher
temperatures more of the solid is converted into liquid and gas. This has also been the
case for most processes described in this chapter. For example, Meszaros [9] illustrated
that as the reaction temperature in the Conrad process was increased less solid product
was produced.
Li et al. [16] also studied the influence of pyrolysis temperature on the pyrolysis prod-
ucts derived from solid waste in a rotary kiln reactor. They used an externally heated
laboratory-scale rotary kiln pyrolyser (Figure 19.8). The length of the rotary kiln was
0.45 m with an internal diameter of 0.205 m. Kiln rotation speed can be adjusted from
0.5 to 10 rpm. The raw materials used in this study were polyethylene (PE), wood and
waste tyres. The results obtained by Li et al. [16] reiterated that as the reaction temperature
profile changes so does the product yield (Figure 19.9).
In summary the operating temperature determines the amount of solid, liquid and gas
products that are produced from a given pyrolysis process. At higher reaction temper-
atures more gaseous and liquid products are produced. However, at lower temperatures
more coke-like solid is produced. Depending on the process and feedstock composition
the optimal reaction temperature can be different. From an economic perspective higher
amounts of gas and liquid products are more beneficial.
380v
1 2 3 4 5 6 2 7 8 910
11
15
14 13 12
Figure 19.8 Rotary kiln reactor. 1 thermometer; 2 bearing; 3 gear transmission; 4 electric
furnace; 5 rotary kiln; 6 temperature controller; 7 seal; 8 tube condenser; 9 filter; 10 total
flow meter; 11 computer; 12 gas sampling device; 13 tar reservoir; 14 feed and discharge
opening; 15 electric motor [16]. (Reproduced with permission from Elsevier)
100
Gas tar semi-coke

80
60
wt,%
40
20
0
550 650 750 850
(°C)
Figure 19.9 Effect reaction temperature on product yield [16]. (Reproduced with per-
mission from Elsevier)
2.4 ROTARY KILN REACTOR VS FLUIDIZED BED
As described previously pyrolysis is a process that thermally degrades organic waste at

high temperatures in absence of air and oxygen. This process can be carried out in a rotary
kiln reactor or in a fluidized bed. In a rotary kiln process the feed material is conveyed
through a rotating drum (i.e. reactor) and is then pyrolysed in the hot atmosphere into
gas and solid residues. The residence time of the reaction is dependent on the rotating
speed of the drum, i.e. the faster the drum rotates the shorter the residence time. The
reactor is heated externally using some of the gases produced by the process and in some
cases by natural gas. Rotary kiln processes are described to have lower capital cost which
makes them an attractive option. However, they have a lower processing capability and
tend to have longer residence times [5, 8, 9]. Furthermore, rotary kiln reactors have large
temperature gradients across their diameter and tend to have poor temperature control.
As a result they tend to have a wide number of products with varying composition.
In a fluidized-bed process the fed plastic is heated by exposing it to a hot medium (i.e.
quartz sand). The advantage of this is that it allows for more uniform heating which in
turn produce a more uniform product in a shorter residence time. A fluidized bed can
have a residence time of seconds to a few minutes. This is due to the even heating of the
fluidized bed. The fluidized bed is heated by indirect heating from heat pipes that carry
flue gases through the bed [5, 17–19]. The following are some general characteristics of
a fluidized-bed process:
• high liquid yields;
• good temperature control;
• difficulties with solid removal;
• low process durability;
• higher capital cost;
• higher processing rate;
• process costs 13–16 cents/lb;
• products may have higher value than those obtained from kiln reactor;
• better heteroatom capture.
However, it should be noted that both processes have the same economic disadvantage.
Both processes are faced with high collection and sorting cost of waste plastic. The pro-
cesses will not be attractive unless some form of subsidies are provided [5]. In summary
both process are available on pilot plant and industrial scale [4, 5, 8, 9].
REFERENCES
1. E. A. Williams and P. T. Williams, Interaction of plastic in Mixed-Plastic Pyrolysis,

Journal of Energy and Fuels, 13(1), 188–196 (1999).
2. T. Bhaskar, T. Matsui, M. D. Azhar Uddin, J. Kaneko, A. Muto and Y. Sakata,
Effect of Sb2 O3 in brominated heating impact polystyrene (HIPS-Br) on thermal
degradation and debromination by iron oxide carbon composite catalyst (Fe-C),
Journal of Applied Catalysis B: Environmental, 43(3), 229–241 (2003).
3. G. P. Bracker, Pyrolytic resource recovery, Conservation and Recycling, 4(3),
161–165 (1981).
4. G. Mackey, A review of advanced recycling technology, American Chemical Society
Symposium, 609, Chapter 14 (1995).
5. J. Scheirs, Polymer Recycling: Science, Technology and Applications, John Wiley &
Sons, Ltd, Chichester, England, 1998.
6. A. V. Bridgewater, Production of high grade fuels and chemicals from catalytic
pyrolysis of biomass, Catalysis Today, 29, 285–295 (1996).
7. E. A. Williams and P. T. Williams, The pyrolysis of individual plastics and a plastic
mixture in a fixed bed reactor, Journal of Chemical Technology and Biotechnology,
70(1), 9–20 (1997).
8. H. P. Wenning, The VEBA OEL technologie pyrolysis process, Journal of Analytical
9. M. W. Meszaros, Advances in plastics recycling, American Chemical Society Sym-
posium, 609, Chapter 15 (1996).
10. R. C. Oeck, Pyrolysis reaction apparatus, US Patent 4412889 , (1983).
11. D. P. Serrano, J. Aguado, J. M. Escola and E. Garagorri, Conversion of low density
polyethylene into petrochemical feedstocks using a continuous screw kiln reactor,
Journal of Analytical and Applied Pyrolysis, 58–59, 789–801 (2001).
low-density polyethylene using a continuous screw kiln reactor, Journal of Catalysis
Today, 75, 257–262 (2002).
13. S. Yusaku and A. Muto, Degradation of polyethylene and polypropylene into fuel
oil by using solid acid and non-acid catalysts, Journal of Analytical and Applied
Pyrolysis, 51, 135–155 (1999).
14. N. Shah, J. Rockwell and G. P. Huffman, Conversion of waste plastic to oil: direct
liquefaction versus pyrolysis and hydroprocessing, Journal of Energy and Fuels,
13(4), 832–838 (1999).
15. P. T. Williams and S. Besler, The pyrolysis of municipal solid waste, Journal of the
Institute of Energy, 65(465), 192–200 (1992).
16. A. M. Li, X. D. Li, S. Q. Li, Y. Ren, Y. Chi, J. H. Yan and K. F Cen, Pyrolysis of
solid waste in a rotary kiln: influence of final pyrolysis temperature on the pyrolysis
products, Journal of Analytical and Applied Pyrolysis, 50(2), 149–162 (1999).
17. W. Kaminsky, Thermal recycling of polymers, Journal of Analytical and Applied
Pyrolysis, 8, 439–448 (1985).
18. W. Kaminsky, B. Schlesselmann and C. M. Simon, Thermal degradation of mixed
plastic waste to aromatics and gas, Polymer Degradation and Stability, 53(2), 189–197
(1996).
19. J. Kim, W. Kaminsky and B. Schlesselmann, Pyrolysis of a fraction of mixed plas-
tics wastes depleted in PVC, Journal of Analytical and Applied Pyrolysis, 40–41,
365–372 (1997).
20
Rotary Kiln Pyrolysis of Polymers

Containing Heteroatoms
ANDREAS HORNUNG AND HELMUT SEIFERT
Forschungszentrum Karlsruhe GmbH, Institut für Technische Chemie, Thermische
Abfallbehandlung – ITC-TAB, P.O. Box 3640, 76021 Karlsruhe, Germany
1 INTRODUCTION
Pyrolysis of polymers means thermal decomposition of the material in the absence of

oxygen. During the process pyrolysis gases or oils are evolved. Today pyrolysis units
use polymers with a wide spread of constitution: mixtures, spilled mixtures as well as
mono fractions. A heterogeneous feed yields a broad spectrum of pyrolysis products, thus
dramatically reducing the economic attractiveness of the process. Present technologies
are melting vessels, autoclaves, tube reactors, fluidized beds, stirred reactors, cascades
of stirred reactors and rotary kilns. Technologies that convert plastic wastes back to
their starting materials or to general decomposition products are a promising develop-
ment in plastics recycling. An initial challenge for these new recycling technologies is
to develop cost-effective and versatile process units which can handle a variety of mixed
plastic resins and additives typically found in post-consumer waste streams. The Halo-
clean Process – a rotary kiln process – documented within this chapter has successfully
met this challenge and demonstrated its applicability to brominated electronic scrap during
extensive parametric studies.
Therefore, rotary kilns are the special application of this chapter and are compared with
competing technologies. A closer look is given to the treatment of thermoplastic, ther-
mosetting or elastomer-based polymers, containing heteroatoms such as nitrogen, chlorine
or bromine.
2 TECHNICAL VARIATIONS
Typically two major types of rotary kilns are used for pyrolysis processes either internally
or externally heated systems. For internally heated kilns a heat exchanger based on steam-
550 A. HORNUNG AND H. SEIFERT
or gas-powered tubes or electrical heaters are used. For externally heated systems we find
steam, gas (direct or indirect) or electrical powered systems. The following three examples
show engineering solutions for processing of highly volatile feeds and their relevance in
processing.
2.1 CONRAD PROCESS
Any post-consumer plastic stream will contain some halogens in the form of polyvinyl
chloride, polyvinylidene chloride, brominated flame retardants, halogenated additives,
food waste, or salt. Therefore, two issues must be considered. First, the gas stream result-
ing from the depolymerization of plastics must be scrubbed to remove any halogenated
gases to satisfy emissions controls. Second, halogens in the liquid product must be min-
imized to increase its value and marketability. Therefore the Conrad process has been
developed. It is a robust process unit that can accommodate a variable feedstream and
produce a consistent product, free of nonhydrocarbon impurities by low feed prepara-
tion costs.
The Conrad recycling process uses a horizontal auger kiln reactor that applies heat to
plastics and/or tires in the absence of oxygen to produce liquid petroleum, solid carbona-
ceous material, and noncondensable gases [1–3]. The control of the pyrolysis process is
decided by temperature and especially auger speed and temperature.
2.2 DOUBLE ROTARY KILN PYROLYSIS
The double rotary kiln pyrolysis is designed for mechanical coupling of a pyrolysis
unit and a combustion unit. The coaxial system of two rotary kilns opens up the pos-
sibility to evaporate organics from the feed material in the inner kiln while the car-
bonaceous residues are transported through the external kiln to a combustion zone.
The process heat of combustion is used to heat the inner kiln while the ashes leave
the system [4]. Both kilns can be equipped with lifters or spiral lifters. A compara-
ble system has been purchased by Kurimoto industries, Japan for drying and calcining
processes.
2.3 PYROLYSIS OF TIRES: FAULKNER SYSTEM
The pyrolysis of tires based on rotary kiln technology started quite early in the 1970s.
A field-scale rotary kiln at Rocky Flats is documented in [5]. Very new developments
can be found in [6]. The rotary kiln developed by Faulkner has several distinct heating
zones independent from each other. The system consists of a rotary feed cylinder that
includes a screw-like flight extending from the inner wall of the feed cylinder. As the
feed cylinder rotates, the flight directs the supply of vehicle tire pieces into the infeed
end of the pyrolysis section. The temperature levels of the kiln zones decrease from a
maximum of 800◦ C to 500◦ C at the end of the kiln. A separation of char and scrap steel
ROTARY KILN PYROLYSIS OF HETEROATOM POLYMERS 551
is performed by a trajectory diverter at the end of kiln. The char passes through the slots,
whereas the scrap steel is transported to the outlet.
2.4 VTA PYROLYSIS: A ROTARY KILN FOR THE TREATMENT OF

PETROCHEMICAL RESIDUES AND HYDROCARBON RESIDUES
The low-temperature carburization LTA process developed by VTA meets the world-
wide need for a process which economically reduces petrochemical and hydrocarbon
residues into recyclable products, feedstocks or clean fuels. The indirectly fired rotary
kiln system can be operated up to 850◦ C. The throughput varies in between 800 and
2000 kg/h.
LTC in a VTA rotary kiln is an economical process, because of process flexibility and
simple design. VTA’s kiln design can process, solids, slurrys, sludges, viscous liquids,
volatile, and materials difficult to handle in other types of equipment. The LTC kiln sealing
system allows operating the system under positive pressure, assuring no leakage of air
which can produce an explosive mixture.
The kiln consists of four operating zones, a vaporization, cracking, polymerization and
carburization zone. The remaining residues are transported out of the system by a screw
flight.
For cleaning the kiln wall from carbonaceous materials and feed, VTA invented a
cylindrical cleaning device lying on the bottom of the rotary kiln, equipped with high-
temperature bearings effective over a temperature range up to 1100◦ C, running up to
8000 h/yr without lubrication. The cylindrical unit is mounted on the infeed side of the
kiln and ends in the carburization zone of the kiln. A cone segment connects to the infeed
zone. VTA is specifies the advantages of the rotary kiln as follows [7]:
• compliance with present-day stringent environmental requirements;
• less capital investment in comparison with incineration units;
• due to the unique sealing system on the inlet and outlet side and the supervisory
monitoring system, the rotary kiln meets or exceeds the most stringent criteria for
emissions;
• high-temperature efficiency and maximum capacity are assured by the patented kiln
wall cleaning device, equipped with maintenance free high-temperature bushings (no
lubrication);
• based on the improved design, the on-stream time of the rotary kiln is increased to
8,000 h/yr operating at 850◦ C continuously.
3 STATE OF THE ART OF ROTARY KILN TECHNOLOGY

(TABLE 20.1)
Use of the rotary kiln technology on a technical scale depends strongly on the eco-
nomics of the process. In the past several process types were tested and applied. Usually
‘operative mode’ or ‘shut down’ were not affected by technical problems, but by the
profitability of the processes. One example is the Siemens-KWU process. It has been
dismantled in Germany due to technical and economic reasons, but is running in Japan
at nine sites.
In terms of tire recycling several approaches were started in the past and are either
shut down today or competing strongly for fuel substitution in cement kilns or as regran-
ulation for use in the building industry. A promising approach in 2002–2003 by Ligmbh
Germany [22] for the treatment of 60 000 tonnes of used tires never reached technical
scale. The rotary kiln technology was implemented for the activation reaction of pyrolysis
coke to activated carbon.
3.1 HALOCLEAN GAS-TIGHT ROTARY KILN
The Haloclean rotary kiln is especially designed for the pyrolysis of high amount of
inert and/or thermosetting containing materials, e.g. electronic scrap. The invention is
based on experience with a vertical reactor system for the conversion of thermoplastics
the so called cycled-spheres reactor [8]. Hornung et al. [9] invented a system improv-
ing the heat transfer to poorly heat-transferring materials such as plastics, ensuring that
decomposition on a laboratory scale can also be described with microkinetic analy-
sis [10]. As shown in [8] the usage of a sphere-filled reaction vessel improves the heat
conductivity by an order of magnitude at least 1. The system used a screw cycling
metal spheres to keep the polymer melt hot and to heat up entering melt to reaction
temperature by ‘mixing’ with metal spheres. Obviously the system was not suitable
in the case of nonmelting plastics. The idea of heat-transferring metal spheres and a
screw which transports not only spheres, but also feed material was transferred to an
industrial-type reaction system, a rotary kiln [11]. To maintain the performance at low
rates of consecutive reactions of the pyrolysis gases as well as low residence times
of the pyrolysis gases in the system, the hollow screw shaft has been equipped with
200 sintered metal plates. These plates are permanently cleaned by the material pass-
ing their surface, thus keeping the inner core of the screw free from pyrolysis prod-
ucts and introducing the purge gas directly where the pyrolysis products are evolved,
(Figure 20.1).
Today, applications in the fields of pyrolysis of shredder light fractions and electronic
goods seem to be the most promising for pyrolysis. For both the feeds strong support
Spheres
Scrap
Oven
Nitrogen
Purge gas inlet by 200 sintered
metal plates on the screw shaft
Figure 20.1 The Haloclean reactor

for recycling is given by European legislation. A detailed discussion of these applications
can be found in the following sections.
A further promising field for application of pyrolysis (not a topic of this chapter) seems
to be the coupling of the pyrolysis units with a thermal plant. The pyrolysis fractions can be
used as precleaned feed support for the combined power plant as shown in Table 20.1 for
ConTherm at Hamm-Uentrop with a capacity of 100 000 t/yr high caloric feed [15, 17].
4 ROTARY KILN PRINCIPLES
The effects of varying the parameters of standard rotary kiln pyrolysis processes on the
pyrolysis product spectrum of shredder light fractions, tires, municipal solid waste as well
as plastics has been investigated in detail by Wanzl, Lee and Co-workers [23–27]. They
clearly showed the problems in transferring analytical data from micro- and laboratory-
scale experiments to rotary kiln applications. Usually the residence time behaviour of the
systems at micro and technical scale is different and therefore affects secondary reac-
tions of the pyrolysis products. This is not a negative effect at all. In the case of longer
residence times and higher temperatures in rotary kilns, especially in case of pyrolysis
oils and gases from shredder light fractions the composition is shifted to more stable
light aromatics. Furthermore, the use of catalyst can improve cracking and isomeriza-
tion as well as chlorine removal [23, 24]. The chlorine removal in case of shredder
light fractions is of high importance due to the fact that these feeds contain up to 10
wt% of chlorine. Chlorine scavenging strategies in general are described in the following
section. Comparing the fluidized bed and rotary kiln technology the results of Wanzl et al.
[23, 24] and Li et al. [26, 27] and Pasel [25] can be summarized as follows. A rotary
kiln (although it provides lower heating rates) is flexible with regard to the residence
time as well as time/temperature profile and can be adjusted to the process requirements
as the length of the kiln can be varied. Moreover, an optimum temperature profile can
be set via different heating zones being independently controlled. For example in com-
parison with a fluidized bed, a rotary kiln may be a suitable alternative for a conversion
reactor in a recycling scheme for plastic wastes as it combines suitable reaction con-
ditions with advantages in the mechanical treatment of the solid reactor feed. Li et al.
[26, 27] checked for the heating rate influences in rotary kiln systems on gas production.
Principally those studies can be transferred to technical application, taking into account
the specific heat transfer conditions in the kiln, temperature levels to be adjusted, feed
temperature and temperature conditions of the infeed zone and finally the feed/energy
supply ratio. In terms of PVC, Li et al. have shown that the overall gas production per
kg of feed can be increased by 80%, in continuous cracking, not only converting the gas
species using temperatures up to 800◦ C, but also lowering the absolute amount of tar and
semi-coke.
5 TREATMENT OF THERMOPLASTICS: PVC
New pathways in plastics recycling and the current status of plastics recycling has
been recently highlighted by Kaminsky et al. [28]. The development of different viable
recycling technologies for plastic waste materials is becoming increasingly important. The
554
Table 20.1 Rotary kiln processes
Company Feed type Site Type Reference Start/feed/

remarks/
status [15]
Siemens-KWU- Plastics/municipal Fürth, Germany Internal tube heat [16] 1997/4 × 5 Mg/h/closed
Schwelbrenn- waste exchanger, 1999/dismantled
Verfahren low-temperature steam,
high-temperature natural
gas
KWU Municipal waste 9 sites in Japan [15] 1996–2003/6–20 Mg/h/
Shredder light operating
fractions
PKA-Kiener Municipal waste Aalen, Germany Low-temperature pyrolysis, [17] 1982/3 Mg/h/dismantled in
internally tube heated 2002
Kobe Tires Akoh, Japan Externally heated drum [18] 200 kg/h/1 Mg/h [18]
Noell Plastic containing Salzgitter, Indirectly heated drum [16] 1996/7 Mg/h/shut down for
special wastes Germany economic reasons
Pleq Soil Herne, Germany Externally heated [15] 1989/7 Mg/h/operating
decontamination
BKMI Burgau municipal waste Burgau, Germany Externally heated, pyrolysis [17] 1984/7 Mg/h/operating
kiln under moderate
pressure
BKMI Shredder light Nassau, USA [15] 1984/5 Mg/h/shut down 1996
fractions
A. HORNUNG AND H. SEIFERT
MVU Rotopyr Cables, rubber, Bochum, Germany Externally heated drum [17, 19]
municipal waste
BC Pyrocom Electronic scrap Lübben, Germany Electrically (externally) [20, 21] Shut down
heated kiln
Conrad Plastics/tires Chehalis, USA Auger kiln, externally [2, 3] Shut down
heated
DAL Municipal waste Plaidt, Germany Externally heated [17] 2 Mg/h/shut down
VTA Municipal waste, Gelsenkirchen, Externally heated/indirectly [15] 2001/2 Mg/h/in operation
chemical Germany/ gas fired
residues Victoria, Texas,
USA
Haloclean Electronic scrap Karlsruhe, Internally and externally [15] Pilot scale, 40 kg/h/technical
Germany (Sea electrically scale expected in 2005,
Marconi, Italy) heated/electrically heated (400 kg/h)
screw with purge gas
supply
ConTherm Municipal waste Hamm-Uentrop, Externally heated, gas fired [15] 2000/2 × 6 Mg/h/
Plastic wastes Germany operating/secondary fuels
for thermal plant
ROTARY KILN PYROLYSIS OF HETEROATOM POLYMERS
555
following overview of the literature offers the prospect of tailored pyrolysis to realize
halogen-free or reduced feedstocks while modifying or optimizing the composition of
pyrolysis products when pyrolysing polyolefines, polystyrene and/or polyvinylchloride.
Kaminsky [29] studied the thermal cracking of polyethylene (PE) in a fluidized-bed
reactor over the temperature range 500–600◦ C. At temperatures below 550◦ C, high yields
of useful products with low yields of gas and aromatics were obtained.
Ding et al. [30, 31] have studied hydrocracking of polyethylene (PE) using catalysts
such as HZSM-5, shifting to more aromatic products. Agudo et al. [32] investigated the
effect of β-zeolite on the degradation of polypropylene (PP), low-density polyethylene
(LDPE) and high-density polyethylene (HDPE) at 400◦ C. In the case of LDPE and PP a
shift to light products (C1 –C4 ) was observed and in the case of HDPE a shift to C5 –C12
products was observed.
A series of studies dealing with the process integrated dehydrochlorination of plastic
mixtures (polyvinylchloride, polystyrene and polyolefines) has been done by Hornung
and Bockhorn [33–35]. By varying the temperature in distinct steps it was possible
to evolve 99.6% of the HCl before the main pyrolysis of polystyrene and polyolefines
appeared.
A detailed study on scavenging HCl by calcium-based sorbents (Ca-C sorbent, consist-
ing of 90 wt% of CaCO3 and 10 wt% of phenol resin) during or after pyrolysis has been
completed recently by Bhaskar et al. [36] and is planned for technical application at a
municipal plastic waste pyrolysis plant at Mizushima, Japan. Calcium-based scavenging
is a strategy already followed in industry and studied deeply for fluidized-bed pyrolysis
of thermoplastics by Sinn and Kaminsky [37–39].
For shredder light fractions, a mixture of polyolefins and polyurethanes containing as
well as polyamides, PVC, polystyrene and blends, Wanzl et al. [23, 24] and Pasel [25]
have shown for the treatment of the pyrolysis gases from rotary kiln pyrolysis that by
using dolomite beds at 500◦ C and a residence time of 20 s, chlorine content can be
reduced from 1000 ppm to below the detection limit of 1 ppm.
With the Conrad process [1–3] a set of experimental runs with a throughput of approx-
imately 100–1000 kg/h with PVC contents of up to 3% in a 60:20:20 HDPE:PP:PS
base mixture have been performed. Typically 70–80% of liquids and 1–3% of solids
are obtained. In scavenging the chlorine from evolving gases by hot calcium oxide and
before condensation of the liquid fraction with a content of about 25 ppm chlorine were
possible. Similar results were obtained by treating the plastics in the kiln with calcium
oxide during pyrolysis. A direct condensation without any calcium oxide treatment led to
concentrations of up to 10 000 ppm chlorine.
6 PYROLYSIS OF MONO FRACTIONS: POLYMETHYLMETHACRYLATE

PMMA
A special case in terms of application of rotary kiln technology is the pyrolysis of mono
fractions such as styrene, PMMA, polycarbonate, or polyethylene terephthalate. Poly-
methylmethacrylate is an example illustrate the advantages in using fluidized beds or
rotary kilns. The feed material does not have a heteroatom problem and the pyrolysis
product can easily be handled as a monomer source instead of feedstock. Therefore the
aim of the pyrolysis is a low amount of by-products and a high yield of monomer. For
this example it has been shown by Sasse and Emig [40, 41] that the fluidized bed is
advantageous. Even both techniques can be applied.
7 TREATMENT OF SHREDDER LIGHT FRACTIONS/SHREDDER

RESIDUES
The treatment of shredder light fractions/shredder residues in rotary kilns is not as common
as in the case of other fractions [42–45]. Due to the mixture of materials today, gasi-
fication, blast furnace, and fluidized-bed pyrolysis are preferred, transforming the feed
into reducing agents, syngas or feedstock. Nevertheless several studies at laboratory and
technical scale have shown the feasibility of rotary kiln application [23–25, 46–49].
Especially in terms of recovery of liquid products [23–25, 46, 47], instead of using
them as reducing agent or to transform them to syngas [42, 43], in combination with
the reuse of the solid fractions in different technological applications such as the ferrous
and nonferrous metals industries and the building industry [49, 48] the rotary kiln tech-
nology seems to be promising. A technical-scale run at Siemens-KWU with 30 tonnes
of shredder residue with a throughput of 143 kg/h and a total run time of 211 h has
shown no problems in terms of the rotary kiln technology [48]. Recent studies have
been performed by Harder [49] with a 500 L kiln at 600–700◦ C, showing a residence
time of about 12 min and an amount of volatiles, excluding water, of 30–35 wt% of
the feed.
A typical composition of shredder light fractions from the automotive industry and
electronic goods is given in [43] with 32 wt% of plastics, 25 wt% of elastomers, 8 wt%
of wood, cellulose and textiles, 4 wt% of colorants, 2 wt% metals, and 29 wt% of minerals,
glass and stone. The composition of automotive shredder shifts slightly to more plastics
with 35 wt%, 17 wt% of metals, and 18 wt% of minerals, glass and stone. Tecpol [43] is
mentions an annual gasifier capacity for shredder light fractions in Germany in 2010 of
about 210 000 tonnes for producing methanol.
The works cited on optimizing the pyrolysis gas composition show the principal dis-
advantage by pyrolysing shredder residues or shredder light fractions compared with
packaging materials, even those containing PVC or mono fractions. The mixture of
aliphatics and aromatics, containing acidic compounds and nitrogen-based pollutants
need further post-treatment if pyrolysis oils are to be used. Presently, recycling quo-
tas can be matched in terms of gasification with combined synthesis gas production
and methanol synthesis and the processes are less sensible in terms of feed material
compositions.
8 TREATMENT OF ELECTRONIC SCRAP
The treatment of electronic scrap is again more complicated and delicate than treating
shredder residues or shredder light fractions. On one hand it is a mixture of thermoplastics
and thermosettings, on the other hand it contains quite high amounts of bromine, precious
metals, nonferrous metals, and useful inert materials. These two aspects are combined
with the tendency of the material to react to high amounts of carbonaceous residue as
well as forming brominated dibenzodioxins, and furans if treated not properly.
Today technologies offer different ways of proper treatment of these fractions such as
co-combustion [50] or use in copper smelters [2, 51, 52]. Both technologies fail to reach
the new European recycling quotas for electronic goods. The main reason is the energetic
usage of the plastic instead of recycling it.
8.1 THE EUROPEAN DIMENSION
Plastics in electrical devices are composed of different additives such as phosphates,

brominated compounds, chlorinated substances or antimony oxides in order to suppress
the evolution of flames and the development of heat in case of fire.
However, especially brominated flame retardants are creating problems when electronic
and electrical equipment reach end of life. If landfilled, toxic brominated flame retardants
may slowly leach out into the groundwater, where they persist for several years or they
can evolve into the air. If waste materials are burned toxic polybrominated dioxins and
furans can be formed [53, 50].
Although phosphates are increasingly replacing brominated additives, there is still a
wide range of manufacturers around the world using them. So waste will continue to
contain these substances. Against the background of the European directive for waste
electrical and electronic equipment introduced on 13 February 2003 and to be transferred
into national law [54] an innovative technology to cope with bromine-containing elec-
tronic devices is required. The recommended quotas for the end of 2006 are given in
Table 20.2.
8.2 THE PYROCOM ROTARY KILN
In the mid-1990s BASF, Ludwigshafen and APME, Brussels had run experiments with
electronic scrap in cooperation with the BC-Berlin Consult plant in Lübben, Germany.
The BC plant consisted of an indirectly heated rotary kiln with 300 mm inner diameter
and 3 m heated length driven at 750–850◦ C [20, 21, 55]. Two types of material were
investigated, a fine fraction and a typically shredded electronic scrap fraction. Up to
Table 20.2 Recycling quotas of the European Union
Category Total quota, including thermal Remarketing and

treatment (%) recycling (%)
1 White goods 80 75
2 Brown goods 70 50
3 Lamps 70 50
4 Tools, electronic/electrical 70 50
5 Toys, electronic/electrical 70 50
6 System control and measurement 70 50
7 IT and telecommunication 75 65
8 Entertainment 75 65
Table 20.3 Pyrolysis products from BC-rotary kiln runs [20]
Trial 1 2 3 4 5
Type Shredder Fine Fine Shredder Shredder
Temp/◦ C 850 750 850 750 750
Coke/wt.-% 72.8 43.1 43.5 74.5 77.1
Oil/wt.-% 11.8 18.9 17.7 9.9 5.2
Gas/wt.-% 11.5 27.4 26.9 13.5 16.1
Others/wt.-% 3.9 10.6 11.0 2.1 1.5
Duration/h 28 14 26 30 74
Feed/kg/h 35 22 16 30 24
Total/kg 1000 313 432 890 1751
1700 kg and feeds up to 35 kg/h were used. The experiments have shown that the metal-
containing shredded fraction has been processed in the kiln without blockage. In terms
of the fine fraction, and due to the high amount of plastics, carbonaceous residues were
formed on the kiln wall and the processing had to be stopped. The pyrolysis products
obtained in the runs are shown in Table 20.3.
8.3 THE HALOCLEAN ROTARY KILN PROCESS
Since 2002 a European consortium has dealt with the transfer of a pilot-scale Halo-
clean rotary kiln system to technical scale (Figure 20.2). By scaling up the pilot-scale
unit with a throughput of about 40 kg/h, a technical scale with a feed of up to 3000
t/a will be realized. The Haloclean process, combined with its post-treatment facilities
transforms electronic scrap into three typical fractions, residues containing metals, pre-
cious metals, carbon, glass and inerts, as well as phenolic-based oils and HBr [11, 51,
56–59].
By reaching the European recycling quotas the process is delivering a residue-based feed
material for copper smelters, an oil low in bromine suitable for gasifiers with combined
methanol synthesis, and HBr by post-treatment reactions.
On a pilot scale (Figure 20.2) several process parameters such as temperature, res-
idence time and rotation speed and modes have been optimized. The temperature has
been varied between 250 and 550◦ C. The residence time was between 1 and 4 h. The
bromine content of all products was determined and especially the amount of brominated
dibenzodioxins and furans in the residue fractions was determined and correlated with
temperature.
Different fractions of electronic scrap were tested and pyrolysed. Figures 20.3–20.6
show feed materials and their related residues. In the case of populated and nonpopulated
computer circuit boards as well as in the case of television boards a non-sticky residue
results.
As worked out for several reaction temperatures and residence times, different materials
such as populated and nonpopulated circuit boards from computers or television sets as
well as housing fractions from computers or monitors can be processed at two distinct
temperature levels of 350 and 450◦ C and residence times of 2 h for each stage. The
residue amount under these conditions can be specified as 65 wt% for nonpopulated
printed circuit boards up to 90 wt% for television printed circuit boards. In the case of
housing fractions the entire feed fraction has been converted in oils and gases. This result
is strongly dependent on the composition of the feed.
Figure 20.2 The Haloclean plant. The Haloclean kiln on top is combined with the Pydra
rotary kiln as a second stage, and a standard rotary kiln, similar to the system used at
Pyrocom
Figure 20.3 Nonpopulated computer circuit boards, pyrolysed at 350 and 450◦ C, 2 h at
each stage and the corresponding residues. If necessary these residues can be sieved in
fractions for accumulation of metals or used in total
Figure 20.4 Populated computer circuit boards, pyrolysed at 350 and 450◦ C, 2 h at each
stage and the related residues
The chosen reaction conditions ensure that all residue fractions consisting of
brominated dibenzodioxins or furans below the given German limits of 1 µg/kg
for 2,3,7,8-tetrabromodibenzo-p-dioxin, 1,2,3,7,8-pentrabromodibenzo-p-dioxin, 2,3,7,8-
tetrabromodibenzofuran and 2,3,4,7,8-pentabromodibenzofuran and lower than 5 µg/kg
for 1,2,3,6,7,8-hexabromodibenzo-p-dioxin, 1,2,3,7,8,9-hexabromodibenzo-p-dioxin and
1,2,3,7,8-pentabromodibenzofuran, as required by the Deutsche Chemikalien Ver-
botverordnung for free transportation of goods [60].
Figure 20.5 Television printed circuit boards, pyrolysed at 350 and 450◦ C, 2 h at each
stage and the related residues
Figure 20.6 Housing fractions, pyrolysed at too low a temperature of about 350◦ C for
2 h, the residues becoming sticky
Finally, Figure 20.7 shows the constitution of the rotary kiln with its screw device
after 1800 h operation with different materials. The screw blades and the screw shaft
are free from carbonaceous residues due to permanent cleaning by metal spheres and
shredded goods.
9 DEHALOGENATION OF PYROLYSIS OILS
This final section deals with the dehalogenation of pyrolysis oils from electronic scrap. In
terms of using those materials for feedstock recycling, synthesis gas production or fossil
fuel substitution, dehalogenation is strongly required. For feedstock recycling a 10 ppm
Figure 20.7 Opening of the unit after 18 months usage and approximately 1800 h
operation
limit of halogens is specified [21]. Various methods for the dehalogenation of pyroly-
sis oils are given by Kühl [21]. He described physical, chemical and thermal methods
which all failed in terms of dehalogenation of pyrolysis oils from Pyrocom runs due to
too high a bromine content. Alternatives are given by Bhaskar et al. [36] for chlorine-
containing feeds and Sakata et al. [61] for chlorine- and bromine-containing feeds from
pyrolysis municipal waste or electronic scrap-related materials using calcium oxide and
Ca-C (a mixture of calcium oxide and a phenolic resin). Blazsó et al. [62] described the
debromination of flame-retarded polymers. Blazsó et al. showed several oxides and cata-
lysts (Na-metasilicate, molecular sieve 5A (Ca), molecular sieve 13 X (Na, H)) suitable for
the decontamination of pyrolysis products, treated directly after evolution during pyroly-
sis. This method seems to be promising, especially for fine treatment of low-contaminated
oils. Experimental studies have been transferred to laboratory- and pilot-scale runs in the
framework of the Haloclean activities.
A very different solution, and one suitable even for the selective production of HBr in
the presence of chlorine, without any catalyst, is the treatment of the pyrolysis oils with
molten polypropylene [13, 63, 56, 57, 59]. Polypropylene acts within a temperature range
of 310–350◦ C as a hydrogen donor. HBr is evolving from the brominated phenols and
substituted phenols are formed in the case of the decomposition of flame retardants such
as tetrabromobisphenol A (Figure 20.8). Together with HBr small brominated aliphatics
are formed. Those can be converted to HBr together with all noncondensable compounds
in a final oxidative cleaning.
Figure 20.8 Dehalogenation of pyrolysis product from tetrabromobisphenol A (a) and

by copyrolysis with PP in a closed ampoule (b), at 350◦ C for 15 min
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21
Microwave Pyrolysis of Plastic

Wastes
C. LUDLOW-PALAFOX AND H.A. CHASE
Department of Chemical Engineering, University of Cambridge, New Museums Site,
Pembroke Street, Cambridge CB2 3RA, UK
1 INTRODUCTION
Microwave pyrolysis of plastic (or plastic-containing) wastes is a relatively new area that
has been studied only in the last decade or so. Because of this, there is considerably less
information in the scientific literature compared with other approaches to the pyrolysis of
plastics. Also, there is a substantial amount of information contained in patents, which
suggests that the development of microwave pyrolytic processes has been more intuitive
rather than strictly scientific. This chapter will summarize the developments in this area
that are described both in scientific and commercial literature.
The chapter begins by introducing the concepts behind microwave heating and the
properties that make plastics transparent to this kind of radiation. This is followed by a
definition of microwave pyrolysis of plastics and the ways that microwave transparency
of plastics can be overcome in order to use this microwave energy as a source of heat for
pyrolysis. A number of microwave pyrolytic processes for materials other than plastics
are also introduced.
The literature review of microwave-assisted or induced pyrolysis of plastics follows.
In this section special attention is paid to the reactor configurations used, comparing
them with the configurations found on more conventional pyrolysis equipment. The most
important findings produced from this research are presented, including product yield,
characteristics and composition. An analysis is presented to assess whether in any example
there is evidence for nonthermal microwave effects promoting the pyrolytic reactions.
The last section will focus on a review of the ‘commercial’ literature, e.g. patents
and companies’ websites. The aim of this section is to analyse the claims made in these
documents in the light of the information present in the scientific studies. Flow diagrams,
equipment characteristics and process results are analysed in a new exercise that shows
570 C. LUDLOW-PALAFOX AND H.A. CHASE
that there is a great deal of work needed to bridge the gap between the research and
the commercial communities. Both communities can provide a substantial amount of
experience and expertise in order to make microwave pyrolysis better understood and as
a result more widely adopted.
2 BACKGROUND
2.1 MICROWAVE HEATING
2.1.1 Microwave Heating Fundamentals

The use of microwave radiation for practical purposes was investigated during the Sec-
ond World War, in the course of intensive research on electromagnetic radiation in the
frequency range from 500 MHz to 100 GHz in the development of high-definition radar.
At that time the magnetron valve was invented; this is a very high-power source of
microwaves with outstanding efficiency. After the war, further development led to the
introduction of microwave radiation to processing equipment by using it for heating,
especially in the food industry.
Microwave heating is categorized as an electric volumetric heating method. Other heat-
ing methods in this group are: conduction (DC to 6 Hz) and induction (50 Hz to 30 kHz)
heating, where a current passes through the workload to cause I 2 R heating; ohmic heating,
which is essentially a variation of the former, but for liquids and slurries; radio frequency
heating (1–100 MHz, often 27.12 MHz), used for workloads with high resistivity where
the workload is placed between electrodes. Microwave heating is performed using frequen-
cies close to 900 MHz (λ = 33.3 cm) and at 2.45 GHz (λ = 12.2 cm). These frequencies
were chosen by international agreement to avoid interference with other bands allocated
for other uses such as mobile telephony. Figure 21.1 shows the electromagnetic spectrum
and some applications performed at various frequencies along with examples of electric
volumetric heating.
Wavelength
300 km 3 km 30 m 30 cm 3 mm 30 µm
Microwave Visible
Power Telephony LW MW SW VHF TV IR UV
bands light
10 102 103 104 105 106 107 108 109 1010 1011 1012 1013 1014 1015
Frequency (Hz)
Microwave
896, 915 MHz
Conduction Induction
2.45 GHz
Radio-frequency
Ohmic 27.12 MHz
Figure 21.1 Electromagnetic spectrum with examples of applications and heating appli-
cations at various frequencies
MICROWAVE PYROLYSIS 571
Microwave heating is a process tool that has a number of advantages over other,
more traditional, heating methods. Conventional heating is normally performed through a
heated surface and is therefore governed by the temperature of that surface. Also, heating
is limited by the physical properties of the material, such as density, heat capacity, and
heat conductivity, i.e. the thermal diffusivity of the material. Microwave heating on the
other hand is associated with a more even distribution of heat that leads to easier control
over the temperature profile in the heated material.
The basic theory of microwave heating is well understood and described in several
textbooks [1–4]. There are basically three mechanisms by which materials are heated in
a microwave field. These mechanisms arise from the displacement of charged particles
in the material when they are subjected to microwave radiation and are summarized as
follows:
• The electrons around the nuclei (electronic polarization) or the atomic nuclei them-
selves (atomic polarization) are displaced from their equilibrium position, giving rise
to induced dipoles, which respond to the applied field. In some materials (such as
water) there are permanent dipoles due to the asymmetric charge distribution in each
molecule. The dipoles, either induced or permanent, tend to reorient under the influ-
ence of a changing electric field.
• Another type of polarization arises from a charge build-up in the contact areas or inter-
faces between different components in heterogeneous systems. This phenomenon is
also known as interfacial polarization and is due to the difference in the conductivities
and dielectric constants (see below) of the materials at interfaces. The accumulation
of space charge is responsible for field distortions and dielectric loss and is commonly
termed ‘Maxwell–Wagner polarisation’.
• Ionic conduction: some materials produce electric currents within themselves when
subject to electromagnetic fields. When these electric currents flow within the structure
of the materials, which in most cases have a relatively high resistivity, the material is
heated.
Although most existing microwave heating processes are used to heat up materials,
mainly water, that have permanent dipoles, some processes use the other two mechanisms.
The extent to which a material is heated when subjected to microwave radiation depends
on two parameters: the dielectric constant ε and the dielectric loss factor ε . The dielectric
constant describes the ease with which a material is polarized by an electric field, while the
loss factor measures the efficiency with which the electromagnetic radiation is converted
into heat. The ratio of these properties gives the dielectric loss tangent or dissipation
factor:
ε
tan δ = (21.1)
ε
which defines the ability to absorb and convert electromagnetic energy into thermal energy
at a given temperature and frequency.
Since microwave heating depends mainly on the characteristics of the workload, when
a material is suitable for this type of heating, the sources of microwave radiation enable
high temperatures and high rates of heating and show excellent efficiencies of conversion
of electrical energy into heat (80–85%). Modern equipment has very high reliability and
is competitive with other heating methods.
As a result, there are an increasing number of industrial processes and applications that
make use of microwaves for energy transfer. Modern microwave systems are used for,
tempering and thawing, continuous baking, vacuum drying, pasteurization and steriliza-
tion [1]. Furthermore, there is a big potential for the use of this kind of technology in
environmental engineering [5].
2.1.2 Microwaves and Plastics

Thermoplastics (with the exception of Nylon) normally have very low dielectric constants
and low loss factors and therefore there is limited scope for the use of microwaves in
their processing. This is further aggravated by the fact that when plastics start to heat and
molecular mobility increases, the absorption of microwaves also increases and, at the gel
transition or melting point, it can increase substantially. This can result in ‘thermal run-
away’ where increasing amounts of microwave energy are absorbed as temperature rises.
This effect could finally result in a poorly controlled pyrolytic reaction or combustion,
depending on the conditions [6–9]. For some thermoplastics there is a ‘critical tempera-
ture’ for microwave heating which has been shown to correspond to molecular relaxations
occurring at microwave frequencies. This means that some molecular segments can move
on a timescale similar to the exciting microwave energy. Further information about the
processability of polymers with microwaves has been described by Chen et al. [10–12]
2.2 MICROWAVE PYROLYSIS
2.2.1 Microwave Pyrolysis of Plastics

As mentioned in the previous section, plastics have very low dielectric constants and loss
factors. This evidently means that they are not able to heat up efficiently or controllably
to a temperature high enough for them to pyrolyse. So the obvious question arises: how
are plastics, that are essentially transparent to microwaves, thermally degraded using
microwave radiation? The most efficient solution involves, mixing plastics (microwave-
transparent material) with a microwave-absorbent material. Microwave-heating of the
latter material results in heat transfer by conduction to the plastic. This is what is know
as microwave-induced (or microwave-assisted) pyrolysis, and will be referred to here
simply as ‘microwave pyrolysis’. In a sense this process utilizes a ‘fourth’ method for
microwave heating since microwaves are used as indirect source of heat. Graphitic carbon
and some inorganic oxides are materials that are used as microwave-absorbents, with
carbon having a predominant role due to its low price and high abundance. When subjected
to an electromagnetic field at microwave frequencies, some molecular structures of carbon
absorb the energy, which is subsequently converted by ionic conduction and dipole rotation
(the third and first mechanism explained in Section 2.1.1) into heat [13–15].
Microwaves are currently used to heat carbon for sintering in the ceramics industry,
achieving good heating rates and high temperatures. Ceramics have very low loss factors
for microwave processing at low temperatures, however, when the temperature reaches
a certain value, the electrical conductivity of the ceramic drastically increases and the
sample rapidly heats. Carbon has been used to accelerate the first stage of the heating
process by applying a very thin coat (0.01 mm) to the ceramic surface [16–18].
Another area where microwave heating is used to heat carbon is in the regeneration
of activated carbons. When spent activated carbon is subject to a microwave field, the
heat generated within the particles produces rapid temperature rises and the release of
other compounds adsorbed on the carbon [19–23]. In a similar process, carbon used as
adsorbent to remove NOx and SOx from gas streams can be regenerated with microwaves
producing CO2 and N2 as gases and elemental sulphur [24].
In microwave pyrolysis of plastics, when carbon (or other microwave-absorbent) is
exposed to a microwave field, it can reach temperatures up to 1000◦ C in a few minutes
(Evidently this depends on the amount of carbon and the power of microwave field. The
given example can be achieved easily with 1 kg of carbon in a 5 kW (normal catering)
microwave oven.) If shredded plastics are mixed with the carbon, prior to or during heat-
ing, the energy absorbed from the microwaves is transferred to the plastics by conduction,
providing a very efficient energy transfer, and if carbon is used as microwave-absorbent,
a highly reducing chemical environment. The latter avoids formation of undesired oxy-
genated organic compounds, in case oxygen is present in the system within molecules
of plastifiers, additives, paints, inks or other materials such as paper or biowaste. The
basic aim of this novel pyrolytic method is to provide a process for the disposal of plas-
tic wastes, making use of the high temperatures that the carbon achieves when subject
to a microwave field, and has advantages over other more conventional pyrolytic pro-
cesses [25]. In summary, microwave pyrolysis combines the advantages of microwave
heating with the environmental benefits and commercial opportunities arising from the
pyrolysis of wastes.
Microwave pyrolysis has been proven to be a useful process to treat some real plastic
wastes. Tests have shown the potential of microwave-induced pyrolysis for the treatment
of plastic/aluminium laminates [26]. These materials, which are a common example of a
waste made of plastic attached to other components, are used mainly as packaging for
food, beverages and other products like toothpaste. A common name used to refer to these
‘drink cartons’, particularly when used to package food and drinks, is Tetrapack (from
the trademark by Tetra Pak Sweden and Switzerland). These drink cartons consist of a
variety of different types of laminates which all contain a thin foil of aluminium, typically
with a thickness of ∼6–30 µm laminated in conjunction with paper and plastic layers.
The thin fragile layer of aluminium foil has caused problems for conventional pyrolytic
processes that attempt to pyrolyse the plastic and simultaneously recover the aluminium.
On the other hand, in addition to the aforementioned advantages, the microwave pyrolysis
process can be operated under gentle conditions and therefore fragile materials, such as
the aluminium foil present in the laminate, can be recovered clean and ready for further
processing. Details of the studies carried out with the microwave pyrolysis process are
presented in Section 3.
2.2.2 Microwave Pyrolysis of Tyres

Considerable attention has been paid over the last few years to the use of microwave
pyrolysis for the processing of scrap tyres. Approximately 2.5 million tonnes in North
America, 2.0 million tonnes in the European Union and 0.5 million tonnes in Japan, of
scrap tyres are discarded per year. As much as 50% of this waste is landfilled which is
clearly causing an increasing unsustainable and unacceptable situation. Other recycling
methods for waste tyres such as retreading, reuse in other areas (barriers, construction
material, etc.), chemical devulcanization and incineration (in cement kilns or power sta-
tions), have technical or demand limitations that prevent them from coping with the
enormous amount of waste tyres generated [27]. In order to tackle this situation, pyroly-
sis and gasification of tyres have been studied for a number of years. In the former case,
the products consist of mainly oils and a solid residue (carbon and ash). In the latter case
the products are a good source of synthesis gas. The solid residue formed during pyrolysis
can be further treated in order to produce activated carbon. Many studies concerning the
conventional pyrolysis of tyres can be found in the literature [28–44].
Tyres are composed mainly of a mixture of rubbers (50 wt%) and, among many other
constituents, they have a considerable amount of carbon black acting as a reinforcing
agent. Similar to plastics, rubbers also have low dielectric constants and loss factors
and hence are not suitable for microwave heating. However, the presence of carbon black
within the tyre formulation, makes this waste a perfect candidate for microwave pyrolysis.
The carbon absorbs the microwaves, heating up and transferring the heat to the rubber
which pyrolyses, producing more carbon, that in turn absorbs microwaves and heats up.
There are no papers in the scientific literature regarding the microwave pyrolysis of tyres;
however, further information about the subject is presented in Section 4 since there is
substantial information available in published patents.
2.2.3 Microwave Pyrolysis of Other Materials

Examples exist of other processes, in which microwave heating of microwave-absorbents
is used as a way to transfer energy to a microwave-transparent material in order to accom-
plish the pyrolysis of the latter. For example, the pyrolysis of chlorodifluoromethane has
been carried out in a microwave-heated fluidized bed with a performance comparable
to that of tubular reactors, the best traditional equipment for the pyrolysis of this com-
pound [45].
The simultaneous decomposition of pentachlorophenol and regeneration of activated
carbon, using microwaves was reported [46], claiming that the quality of the carbon was
maintained or actually increased after several adsorption/microwave-regeneration cycles.
Carbon, in graphite form, has also been used as a microwave absorbent for the microwave
pyrolysis of urea [47].
Similarly, microwaves have been used for pyrolysis of coal, which is known to have
very poor microwave absorption, by mixing it with inorganic oxides (very good microwave
receptors) or with carbon. After the initial stages of pyrolysis the coal undergoes some
graphitization, turning into carbon black that further absorbs microwaves [48, 49].
Microwave pyrolysis has also been tested with materials that, even though they are
dielectric, contain some molecules responsive to microwave fields and can therefore
absorb microwaves, heat up and pyrolyse. Example are wood blocks [50–52] and oil
shales [53].
Another material treated with microwave pyrolysis has been sewage sludge. Disposal of
this material, which is a by-product in wastewater treatment processes, is a considerable
problem and currently accounts for up to 60% of the operational cost of wastewater treat-
ment plants. Microwave pyrolysis of sludge provides a rapid and efficient process with
reduced process time and energy requirements compared with conventional pyrolysis [54].
Furthermore, the condensables from microwave pyrolysis contain less carcinogenic com-
pounds than those produced in conventional pyrolysis [55] and the noncondensables have
a higher concentration of CO and H2 (synthesis gas) after microwave pyrolysis than after
conventional pyrolysis [56].
3 MICROWAVE PYROLYSIS OF PLASTICS IN THE SCIENTIFIC

LITERATURE
3.1 MICROWAVE PYROLYSIS EQUIPMENT
3.1.1 Thermogravimetric Microwave Pyrolysis Equipment

Pyrolysis has been used for some time as an analytical technique for the identification of
products and the elucidation of kinetics during the degradation of plastics and many other
organic materials. In this kind of application, microwaves have been used as the heating
source in some of the analytical equipment. Examples include an apparatus to perform
thermogravimetric analysis (TGA) which included a novel method for the temperature
measurement and control [57], and the so-called microwave differential thermal analy-
sis. The latter works in the same way as conventional DTA, by detecting changes that
result from the energetics of the process, but it can also measure differences that result
from changes in the microwave heating capacity of the material (changes in dielectric
properties) [58–60].
At the same time, a similar system was developed with the specific aim of perform-
ing thermogravimetric (TG) experiments during the microwave pyrolysis of plastics and
plastic/aluminium laminates [26]. The schematic diagram of the apparatus developed is
illustrated in Figure 21.2.
In summary, the apparatus comprised a conventional (domestic) microwave oven with a
maximum power output of 1.2 kW (1). The reactor (2) was a fused silica crucible placed
in a moulded microwave-transparent insulating brick (3) that was suspended from the
400 g 4
256˚C
1
5
N2
6
2
3
Figure 21.2 Schematic diagram of the microwave pyrolysis thermogravimetric appa-

ratus. First published at the 6th World Congress of Chemical Engineering
bottom hook of an analytical balance (4). Carbon was used as the microwave-absorbent
and its temperature monitored using a type-K thermocouple (5). A glass pipe (6) was
used to carry a small flow of purging gas (N2 ) that was introduced above the carbon bed
to limit the presence of oxygen near the reaction zone. The thermocouple and the balance
were connected to a computer which ran a data acquisition program in order to record
the temperature and the sample weight at a rate of 1 Hz. A more detailed description of
the apparatus and the experimental method can be found elsewhere [26]. This equipment
was built with the purpose of acquiring initial ‘know how’ about the microwave pyrolysis
process and its characteristics and therefore a number of its components did not provide
the same level of accuracy as commercial TGA equipment. Nonetheless, it is believed that
further improvements to the apparatus could lead to equipment matching the functionality
of many well-known conventional commercial systems.
3.1.2 Semi-batch Microwave Pyrolysis Equipment

The majority of the scientific literature devoted to pyrolysis of plastics is focused on
the development of equipment or processes having recycling as their ultimate goal.
Many of these have been introduced in previous chapters and include studies using flu-
idized beds [61–77], cycled-sphere reactors [78, 79], fixed-bed reactors [80, 81], rotary
kilns [82], screw reactors [83] and rotating cone reactors [84]. In all these studies the
chemical analysis of the pyrolysis products has been an important goal in order to asses
the behaviour of the pyrolysis of plastics.
With this in mind a bench-scale semi-batch microwave pyrolysis apparatus was devel-
oped. A schematic diagram is shown in Figure 21.3. It consisted of a modified 5 kW
catering microwave oven (1). The reactor (2) was a quartz vessel placed in a specially
moulded base made of a microwave-transparent/insulating material. The agitation system
for the reactor consisted of an impeller, shaft and a motor (3). The temperature of the
carbon load was monitored using three thermocouples and automatically controlled using
a computer. The reactor was gravity fed using the top feeder (4). The flow rate of purg-
ing/carrier gas (N2 ) was monitored using a rotameter (5). The products of pyrolysis left
the reactor and pass through a system of condensers that had a main collection vessel
(6), two water-jacketed columns (7) and two cold traps (8,9). After the two cold traps
the uncondensable gases flowed through a cotton wool filter (10) to collect any aerosols
present, before leaving the system. Gas samples were collected after the filter. A more
detailed description can be found elsewhere [85].
As mentioned above, the main difference between microwave and conventional pyrol-
ysis is the initial source of thermal energy and the way this is transferred to the plastic.
Nonetheless, there are other differences, particularly when microwave pyrolysis is com-
pared with fluidized-bed pyrolysis equipment: in the latter, the primary reaction products
are carried out of the reactor by a hot gas stream which enables these products to take part
in secondary and tertiary reactions. On the other hand, in microwave pyrolysis, once the
pyrolytic products leave the carbon bed, they stop receiving heat by conduction from the
hot carbon and come in contact with a relatively cold carrier gas. This has an important
effect in the number of consecutive reactions occurring and therefore, on the nature of
the products, as is shown in Section 3.2.2.
3
N2 Gas
sampling Vent
5 4
N2
10
1
7
2
6 8 9
Figure 21.3 Schematic drawing of the microwave-induced pyrolysis apparatus. (Num-

bers refer to components described in main text) [85]. (Reproduced by permission of the
An extra feature of the equipment shown in Figure 21.3 is the design of the con-
densation train. It is known that under certain conditions, the pyrolytic products when
condensed, form a mist or aerosol, similar to the smoke produced by cigarettes or a bar-
becue. These aerosols, may accumulate as a wax on the walls of condensers, but often
they do not settle inside collection vessels. This problem was solved by making the gases
flow upwards through a vertical condenser, effectively creating a reflux-like effect, sim-
ilar to a distillation column. Furthermore, this condenser was operated at a temperature
that cooled the products to a point at which they condensed, but did not solidify, and
allowed the liquid droplets to coalesce and hence be collected. The optimal operation of
the condenser was with water at temperatures between 50 and 60◦ C [86].
Due to the novelty of the microwave pyrolysis process, there are no other reports in the
scientific literature, with details of equipment for the degradation of plastics. However,
for the degradation of other materials, details of the apparatus utilized for the microwave
pyrolysis of wood have been presented [50, 51].
3.2 RESULTS FROM THE MICROWAVE PYROLYSIS OF PLASTICS
3.2.1 Themogravimetric Experiments

The results for the TG experiments performed with the equipment shown in Figure 21.2,
showed typical exponential weight-loss curves that are consistent with the use of the sim-
ple power-law model (pseudo-first-order reaction) in order to model the overall process.
Figure 21.4 shows the results obtained for the degradation of three kinds of materials,
when the experimental weight loss curves were averaged and transformed into conversion
curves.
Heat transfer limitations are important restrictions for pyrolytic processes because of
the low thermal conductivity of plastics. In general the heat flow from the surface of a
plastic particle to its core (internal heat flux) is rather slow compared with the heat flow
1.0
0.9 C
0.8
B
0.7
0.6
Conversion
A
0.5
0.4
0.3
0.2
0.1
0.0
0 100 200 300 400 500 600
Time (s)
Figure 21.4 Pyrolysis of (A) HDPE pellets, (B) HDPE powder and (C) toothpaste laminate
at 550◦ C using a microwave pyrolysis thermogravimetric apparatus [26]. First published
at the 6th World Congress of Chemical Engineering
from the hot medium to the particle surface (external heat flux). Consequently, pryrolytic
TGA studies have to be performed with small particle and sample sizes, for example,
samples of ∼10 mg and 63–90 µm diameter [87]. Moreover, in microwave pyrolysis
this difference in heat fluxes is further increased because of the large transfer coefficients
for heat conduction between the hot bed of microwave-absorbent and the plastics.
The experiments illustrated in Figure 21.4 however, were carried out with 4 g of mate-
rial because, as was mentioned before, the aim was not to elucidate the reaction pathway
or the kinetics parameters of the pyrolytic reaction, but to provide ‘know how’ about the
microwave pyrolysis process. Therefore as can be seen in the figure, the fastest degra-
dation was achieved with the laminate because of its smaller thickness (plastic layer
90–150 µm) in comparison with the average diameter of the HDPE powder (150 µm)
and pellets (3 mm diameter, 1 mm high).
As an approximation, the apparent reaction rate constant was calculated, assuming that
the temperature was constant once the polymer started to degrade. From the correlated
data the apparent reaction rate constant was calculated for the three materials at 550◦ C.
Table 21.1 shows the values obtained and compared with values calculated at 550◦ C,
from kinetic data in the literature.
The results shown in Table 21.1 do not imply that microwave pyrolysis is slower
than conventional pyrolysis, but confirm the need to consider heat and/or mass transfer
limitations because of the particle and size samples used in the experiments [26].
3.2.2 Bench-scale Semi-batch Experiments

The degradation of HDPE pellets and toothpaste tube laminate was performed at a range of
temperatures between 450 and 700◦ C using the equipment shown in Figure 21.3. Details
of the experimental method can be found elsewhere [85].
Table 21.1 Apparent reaction rate constants for the pyrolysis of PE with a first-order reaction
model
k (s−1 )
Microwave pyrolysis laminate [26] 0.011
Microwave pyrolysis PE powder [26] 0.006
Microwave pyrolysis PE pellets [26] 0.003
Conventional pyrolysis PE powder [88] 0.052
Conventional pyrolysis PE powder [89] 0.208
40
30
Volume (ml)
20
A B
10
0
0 50 100 150 200 250 300 350
Time (s)
Figure 21.5 Cumulative yield of condensable products for the microwave pyrolysis of
HDPE pellets pyrolysis at (A) 500◦ C and (B) 600◦ C [85]. (Reproduced by permission of
Figure 21.5 shows the cumulative volume of oils/waxes collected at two temperatures
as a function of reaction time.
The temperature had a major effect on the rate of reaction/decomposition, observed by
the rate of condensation in the main collection vessel. If this figure is compared with the
results in the absence of agitation (Figure 21.4), the same shaped curves are found and
the same order of magnitude in the rate of degradation can be noticed. Nevertheless the
apparent shorter reaction time demonstrates the effect of improved heat and mass transfer
in the semi-batch equipment due to the agitation system.
Table 21.2 shows various results for product (phases) yields for the degradation of PE
at 500 and 600◦ C along with the results obtained using microwave pyrolysis. As can be
seen in the table, in the latter case the increase in temperature caused little difference in
the yields of the products. These results, which seem to contradict most previous findings,
may be explained by the configuration of the microwave pyrolysis equipment.
It is known [90, 91], that the final yield and hence product composition of pyrolysis
products are determined mainly by the secondary and tertiary reactions that occur after
Table 21.2 Product yield (wt%) from the pyrolysis of PE reported in the literature (NR = not
reported) [85]. (Reproduced by permission of the American Chemical Society)
500◦ C 600◦ C
Gas Oil/wax Solid Gas Oil/wax Solid
Batch fluidized bed [72] ∼7–16 NR NR ∼18–60 NR NR
Fixed bed [90] ∼8–12 ∼83–90 ∼2–5 ∼20–35 ∼55–74 ∼6–10
Fluidized bed [74] 10.8 89.2 0 24.2 75.8 0
Microwave-induced pyrolysis [85] 19.0 81.0 0 20.9 79.1 0
the polymer molecules have first been cracked. Considering this and the increase in the
reaction rate with temperature, the results in Table 21.2 are explained as follows: for the
microwave pyrolysis results, as temperature increased, the reaction rate increased with
the consequent increase in the production rate of primary gaseous products. The constant
volume of the reactor leads to an increase in pressure in the reactor that resulted in a
more rapid flow of gas out of it; the residence time therefore became dependent on the
reaction temperature. In other words, with the reactor configuration and dimensions used,
the increase in the level of molecular cleavage due to an increase in temperature range
shown was counterbalanced by a decrease in the residence time in the reactor [85].
The gas chromatography/mass spectrometry (GC-MS) analysis of the pyrolysis prod-
ucts helped to prove the relationship between reactor temperature and the residence time
described in the previous paragraph. Furthermore, the analysis showed that microwave
pyrolysis generates the same kind of products as produced in other conventional pyrolysis
process. The total ion chromatogram (TIC) for the condensable products was very simi-
lar to those obtained with conventional heating systems [85]. The distribution of degrees
of polymerization obtained from the GC-Ms analysis also confirmed that at 600◦ C the
effect of higher temperature compared with 500◦ C was balanced by the reduction of the
residence time. At 700◦ C the temperature effect dominated, causing the same level of
cleavage as at 500◦ C, but in a much shorter reaction time [85].
In terms of the individual compounds found in the condensable products, as with
conventional pyrolysis, α-alkenes alkanes and dialkenes were the most abundant com-
pounds. A large number of other aliphatic and aromatic compounds ranging from C3 to
approximately C56 were also found, including: methylcyclopentene, benzene, cyclohexene,
toluene, ethylbenzene, xylene, propylbenzene and methyl-ethylbenzene. The analysis also
showed that the condensables obtained at 500 and 700◦ C, although possessing similar lev-
els of cleavage, showed important differences in the individual compounds present [85].
The main compounds in the noncondensable gaseous products were linear alkenes and
alkanes, ranging from C1 to C7 and accounted for almost 90% of the mixture, with the rest
consisting mainly of cyclic aliphatic compounds. In terms of individual compounds, the
gaseous mixture was composed of compounds similar to those found in the conventional
pyrolysis of PE [72, 74, 92], with the difference however that negligible amounts of
hydrogen were found [85].
As mentioned in Section 2.2.1, the recovery of clean aluminium from real plastic-
containing wastes has been one of the main focuses of the research into microwave
pyrolysis. With the semi-batch apparatus shown in Figure 21.3, experiments were per-
formed using toothpaste tube laminate and depulped drink carton laminate (a Tetra Pak
type of material after a paper recovery process). During these experiments 29.4 and 14.5%
of clean aluminium (weight based on the initial load of waste) was obtained with the two
laminates respectively, in agreement with the expected theoretical amount (30 and 13.8%
by mass). The solid aluminium was separated easily from the carbon by sieving and
showed a shiny and clean surface. There were no important differences in the products
obtained from the pyrolysis of toothpaste tube laminates compared with the degradation
of HDPE pellets [26, 85]. During the degradation of drink carton laminate however, the
residual paper present in the material caused substantial differences in the nature of the
products: there was a substantial amount of ash formed, the yield of condensables was
higher and, as expected, the presence of oxygen-containing compounds (in the condens-
able and noncondensable phases) such as phenol and acetic acid was observed. Moreover,
an important observation was that levoglucosan, one of the main pyrolysis products from
cellulose [93, 94] was not detected [95]. Figure 21.6 shows samples of the initial laminate
and the recovered hydrocarbon and aluminium products.
3.3 MICROWAVE EFFECT IN MICROWAVE PYROLYSIS?
Although it is possible that some chemical reactions are directly promoted by the pres-
ence of microwaves, particularly in organic chemistry [96], there is much speculation
on whether this so-called Microwave effect truly exists [97]. In the 1980s, this effect
was thought to promote chemical reactions, increase reaction rates by diminishing acti-
vation energies and explain other phenomena observed in the presence of microwave
fields. Following further investigations, many researchers claimed that microwave-induced
Figure 21.6 From left to right: original laminate, recovered condensable products and
recovered aluminium. Top row, toothpaste tube laminate. Bottom row, depulped drink
carton
chemistry did not exist. Extensive studies analysed the differences between microwave
and other conventional processes in order to establish substantiated conclusions.
Supporting those who believe that there is a nonthermal effect, there are reports claim-
ing that reactions occur at lower temperatures using microwave heating [98] or that there
are distinct catalytic effects as a consequence of dipole formation [99]. Likewise its been
claimed that the microwave pyrolysis of urea (using carbon as microwave-absorbent) pro-
vided advantageous selectivity of reaction routes, promoting favourable chemical reactions
and thereby enhancing the yield of desired products [47].
Supporting those who believe that a nonthermal effect does not exist, there are reports
that maintain, for example, that claims of the ‘microwave effect’ were probably due
to experimental mistakes when researchers tried to extrapolate concepts of conventional
heating into microwave heating [100]. It has been claimed that the possibility of ‘reduced’
reaction temperatures reported in some cases were nothing but mistakes in the measured
temperature due to heat losses that occurred because of conduction through thermocouple
guards [101].
The debate continues, but as a result of the research generated so far, it is generally
accepted that microwaves do have an important role in promoting chemical reactions, not
via a nonthermal effect, but because the heating they induce has the advantages that were
described earlier in this chapter: high power density, volumetric dissipation, even heating
and good heating control [102]. Examples of modern methods in which microwaves are
used routinely in chemistry include a variety of equipment for the performance of organic
digestions and, in direct relation to this chapter, the heating of solvolysis agents to achieve
the degradation of waste plastics in solution [103–105].
In relation to microwave pyrolysis and taking into account the findings of the stud-
ies mentioned above, it is generally believed that microwaves do not pyrolyse organic
materials via a nonthermal effect. As will be seen in Section 4, there are a number of
patents that claim otherwise, but often lack the necessary evidence to validate their find-
ings. Furthermore, even regarding claims where wastes (such as plastic or clinical wastes)
were degraded by microwave energy without the presence of microwave-absorbents, it
is highly probable that the reactions occurred initially by thermal effects. As has been
mentioned previously, even if plastics have low dielectric constant and loss factors, they
still can heat up with microwaves, inefficiently at first, but with increasing efficiency at
the glass transition or melting point. This applies even more to other materials such as
wood or clinical wastes, that contain within them a considerable number of compounds,
many of which are susceptible to microwave heating and that therefore can be ‘initiators’
of the heating that leads to pyrolysis.
The advantage of microwave pyrolysis over conventional pyrolysis methods do not
rely on changes in chemical pathways, but in the advantages that have been mentioned
previously.
4 MICROWAVE PYROLYSIS IN THE COMMERCIAL LITERATURE
4.1 PATENTS HISTORY AND COMPARISON WITH SCIENTIFIC LITERATURE
Early patents in the field of microwave pyrolysis were filed in the late 1960s, describing
processes for the liquefaction of coal [106, 107] for the production of organic compounds.
Soon after, when waste management became more important, other materials started to
be considered for treatment by this kind of process, not only as a source of valuable
chemicals, but also as a method to manage production and postconsumer waste. Thus,
patent US 3,843,457 entitled ‘microwave pyrolysis of wastes’ presented a process that,
regardless of the name, consisted in fact in a gasification process and an apparatus, for
the recovery of organic compounds from organic wastes. The explanation given claimed
that the wastes would decompose because of cleavages caused directly by microwaves in
the carbon–oxygen bonds in the material, but did not provide more detail or experimental
proof [108].
In the 1970s, industrial research in the area was led by the tyre industry in the light of
the, increasing problem of waste tyre disposal. Consequently processes for the ‘devulcan-
ization of rubber using microwave energy’ were presented [109, 110]. Simultaneously,
based on the document mentioned in the paragraph above, Patent US 4,118,282 was the
first document to mention the idea of mixing a microwave-absorbent with other materials.
The patent talked about a process and apparatus in which ‘high molecular weight organic
materials’ were mixed with ‘carbon or other catalysts’ and subjected to microwave and
ultrasound energy in order to obtain volatilization products [111]. The document admit-
ted that the ‘chemistry of the process is not completely understood’ and again, wrongly
claimed that ‘the microwave energy is sufficient to crack or rupture bonds in the high
molecular weight material’. The patent established that cracking resulted because of arc-
ing occurring between carbon particles, which is partially correct; however, it failed to
provide accurate explanations of the phenomena involved and often incurred assumptions
that at present are believed to be false.
The 1980s saw many more patents filed and published, explicitly using the concept of
microwave pyrolysis and with an increasingly obvious environmental drive; for example, a
patent entitled ‘recovery process’ describes a method and an equipment for the microwave
pyrolysis of the char formed by the initial conventional pyrolysis of waste tyres [112].
However, even though the number of patents increased, many of these still did not describe
the nature of the process and the role of the microwave-absorbents. Patent EP 409835
for example, described a method and apparatus for the destructive distillation of organic
material; this ‘destructive distillation’ being the pyrolysis of said material [113]. The
invention described an equipment to carry out the process with a preheating stage (using
the recycled pyrolytic gases) followed by microwave pyrolysis of the preheated waste.
The description incorporated more details for the equipment and the process conditions
compared to previous patents and presented innovative ideas to help achieving higher
process efficiencies. However, it also established that ‘the material being subjected to
destructive distillation is such that it contains a substantial proportion of carbon–carbon
bonds (such as a hydrocarbon or carbohydrate material)’. Examples mentioned included
agricultural waste, sewage and slurry; however, it is known nowadays that some of these
wastes do not pyrolyse by the simple action of microwaves and need a microwave-
absorbent. Sewage sludge, for example, does not contain on its own enough carbon black
to absorb enough energy to pyrolyse and hence, subject to microwave radiation, it dries
only by evaporation of water [54, 56]. Similar inaccuracies exist in a number of patents,
essentially variations of EP 409835, describing processes for the production of carbon
black via microwave pyrolysis [114].
Patent EP 393030 first described with more accuracy the microwave pyrolysis process,
defining it as: a method for the destruction of macromolecular waste material which is
not itself susceptible to microwave heating, by contacting it with a material susceptible to
heating by microwave radiation, in an atmosphere which is such that flame generation is
substantially prevented [115]. There are also several patents for several countries that are
in essence just variations of this one, for example, Patents EP541641 and GB2,256,435.
These, even though they do not appear as equivalents in the patents offices, have been
studied and do not provide anything new to the concepts already included in those men-
tioned above. Furthermore, Patent EP 393030 mentions plastics as an example of the
waste material and suggests ‘carbon black or other material that upon degradation, pro-
duces carbon black such as waste tyres’, as microwave-absorbent. Figure 21.7 presents
the block diagram described in this patent, showing the typical sequence of operations
in an example of the invention for combined microwave pyrolysis of tyres and plastic
waste.
However, even if the process definition was better accomplished, the suggestions in the
patent for process embodiments (equipment configurations) are nondetailed. Moreover, the
patent also contains suggestions that seem inaccurate in the light of current knowledge.
For example, a process temperature of 400–800◦ C was suggested for the pyrolysis of
PE or Nylon, but at least 800◦ C for more ‘thermally resistant plastics and halogenated
plastics (such as PTFE or PVC)’. There is no evident reason to suggest that higher
temperature provides better process efficiency for the pyrolysis of PVC; on the contrary,
the use of initial moderate temperatures for the pyrolysis of PVC is an extremely useful
way of performing the dehalogenation of the waste prior to the pyrolysis of the polyene
backbone [116]. Also, the patent claims that the waste material should be fed to an upper
part of the bed of microwave-absorbent in order to maximize contact between the two
solid phases, as the former sinks through the bed. The justification for this claim is that the
bulk specific gravity of carbon is 0.5 whereas that for plastic is about 0.8–1.0. However,
it has now been proved that when HDPE pellets are placed on top a bed of carbon in
order to carry out microwave pyrolysis, the process is very inefficient, the plastic does
in fact not sink within the carbon bed and a considerable amount of char is left on the
surface of the bed [86].
Inert gas out
Scrap vulcanised
tyre compound Pulverisation Mixing Microwave irradiation Inert gas in
gas and liquid

Separation
Scrap plastics Solids
Classification
Disposal
Figure 21.7 Process flow diagram for the destruction of macromolecular waste. Figure 1
in Patent EP 393030
In the 1990s additional microwave pyrolysis patents were filed with special emphasis
on tyre degradation. An ‘improved’ method and apparatus for the destructive distilla-
tion of organic materials, tyres in particular, using microwave energy was presented,
using a variable-power microwave generator so that the applied power could be increased
once the pyrolytic temperature was reached (with an alleged improvement in process effi-
ciency) [117]. A mobile apparatus for the same purpose with a cylindrical rotating reactor
which aids the reaction and allows the separation of solid and liquid products during the
process is also claimed [118]. Likewise, another rotating devise is claimed through Patent
WO01/03474 in which a tyre or tyres are rotated inside an annular enclosure and around
two arms that deliver microwave energy to both internal and external surfaces of the
tyre [119].
Specifically with regard to the pyrolysis of plastics, new patents have been filed recently
containing variable degrees of process description and equipment detail. For example,
a process is described for the microwave pyrolysis of polymers to their constituent
monomers with particular emphasis on the decomposition of poly(methylmethacrylate)
(PMMA). A comprehensive list is presented of possible microwave-absorbents, includ-
ing carbon black, silicon carbide, ferrites, barium titanate and sodium oxide. Further-
more, detailed descriptions of apparatus to perform the process at different scales are
presented [120]. Similarly, Patent US 6,184,427 presents a process for the microwave
‘cracking’ of plastics with detailed descriptions of equipment. However, as with some
earlier patents, this document claims that the process is initiated by the direct action of
microwaves initiating free-radical reactions on the surface of ‘catalysts or sensitizers’ (i.e.
microwave-absorbents) [121]. Even though the catalytic pyrolysis of plastics does involve
free-radical chain reaction on the surface of catalysts, it is unlikely that the microwaves
on their own are responsible for their initiation.
Another patent in which there is some doubt about the underlying chemistry, is US
6,133,500 which shows a method and apparatus for the controlled ‘non-pyrolytic’ reduc-
tion of organic material. The patent presents an innovative design for the application of
microwaves to the reactor. Nonetheless, regardless of this potentially efficient idea, the
document claims that: ‘the microwave energy results in the severing of weaker molecular
bonds in longer chain molecules to reduce those molecules to simpler forms. This is in
effect a de-polymerization process. The process is controlled to avoid pyrolysis of the
organic material’. However, the typical process temperature mentioned was 350◦ C which
is well into the pyrolytic temperature for many organic materials and in particular for the
ones mentioned in the patent (tyres, plastics, etc.). Clearly the invention is a pyrolytic
process with a different name [122].
Patent US 6,152,306 describes a whole plant for the reduction of municipal solid waste,
including plastics. The plant is said to include a microwave reduction chamber in which
pyrolysis presumably occurs. However the document did not contain any detail regarding
the chemical reactions or the mechanisms involved [123].
4.2 COMPANIES
There are a few companies that advertise on the Internet proprietary processes for micro-
wave pyrolysis of wastes. Not surprisingly, considering what was presented in the previous
section, most of these refer specifically or specially to the pyrolysis of waste tyres.
One of the most active companies dedicated to the treatment of wastes using microwave
heating has been Environmental Waste International (www.ewmc.com) based in Canada.
The company owns the rights to patent US 6,133,500 presented above, commercializing
it as a ‘leading edge Reverse Polymerization Process where direct microwave energy
breaks down organic waste to create profitable and sustainable solutions’. According to
the information presented on the website, the feasibility of their waste tyre recycling
process was proved using a pilot plant operating from 1994 to 1998. Even though there
are no references to installations of full commercial plants for waste tyres, the company
has operational plants working with other biological and medical wastes. In May 2004
they finished installing a liquid biological waste treatment process for the United States
Department of Agriculture.
Amat, Ltd (www.amat-ltd.com) based in the United Kingdom, presents on their web-
site ‘The world’s most advanced environmental technology’. Amat stands for Advanced
Molecular Agitation Technology. The company’s technology is based in their Patent
WO01/03474 presented above and has being commercialized as Z3A Process and Technol-
ogy (from Zero Environmental Damage, 3rd alternative; landfilling and incineration being
the first two). The company has received three awards since 2000 that have enabled them
to continue their work in the area and are looking for partners for the commercialization
of their technology.
Reactive Energy, LLC (www.reactiveenergy.com) is a company based in the United
States whose ‘mission is to pursue the development and commercialization of processes
utilizing chemical reactions facilitated by microwave energy’. Currently, the company is
focused on the development of three primary applications using microwave technology.
One of these, called Climax PlusTM, is commercialized as a patented a method for
converting mixed plastic waste into low-sulphur fuel oil. It is believed that this technology
is based on Patent US 6,184,427 described above.
Likewise, another company whose technology may be based on a patent described in
this chapter is T.R. Environtech Co. Ltd (www.trrecycling.co.kr). A Korea-based firm,
their website mentions that their technology is based on the work performed by the
person who some years earlier invented Patent US 4,118,282. However, even though the
company claims to have a process for the ‘low temperature pyrolysis for tyre waste and
rubber waste’, the website does not mention microwaves as the heat source for the process.
Finally, Molecular Waste Technologies Inc. is another US-based company developing
microwave technology for waste disposal. The website mentions that they have collab-
orated with Amat (above), but that they have their own proprietary process, covered by
patent US 6,152,306. The company establishes that a plant using its process could be opti-
mized to process 600–700 tonnes of MSW per day, producing nearly 400 kg of carbon
black and 175 litres of oil per tonne of MSW.
5 CONCLUSIONS
Microwave heating is a process tool that has a number of advantages over other, more tra-
ditional, heating methods. These advantages include a more even distribution of heat, high
heating rates and easier control over the temperature. Although most existing microwave
heating processes are used to heat up materials that have permanent dipoles, mainly water,
other materials, such as carbon, can also be heated.
Mixing carbon with microwave-transparent materials, particularly plastics, and subject-
ing the mix to microwave radiation, is a very efficient way to heat up such materials,
increasing their bulk temperature to a point where pyrolysis occurs. In this chapter the
main characteristics of a number of microwave pyrolysis processes, for plastics and other
materials, have been introduced, showing that these processes combine the advantages of
microwave heating with the commercial and environmental opportunities intrinsic to the
pyrolysis of wastes.
Scientific studies have found that the differences between microwave and conventional
pyrolysis go beyond the obvious difference in the source of heat. Other differences arise
from the very high rates of heat transfer from the microwave-absorbent to the waste, the
amount heat received by the primary pyrolytic products once they leave the absorbent bed
and the highly reducing environment. These three aspects have been shown to have an
important effect in the final products since they modify the extent of secondary and tertiary
reactions. Moreover, the scientific studies have shown that a nonthermal microwave effect
in these processes is unlikely to exist. Tests have showed the potential of the microwave-
induced pyrolysis process for the treatment of real plastic-containing wastes and it is
believed that a commercial process could be developed, for example, to recover clean
aluminium from plastic/aluminium laminates. Other materials, in particular tyres, coal
and medical wastes are very good candidates to be treated/recycled using microwave
pyrolysis and there have been a considerable number patents filed with this goal in mind.
The research and development carried out so far in has shown that, even though
microwave pyrolysis will not be the solution to the whole problem of plastic disposal, it
certainly has the potential to help reducing the number of resources currently committed
to landfill. Evidence of this potential is the number of companies interested in the devel-
opment of the process and that are currently active, trying to commercialize proprietary
microwave pyrolysis processes. However, this chapter has shown that in order to accom-
plish a more widespread utilization of this kind of processes a better communication
between the commercial and scientific communities is needed. The companies with their
patents would be able provide many innovative ideas that may help to increase processes
efficiency and the scientific community would provide explanations for the improvements,
that would in turn generate even more ideas in a self-sustaining cycle of improvement.
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22
Continuous Thermal Process

for Cracking Polyolefin Wastes
to Produce Hydrocarbons
JEAN DISPONS
Chemical Engineering Adviser
France
1 BACKGROUND
The viability of obtaining hydrocarbons through thermal decomposition (i.e. pyrolysis or
thermal cracking) of polyolefins has been known ever since polyolefins were discovered,
more than 70 years ago. However, the ecological and economic needs for this decomposi-
tion have only been appreciated when it came to treating huge amounts of wastes of these
materials that are increasing every year. Nevertheless, it is necessary to mention an initial
application relating to polyolefin thermal cracking for the production of polyolefin wax,
but this process used only new materials, as distinct from wastes. The patent 1457575 for
Leuna Werke – Walter-Ulbricht was an example of this in 1965.
Contrary to an apparently widespread idea, the reuse of polyolefin wastes after sat-
isfactory cleaning and sorting, as a ‘regenerated’ plastic material is rarely practical in
technical and economic terms. Firstly, polyolefins are easily attacked by oxygen in the
air and ultraviolet radiation. When polyolefin waste is left exposed to outdoor conditions
for months, as is the case with most wastes, it can become too degraded to provide good-
quality plastic material that conforms to the standards (with probably the only exception
being films that are highly carbon-filled).
Secondly, the cleaning of the wastes must be thorough, for the purposes of both the final
quality of the product as well as for the protection of the injection moulds and extruders
that process it. However, such a standard of cleaning is difficult and requires considerable
labour such that the waste thus cleaned can cost more than the starting raw material. In
conclusion, only the ‘new’ wastes, such as fabrication scraps, injection runners and gates,
etc. can be economically regenerated, which represents a very small percentage of the
total waste stream. Hence, if we wish to valorize polyolefin wastes, we are left with only
one solution consisting of producing high-quality hydrocarbons by thermal cracking.
596 J. DISPONS
2 INTRODUCTION
Hydrocarbon thermal cracking (or pyrolysis) has been practised in the petroleum industry
for more than a century, and the problems raised by such an operation are now largely
solved. Thus, this work deals only with the questions specific to the polyolefin cracking
based on common practice and procedures.
Polyolefins consist of very long chains of the alkene type with thousands of carbon
atoms, but possessing only one final double link in the α position. Theory shows that
thermal cracking leads to shorter molecules, but of the same type. These shorter chains
generally possess only one final double link in the α position. Most of these molecules
are therefore α-olefins.
The energy necessary for cracking the polyolefin wastes is provided in the form of
heat, and the most rational way of obtaining it lies in burning a part of the hydrocarbons
resulting from the cracking itself. The question is then: ‘How much would be consumed
for this operation?’ The answer, to a great extent, depends on the operational conditions,
but this chapter will provide some of its theoretical elements. The solution is in breaking a
certain number of links between the carbon atoms in the polymer chain. This number will
determine the result obtained. Only cracking leading to the array of liquid and gaseous
hydrocarbons most commonly obtained will be dealt with here.
The average energy of the C–C link is considered to be 313 kJ mol−1 (75 kcal/mol).
A simple calculation shows that to pass from the polymer to the average hydrocarbon
obtained during the intended cracking, seven links per polymer kg must be broken, which
represents less than 2200 kJ/kg (less than 525 kcal/kg). The energy needed for heating, for
the polymer fusion and for the vaporization of the hydrocarbons obtained must be added,
making a total of less than 600 kJ/kg. The total is lower than 2800 kJ/kg (670 kcal/kg).
This energy can be easily obtained by burning 0.1 kg of hydrocarbons (taking into con-
sideration the poor heat yield). Therefore, it is apparent that the combustion of 10% of the
polymer contained in the wastes is sufficient to guarantee their complete cracking. Some
wastes with high water and impurities content may require more energy. While this is so,
it is noticeable that cracking yields between 15 and 20% of gas that is noncondensable at
room temperature. The combustion of this gas more than adequately provides the energy
needed for the cracking (this method of heating is the object of a French patent lodged
by the author in 1992 under the French Patent 92 13189).
One important point to be stressed is that, for a given temperature, the longer the
molecule the faster is the cracking. On the other hand, in practical terms, it should be
noted that in the absence of oxygen, the cracking of alkanes in particular begins at around
300◦ C and increases sharply at around 360 – 380◦ C, at which temperatures the output
products are converted to the vapour state (except for the tar and the coke). Therefore,
boiling of the plastic charge being cracked can be observed.
Whatever the chosen pyrolysis procedure is, we obtain at least 15–20% of >C5 com-
bustible gases where combustion produces a heat that is largely sufficient to undertake
the whole pyrolysis process. All the cracking procedures that take into account this fact
will be self-sufficient in terms of energy. In addition, the cracking, being undertaken in a
closed vessel without a significant pressure, is an operation that is neither polluting nor
dangerous and can be undertaken using cost-effective equipment.
Moreover, it should be noted that catalytic cracking can be considered only in the
liquid or the vapour phase and only with sufficiently purified hydrocarbons. It is practised
CONTINUOUS THERMAL PROCESS TO PRODUCE HYDROCARBONS 597
according to techniques that are already well known, which can be found in the literature in
order to allow the production of some preferred products. In the case of waste pyrolysis,
this type of cracking can be undertaken only after a preliminary cracking would have
transformed the wastes into liquid or gaseous hydrocarbons. However, the liquids obtained
through the cracking of impure wastes are themselves contaminated with impurities and in
general too contaminated for a direct catalytic cracking operation. Thus, catalytic cracking
is best undertaken with a second phase and only thermal cracking vapour obtained in the
first phase.
3 THE TWO PRINCIPAL PHASES OF POLYOLEFIN WASTE CRACKING
Presented here are only the methods that the author has tested in practice on plastics
wastes. The first attempts were undertaken in 1986 in a small pilot unit that dealt with
wastes of polyolefin films used for packaging. Those wastes were nonpigmented, transpar-
ent and rather clean. They were provided by waste collectors in blocks of approximately
30 kg, intended for factories producing ‘regenerated’ granules (recyclate). The intention
was to show the potential of producing a polyolefin wax to be used in polish applications
or in ‘hot-melt’ glues from those wastes.
The procedure that was developed then was based on the idea that molten polyolefin
was totally decomposed at around 360◦ C, yielding more than 90% of polyolefin liquid
wax. The remaining part, being made of combustible vapour whose combustion produced
enough heat to ensure this decomposition. The produced wax was collected in a continuous
process, rapidly cooled and transformed into powder. It was only slightly coloured and
was successfully tested in the fabrication of polishes, as a lubricant for the extrusion
of PVC and in compositions of hot-melt glues in combination with petroleum resins.
This pilot unit was beneficial for familiarization with the practical problems encountered
during the treatment of polyolefin wastes of all sorts, coloured and polluted with food or
soil impurities, and to test and develop many efficient continuous operations allowing the
pyrolysis of these wastes without precleaning.
The pyrolysis treatment of unclean polyolefin wastes may yield two commercial products:
1. In the particular case of transparent and sufficiently clean wastes, the production of
polyolefin wax can be considered as described above. Such products have a higher
commercial value than that of the new plastic material itself.
2. In the general case of wastes of all sorts, coloured or printed and filled during the
pyrolysis with a variety of harmless impurities (food or soil impurities), also in addition
mixed wastes containing EVA or polypropylene, it is no longer possible to stop at the
stage of the wax produced in the first phase of the cracking. Indeed, this wax is in this
case commercially worthless due to its high level of colours and impurities. Therefore,
it must be pyrolysed and transformed into hydrocarbon vapours which will leave the
nonvolatile impurities in the wax cracking chamber.
A second phase will follow the cracking of these pyrolysis vapours, involving when
needed, catalysts in classical cracking tubes in a way that will favour the formation of
the desired products whenever possible. The final vapour obtained is generally rapidly
cooled (quenched) at approximately 400◦ C, before being fractionated in a column where
the components are separated and condensed in portions at convenient intervals. This
598 J. DISPONS
second phase is well known, but it can only be undertaken after the first phase which
provides it with its raw material, has taken place with the maximum efficiency and yield.
Therefore, in all the following sections, there is emphasis on the procedures of this first
phase which terminates when all the wastes are transformed into hydrocarbon vapours.
4 THERMAL VALORIZATION OF POLYOLEFIN WASTES
The methods that will be dealt with here are those used to obtain hydrocarbon vapours
from this first phase. The treatment of plastic wastes of all sorts by pyrolysis, being still in
its early stages, workers keeping practised procedures confidential, and often protects them
by patents. As a consequence, this chapter deals exhaustively only with the procedures
that have been personally tested and developed by the author. The general principle of
polyolefin waste pyrolysis consists of heating plastic materials in isolation to a sufficient
temperature such that the polymers decompose into small hydrocarbon molecules.
The first problem that is encountered is to study the possibility of continuous operation
with various solid wastes. Indeed, from an industrial point of view, a batch process reactor
that must be filled, emptied and cleaned after every operation does not allow a rational
adaptation of the two pyrolysis phases, since the second (cracking the pyrolysis vapours
resulting from the first operation) is essentially continuous. However, it is possible to
solve this problem by using multiple reactors operating in parallel; each one is periodically
stopped for cleaning and filling while the others are working. This technical solution is
absolutely valid, but it still has the drawback of requiring considerable equipment, if huge
amounts of waste plastic are to be treated.
The author has developed a totally continuous process while continuing to tolerate the
pyrolysis of all sorts of wastes, including those heavily loaded with impurities without
any treatment or precleaning. Despite the fact that the processes that are described below
tolerate the treatment of all types of polyolefin wastes, they were developed while consid-
ering the most common wastes and those accumulated in large quantities in specialized
centres. Therefore, there was a special consideration of domestic packing wastes coming
essentially from post-consumer domestic waste sorting centres (bags, wrapping sheets,
bottles, containers, pots, etc.) as well as from wastes of agricultural sheets (greenhouses
and cultivation tunnels). These types of wastes are easily compressible and their impurities
are not harmful since they are in contact with food products. However, they sometimes
contain considerable quantities of agricultural matter or soiled food impurities. The pro-
cesses that have been developed by the author enable the treatment of polyolefin wastes
containing occasionally up to 70% by mass of humid soil impurities.
5 CONTINUOUS FEEDING OF THE CRACKING REACTORS
The feeding system in continuous operating mode of the cracking reactor is as follows:
polymeric mixed wastes are transferred by a moving conveyor, and drop into a feed
container (a hopper) with an opening large enough to receive them. At the hopper base,
the plastic wastes are taken up by a piston operated by a jack, and compressed into a
feeding tube situated at the axis of the piston motion. This tube is of a diameter between
0.3 and 1.2 m, depending on the load to be treated and the downstream process.
The head of the piston is equipped with hollow points, of a trocar type, parallel to the
axis of the feeding tube and intended to pierce and to tear the garbage in order to facilitate
at the time of compression the evacuation of the maximum possible air and water that it
may contain. This water and air is evacuated through perforations in the anterior part of
the feeding tube, as well as through the hollow points of the piston.
The feeding tube with a length of 2–4 m, depending on its diameter, opens into a
closed reactor where the wastes are heated up to approximately 360–380◦ C, at which
temperature they are transformed into polyolefin wax after being cracked.
The problem of watertightness is solved by the compression mechanism of wastes so
that they constitute a hermetic stopper at the outlet of the feeding tube. This compres-
sion is undertaken simultaneously by the piston action and by a slight constriction of
the feeding tube diameter at the inlet of the rector. Anti-return moving lugs prevent the
compressed waste stopper from returning when the piston backs up. It is useful to employ
a water radiator for cooling the part of the feeding tube where the plastic ball is formed
so that the molten wax in the reactor does not make it melt prematurely. This method of
continuous feeding was tested at scaled-up dimensions and yielded satisfactory results.
The feeding tube and the reactor extending from it on the same axis are slightly tilted to
allow the downward flow of the wax.
6 HEATING METHODS
The classical processes of melting organic solid matter consist of tossing and mixing it, and
having intimate contact with the heated wall of the container. However, polyolefin wastes
are poor conductors of heat and direct heating by the heated wall leads to overheating
that generates coke and char. It is only through vigorous mixing, together with constant
scraping that this can be avoided. This requires complex equipment.
To avoid having to resort to this apparatus, the author used a different technique. This
consisted of heating wastes arriving in continuous mode to the reactor. Such a method
distinguishes the two processes that I will describe below.
The author’s first process, still under valid patent, submitted in 1992 under French patent
92 13189, calls attention to the fact that polyolefin is very absorbent in the infrared. This
allows it to be heated by the radiation emitted by the bright red-hot walls, at a score of
centimetres from a cylindrical grid made of stainless steel and having large rings inside
which repel the polyolefin coming through the feeding tube so that it remains confined
as long as it is in the solid state. The reactor walls are heated to red-hot by gas burners
situated at the exterior of the walls and fed by the noncondensable gases produced by the
cracking process itself.
A possible sweeping of the reactor by the superheated water vapour produced by an
exchanger using the lost heat of the gas burners constitutes an excellent improvement by
realizing a vapo-cracking, minimizing the formation of tar and coke.
The molten wax flows along a receiving channel situated under the grid and is extruded
gravitationally outside the tilted reactor through a purpose-made hole, at the same time as
the vapour produced during the cracking. This wax is led to a second phase of the treat-
ment. The organic impurities of the wastes are in turn decomposed yielding essentially
water vapour and carbon while mineral impurities yield sand and baked clay.
600 J. DISPONS
These impurities are swept and released with the wax flowing outside the reactor. This
wax is very fluid and can be easily decanted and filtered with traditional equipment, highly
heat-proofed after its extrusion from the reactor without being too cooled. Therefore it is
sufficiently purified to be treated in a second phase.
The possible heavy impurities that may remain in the receiving channel of the reactor
are periodically scraped by a traditional mechanical apparatus and are collected in a
container prepared for the purpose of evacuating them easily.
The author’s second process, patented in March 2002 under French patent 02 02737,
utilizes the same feeding system for the reactor as well as waste confinement in a cylin-
drical grid with the same diameter of the feeding tube (Figures 22.1, 22.2). The reactor
walls are always at some distance from the grid, but now they are thoroughly insulated on
their external side and not heated at all. The necessary heating for the primary cracking
stage is then undertaken by the steam superheated to around 500–600◦ C which attacks
the wastes directly through the openings of the grid. The effect of the steam thus over-
heated and coming directly in contact with the wastes is analogous to that of a naked
flame. Polyolefin undergoes a very rapid partial cracking during the time that the attack-
ing water vapour cools to around 350–400◦ C. The nonvaporized part makes a wax that
flows through a channel made for the purpose. Then, this wax is evacuated and purified
as described in the first process. The impurities are extruded in the same way as described
above.
The uniqueness of this process results from the fact that the steam provides the total
heat necessary for the primary cracking stage. It is not therefore a simple vapo-cracking.
This process intervenes simultaneously while suppressing to the maximum the formation
of tars and coke by dilution of steam and partial reduction of the steam pressure resulting
from the heavy hydrocarbons produced. Additionally, this process is very flexible and it
is suitable for the treatment of highly variable feed rates of waste.
Experience showed that the optimum length of the grid confining the waste can vary
from 2 to 3 m and that it is certainly possible to work with several grids mounted in
parallel and supplied separately. For example, one can accommodate three grids of 0.5 m
diameter and 2.5 m length, side by side in the one reactor, separated by 0.3 m. This
example corresponds more or less to a capacity of continuous cracking process of one ton
Hopper for plastic wastes
Reactor
Feeding
tube
Piston with Confinement grid tube
hollow
points Outlet tube for
hot vapours
Figure 22.1 Schematic illustration of the principle of cracking of waste by steam

Figure 22.2
602
Figure 22.2 The initial cracking is done in a closed vessel, sealed from atmospheric oxygen, using heat from direct contact with
very hot chemically inert or unreactive gases heated by burning noncondensable gases from the cracking process itself. A classic
feed system such as a piston pushes the plastic wastes continuously into a cage in the vessel which keeps them a small distance
from the vessel walls. The very hot gases providing the heat are chemically inert or react very little in the cracking conditions.
The solid, liquid and gaseous products from this first cracking phase flow freely to the bottom of the vessel in a sealed chamber
which acts as a separator. The gaseous products escape from the separator to be burned in the second stage of cracking; the solid
products are retained by a sieve and the liquid products are collected in the bottom of a boiler below the separator together with
the superheated steam. These collected liquids undergo a second cracking by boiling heated by one or more gas burners fed by
the noncondensable gases from various cracking stages. During a third cracking stage vapours from the boiler pass through a
tube bundle reactor heated to between 400 and 600◦ C where the vapours decompose into fractions whose boiling point is not
greater than that of diesel (about 360◦ C). Superheated steam is injected during the second and third cracking stages to obtain
steam cracking conditions. The vapours leaving the reactor are sent to a classic fractionation column where they are fractionated
into liquid cuts with different boiling points, chosen according to need, and into gases noncondensable at ambient temperature.
The latter are sent to a gasometer to feed the gas burners in the various cracking phases, with the surplus gas forming a primary
material rich in α-olefins. Steam is injected near the burner flame(s) in the first cracking stage at low pressure superheated to
500◦ C. The heat lost in the burned gases in the various burners is recovered in a water tube exchanger producing low-pressure
superheated steam between 400 and 600◦ C for use in the third cracking stage. The gases and vapours from the first cracking stage
are separated from the liquid and solid products in the separator are burned using additional air in the burners heating the boiler
and reactor in the second and third stages. An independent claim is also included for the use of a particular version of this process
where the wastes are compressed by a piston (1) in a tube (2) which is several millimetres thick, with a diameter of between 0.3
and 2 m, preferably between 0.3 and 0.5 m and a length three or four times its diameter. The surface of the piston is covered
with strong points not more than 0.3 m long, parallel to the axis of the tube and the first third of the tube is perforated, allowing
water to flow through. The tube is extended at its end by a mesh cylinder (3) in refractory metal for 2–6 m, closed at the end
by a grill. This mesh part is enclosed in a cylinder (4) of refractory steel several millimetres thick, coated externally with a classic
insulating layer. The walls of this cylinder are several centimetres from the mesh cylinder except at its end, where the cylinder
extends beyond the mesh cylinder by about one diameter to form a cylindrical chamber closed by a flat or dished base with a
closeable opening for combustion gases (20) and a superheated steam injector (21). Key: 1 piston; 2 feeding tube; 3 grid; 4 reactor;
5 collar; 6 end of reactor; 7 exit of wax and vapours; 8 decanter; 9 sieve; 10 exit of vapours; 11 tube for extrusion of wax decanted;
12 door to evacuate impurities; 13 boiler-exchanger; 14 second exchanger; 15 exit of exchanger; 16 column; 17 kiln; 18 gas burners;
19 chimney; 20 special case, admission of hot neutral gas (if steam not used); 21 general case, admission of superheated steam;
23 boiler-exchanger for steam
J. DISPONS
per hour of polyolefin contained in waste with a 20% level of impurities. In general, a
well-designed grid associated with a good distribution of the superheated steam injectors
permits the cracking of 100 kg/h of polyolefin per m2 . Finally, the two described processes
lead to the same results. However the superheated steam process on the whole produces
a more advanced cracking than the ‘radiation’ process which provides more wax.
The second part of the first phase consists in converting the formed wax into hydro-
carbon vapours. For this, the wax coming from the reactor is heated in a boiler to the
boiling point (∼ 380◦ C), preferably by injection of superheated steam (to a temperature
depending on the intensity of the desired cracking) after its purification by decanting
and filtration. In general, the cracking vapours produced by this boiling point contain all
the hydrocarbons ranging from C30 to methane (and even hydrogen) and their fractional
condensation gives on average about 10% of noncondensable gas, 35% of a mixture of
light and heavy gases, 40% of light fuel oil and 15% of viscous products.
The steam and the hydrocarbons coming out of the reactor at around 380◦ C simulta-
neously with the formed wax, can be sent either after reheating or without reheating, to
the bottom of the boiler where they will contribute to dragging the steam coming from
the boiling wax, or mixed with this steam after its formation so that it undergoes the
complementary cracking of the second phase in both cases.
All the steam necessary for the process is produced by plates heated by the remaining
heat of the fumes from gas burners after having swept the cracking tubes of the second
phase. The superheating of this steam is assured by taking the tubes carrying it past a
region close to the burners.
After the first phase, there arises the question of the objective of the second phase. The
response depends on commercial considerations. It is important to recall that the cracking
is by nature a statistical operation that affects all the existing molecules. This makes
it impossible to avoid the cracking of some molecules that one would wish to keep,
since otherwise it would be difficult to extract them rapidly enough from the reaction
environment. At the termination of the process, the whole range of molecules foreseen
by theory at a given temperature and time of cracking is obtained. Another consideration
is that the elevation of the temperature of cracking increases the formation of coke and
light products. Nonetheless, it is possible to favour the formation of some commercial
products to a certain extent.
If one tolerates the necessarily marginal wax production, one can estimate that the
commercial products obtained can be classified either into fuels or other combustible
products, solvents, or products intended for the chemical industry. The author estimates
that this last market is the most promising, although it has not yet been investigated
seriously. Indeed the hydrocarbons obtained by polyolefin cracking (even from impure
garbage) consist essentially of a mixture of a low percentage of alkanes and a large
percentage of α -olefins. Importantly, the α -olefins are the raw material of choice for
petrochemistry and for the oxo synthesis in particular.
However, as a first step, it will be certainly easier to exploit the energy aspect and to
propose use as a fuel or hydrocarbon. In these conditions there are only two possibilities:
(i) to encourage the production of fuels for diesel engines (diesel oil); or (ii) the production
of LPG and fuels intended to supply generators propelled by gas turbines.
The production of diesel oil will always be limited by the simultaneous formation of
other hydrocarbons for which it will be necessary to find uses as well. One can favour
604 J. DISPONS
the formation of diesel oil by practising cracking at a minimum severity in the presence
of water vapour superheated to 450◦ C with repeated recycling of the products. This will
have the effect of preserving to the maximum products ranging from C12 to C16 of a more
advanced cracking.
Of course the hydrocarbon vapours can also be treated catalytically (on zeolites for
example), but this will not prevent the recycling of the load component that is insufficiently
cracked. In any case, there will always be about 20% of gas whose combustion can largely
provide the energy necessary for the whole operation and a fraction of heavy and light
gases will remain. This will be very difficult to reduce below 30% of the starting load.
But these substrates are excellent solvents, a very good equivalent to the usual degreasing
solvents available in the market. This should assure them a ready market. In the domain
of fuels, there is also a possibility to encourage the formation of combustible gases solely,
without obtaining liquid hydrocarbons (i.e. C4 at most).
If one makes this choice, it is necessary to resort to cracking at a high temperature
with the recycling of the fractions insufficiently cracked after a first process, and to accept
increasing formation of coke that may reach 5% or more. However, the required equipment
will never require the fractionation of the vapours and the condensation in more or less
heavy fractions. It will therefore be possible to get rid of a costly distillation column in
the design. The gas obtained must be sent to a gasometer of several cubic meters volume
from where it is taken up by a compressor to be stored.
Beforehand, it will be necessary to separate the gas into two categories:
1. A mixture of C3 and C4 , alkanes and alkenes of LPG type, easily liquefiable and
storable in standard containers.
2. A mixture of methane, hydrogen and ethane that can be stored for example under a
pressure of 50 bars.
Although the liquefiable gas generally predominates, the respective percentages are
difficult to foresee and depend extensively on the cracking conditions. The LPG gas is
perfectly adapted to the gaseous fuel used in cars whose engines are designed for gas.
The total absence of sulphur is an additional advantage.
With regard to the nonliquefied gas, a part is indispensable to provide the energy
necessary for the whole installation. The remaining quantity (typically more than half)
can be used to produce electrical energy by supplying a gas turbine generator. The gas
turbines operate on heavy fuels in general, but adapt very well to a gaseous fuel. Other
processes are being investigated and some have even been the subject of patents, but
the time for their assessment has not been sufficient. In any case, the polyolefin waste
pyrolysis industry is expected to achieve a significant and rapid development throughout
the world, as much to recover precious molecules as to preserve our environment.
23
Waste Plastic Pyrolysis in Free-Fall

Reactors
ALİ Y. BİLGESÜ, M. ÇETİN KOÇAK, AND ALİ KARADUMAN
Ankara University, Engineering Faculty, Chemical Engineering Department, Tando an
06100 Ankara, Turkey
1 PYROLYSIS
Pyrolysis is an ancient method of decomposing solid matter by heating to high tempera-

tures; examples are production of metals, coke furnaces, and obtaining of chemicals from
coal prior to petroleum. There are many kinds of pyrolysis: batch, semi-batch or con-
tinuous; catalytic or non-catalytic; out under vacuum or at atmospheric or high pressure.
Its medium may be inert, oxidative or reductive. Heating rate, temperature, and time are
important pyrolysis parameters.
With regard to the applied temperature and heating rate, pyrolysis may be classified
under two groups: (i) pyrolysis at a slow heating rate; (ii) pyrolysis at a rapid or flash
heating rate. In the first group, the residence time of the solid in the reaction zone is of
the order of minutes to hours. During rapid or flash pyrolysis the corresponding time is
milliseconds to seconds.
Free-fall reactors (FFR) are a good choice for rapid or flash pyrolysis. They have been
widely harnessed to pyrolyze coal and, more recently, biological mass. A pioneering group
at Ankara University was the first to attempt pyrolysis of waste plastics in a FFR. Their
results are very promising indeed compared with other alternatives in the literature.
2 PREVIOUS PYROLYSIS WORK
Until fairly recently, no significant publications were produced on rapid or flash pyrolysis
of waste plastics harnessing a FFR. A review of FFR developments is therefore given
below regarding coal or biomass applications.
Badzioch [1] summarized the volatile yields in the pioneering studies carried out at rel-
atively low temperatures in a publication on rapid pyrolysis containing three introductory
606 A.Y. BİLGESÜ ET AL.
sections and a collection of twelve papers by various Russian authors. According to
Badzioch, Shapatina et al. authored the earliest publication on the kinetics of the devolatil-
ization of coal particles in suspension in 1950. Their main interest was the variation of
volatile products with heating rates. They showed that the gaseous products from rapid
pyrolysis were more useful than in slow pyrolysis.
High heating rates were applied in fluidized-sand-bed experiments by Pitt [2] who
studied the kinetics of volatile product evolution from coal. He measured evolution rates
in a fluidized carbonizer at temperatures from 300 to 650◦ C, over a time period 10 s
to 100 min.
Loison and Chauvin [3] studied fast heating in the range of 1000◦ C/s by means of two
types of apparatus: a vertical furnace in which a coal flow carried by gaseous nitrogen is
heated by radiation; and a belt furnace in which the particles of the coal are introduced
into the meshes of metallic cloth which is heated by resistance. The material balance was
established for the pyrolysis of seven coals of different ranks. The results showed that
volatile matter yield was sometimes greater than that obtained by the standard method
and always greater than the change in proximate volatile matter between the original coal
and resulting char. Fast pyrolysis gave a high tar/gas ratio. The tar yield was maximum
(27%) for bituminous coals having a carbon content of about 86%.
Edinger et al. [4] studied rapid decomposition of coal in a transport-type reactor, with
residence times 8–40 ms (COED-FMC). They found that pyrolysis atmosphere affects the
products. Coal particles never reached the reactor temperature, even at the lowest particle
transfer rate; 59% of the coal volatilized when the reactor temperature was 1300◦ C. This
is far above the 41% indicated by the ASTM volatile-matter determination.
Howard and Essenhigh [5] pyrolyzed coal particles, burning them in a one-dimensional
plane-flame furnace. They measured the solid composition and the flame temperature
along the axis of propagation. Particles attained a temperature of about 1100◦ C without
ignition or significant devolatilization. They found that devolatilization of 0–200 µm
particles seems to be a volumetric reaction that is independent of particle size.
Kimber and Gray [6] studied the kinetics of devolatilization of a series of coals at
temperatures between 700 and 1200 K with heating rates of 104 –105 K/s. They concluded
that the ratio of dry ash-free weight-loss to change in the dry ash-free volatile matter by
proximate analysis is greater than one.
Jüntgen and Heek [7] studied ethane release from a finely ground coal (19.1% volume to
mass) as a function of heating rate. Their heating rates were between 102 and 105 K/min.
Menster et al. [8] used electrical pulse heating to apply a heating rate of nearly 104 ◦ C/s
to a number of coals. The total volatile yield from low-rank hVC and hVA coals displayed
a maximum in the temperature region 700–800◦ C. The peak volatile yields exceeded the
volatile matter contents of the coals as determined by the standard ASTM method.
Badzioch and Hawksley [9] carried out experiments on the pyrolysis of 11 British coals
of various ranks in a laminar flow reactor. They studied pyrolysis at temperatures up to
1000◦ C, heating coal particles to decomposition in 30–110 ms at a rate between 25 000
and 50 000◦ C/s. The volatile product yield in rapid heating was 1.3–1.8 times higher than
that found from the difference between the proximate volatile matter of coal and that
of char.
Anthony et al. [10] studied rapid devolatilization of monolayers of lignite and bitumi-
nous coals supported on wire mesh heating elements in helium. They calculated
FREE-FALL REACTORS 607
devolatilization rates by weighing samples before and after experiments of known dura-
tion for different residence times (0.05–20 s), temperatures (400–1100◦ C), heating rates
(102 –104 ◦ C/s), pressures (0.001–100 atm), and particle sizes (50–1000 µm). They ob-
served that the weight loss from either coal was essentially complete within a fraction of
a second, to a few, seconds, depending upon temperature, and increased with increasing
final temperature up to 900–950◦ C. Weight loss (corrected to its value at a fixed tem-
perature) was found to be independent of pressure, heating rate, and particle size, for the
lignite, depending only on temperature and time; for the bituminous coal, it increased
with decreasing pressure, decreasing particle size, and, to a small extent, increasing
heating rate.
Belt and Roder [11] investigated rapid-entrainment carbonization of powdered coal
under pressure in a partial hydrogen atmosphere as a means of producing low-sulphur
char for use as a power-plant fuel. They utilized a 4-inch diameter and 18-inch high
carbonizer. A char containing 0.7% sulphur produced at 1000◦ C, 400 psig, and 91%
hydrogen-in-nitrogen from the 2.55% sulphur-containing parent coal.
Green [12] studied synthetic fuels from coal using the Garrett process. This process
produces high yields of volatile fuels from coal through a novel ‘flash pyrolysis’. The
reactor consists of a ten-foot length of a nominal one-inch pipe. The reactor temperature
is maintained by means of electrical heaters. Pulverized coal is fed into a T-connection
from a screw feeder where it is picked up by a stream of carrier gas and conveyed
through the reactor at high velocity, becoming devolatilized. The hot products first pass
through a series of cyclones to recover the char and volatiles and then are cooled to
separate the liquid products. High-volatile bituminous Kentucky coals were used in an
attempt to determine the optimum pyrolysis temperature for liquid yields in the range
540–650◦ C. The maximum tar yield reached about 40% on moisture-ash-free basis which
is more than twice that obtained in the standard Fischer assay test for this coal. It was
proposed that flash pyrolysis to gasify carbon at the higher temperatures tends to reduce the
hydrogen/carbon ratio in the char, decrease the tar yield, and increase the hydrogen/carbon
ratio in the gas.
Kobayashi et al. [13] studied devolatilization of a lignite and a bituminous coal at high
temperature under rapid heating conditions. Devolatilization rates were measured in a flow
furnace designed to render heating rates of 104 –2 × 105 ◦ C/s (with typical temperatures of
725–1825◦ C and residence times down to a few milliseconds). The volatile yields were
determined by differences in weights of coal fed and char collected, and by use of ash as
a tracer. 0.1–0.3 g of graded coal particles (+400–325 Tyler mesh) in an argon carrier
gas was injected through a 1.2-mm I.D. water-cooled stainless steel tube along the axis of
the furnace into plasma-preheated argon stream, confined by a 50.8-mm I.D. cylindrical
graphite muffle tube. At 1825◦ C both coals yielded 63% volatile which was significantly
greater than the ASTM volatile matter of 46% (m.a.f.).
Ubhayakar et al. [14] studied rapid devolatilization of pulverized coal in hot combustion
gases, varying the input gas temperature between 1525 and 1975◦ C. They used three par-
ticle size distributions for the same type of coal: as received, the fraction which remained
on a 200 mesh screen; and that which passed through the screen. The residence time in
the gasifier was 7–70 × 10−3 s. The tests were conducted at a pressure of 1 atm, heating
rates up to 105 ◦ C/s, and volatile product yield up to 68% of the original dry-ash-free coal.
Nskala et al. [15] studied characteristics of chars produced by pyrolysis following rapid
heating of pulverized coal. They used a furnace 5 cm I.D. to study fast pyrolysis of
size-graded pulverized coal particles. The study was carried out as a function of isother-
mal pyrolysis time (0.018–0.025 s), particle size (50–181 µm), and parent coals (three
lignites). The following experimental conditions were kept constant throughout the inves-
tigation: coal feed rate ∼0.5 g/min; volumetric flow rate of nitrogen (which was used
as the pyrolysis medium) into the pyrolysis furnace 32 L/min; temperature 808◦ C; and
atmospheric pressure. Under these conditions the heating rate of the coal particles in the
pyrolysis furnace was of the order of 8 × 103 ◦ C/s, and they calculated the weight loss
using ash as a tracer. They proposed that: (i) a monotonic change in the physical proper-
ties of chars occurred with increasing pyrolysis time; (ii) there was some dependence of
weight loss (i.e. volume per mass yield) on particle size; (iii) the three lignites underwent
pyrolysis to a comparable extent, presumably because of their similar initial chemical
composition; (iv) there was an appreciable influence of temperature and heating rate on
weight loss in the Parr crucible; and (v) there was a significant influence of the mode
of pyrolysis (i.e. entrained vs fluidized bed) on the nature of the char produced. From a
theoretical treatment of gas–solid interactions they also proposed that all coal particles
smaller than 200 µm diameter were heated from their initial room temperature to the pre-
determined gas temperature of 808◦ C so fast that no appreciable gradient was established
between their surface and their core. They used an empirical equation in conjunction with
experimentally determined kinetic constants to calculate the weight loss in the laminar
flow reactor. They found that: (i) for pyrolysis times ranging up to about 0.2 s, the agree-
ment between experimental and calculated values of weight loss was good; but (ii) for
pyrolysis times greater than 0.2 s, the disagreement between these values became more
pronounced. They suggested that: (i) the pyrolysis furnace can be used effectively for
studying the pyrolysis of size-graded, pulverized, coal particles under essentially isother-
mal conditions; and (ii) it may be most important to examine the resulting chars and
determine changes in physical and chemical properties due to rapid heating because of
the relevance these may have in coal conversion processes.
Torrest and van Meurs [16] studied the rapid pyrolysis and desulphurization of Texas
lignite on a laboratory scale. As a reactor they used a pyrolysis tube 100 cm long and
5 cm diameter. Preheated steam or nitrogen entered the bottom of the tube, with flow rates
and particle sizes chosen so that particle residence times were of the order of seconds.
Particle sizes ranging from 100 to 1000 µm were tested. Most of their work was carried
out on 200–350 and 500 µm beneficiated particles. The heating rate for that size was
1000◦ C/s and the terminal settling velocity was about 100 cm/s. The average velocity of
the steam at 760◦ C was 64 cm/s. They found that rapid heating of lignite particles during
free fall, through a counter-flowing pyrolysis gas, was an effective method of producing
a low sulphur char. For 200 µm particles with residence times of seconds in steam, the
organic sulphur of the lignite was reduced from 1.3 to 0.8% by weight over a temperature
range 700– 800◦ C.
Zanzi et al. [17] studied rapid pyrolysis of biomass, wood and agricultural residues
using a FFR, and concluded that the char reactivity is very strongly influenced by treatment
conditions and may be significantly increased by using high heating rates, small particle
sizes of the fuel and short residence time at higher temperature. A longer residence time
results in the formation of lower reactivity char. This may be seen both in the gasification
tests and in the tests on final char pyrolysis. The char reactivity in steam gasification
increased when residence time decreased.
Char is a main product in hydropyrolysis of coal. It is used in general as feedstock
to steam gasification to produce hydrogen, which is in turn harnessed for hydrogasifica-
tion. Thus char reactivity is an important parameter for the design and development of
a hydropyrolysis process. Xu and Kumagai [18] investigated nitrogen evolution during
rapid hydropyrolysis of coal in a continuous FFR whose length was 1300 mm and diam-
eter 10 mm. They employed three coals in the particle size range 70–90 µm, giving a
residence time of 2 s. The temperature varied from 923 to 1123 K and hydrogen pressure
was up to 5 MPa. The dominant nitrogen gaseous species was ammonia accompanied by
a little HCN because most of the latter was converted to the former through secondary
reactions. They concluded that the evolution of nitrogen in coal is caused mainly by
devolatilization at temperatures below 973 K, while the evolution of the volatile nitrogen
in char is accelerated with increasing temperature and hydrogen pressure. Gas residence
time has a significant effect on product composition. Xu et al. [19] utilized the same FFR
in a similar study raising this pressure to 7 MPa. At a hydrogen pressure of 1 MPa one
of the coals gave 50, 48, 47, and 46% C yield in char respectively at 873, 973, 1073,
and 1123 K. The corresponding C yields in tar were 26, 19, 12, and 9. Thus temperature
has a much more pronounced reduction effect on the tar yield. Tar decomposes at high
temperatures to form methane, ethane, and HC. This indicates the importance of opera-
tion temperature in flash pyrolysis. The authors present a comparison of different works
employing FFR, Curie-point pyrolyser, and rapid heating batch reactors. Both Curie-point
pyrolyser and batch reactors apparently give slightly smaller weight loss than FFR despite
the shorter reaction time in FFR. They suggest that this may be due to the better solid–gas
contact in FFR.
Sugawara et al. [20] harnessed a FFR to study hydropyrolysis in a hydrogen stream
at atmospheric pressure. They rapidly pyrolyzed five noncaking and two caking coals at
temperatures up to 1233 K with a heating rate of 6000 K/s. Both volatile matter yield and
internal surface area of char were measured for several treatment times ranging from 0.1
to 0.4 s. Pyrolysis rate was determined from changes in particle temperature, diameter,
and apparent density. Rapid-hydropyrolysis char was more favourable for gasification
than slow-heating pyrolysis char.
Flash pyrolysis in FFR is a useful means to remove sulphur from coal [19, 21]. As
shown by Li et al. [22], it can also be utilized to remove heteroatom molecules from
biomass. Both the yield and the composition of the resultant gas depend on the biomass
composition. The gas output is richer in hydrogen in the case of cellulose and hemicel-
lulose than in the case of lignin. Smaller biomass particle sizes and higher fast pyrolysis
temperatures also boost hydrogen content. The total of carbon monoxide and hydrogen
content is reported to be 65.4% for legume straw and 55.7% for apricot stone.
3 DESIGN ASPECTS OF FFR TO BE USED IN PYROLYSIS

The literature surveyed above and our own experience [23–27] identify several important
aspects for FFR design to be employed in waste plastic pyrolysis:
1. Depending on the reactor length, there is a threshold for particle size to begin to
influence free fall or reaction time and hence products. The reactor length should
mesh with the size and density of the particles to be processed. This needs to be
investigated with a view to product quality.
2. All possible means, including provision of multiple exit points along the reactor, use of
a carrier gas, and application of vacuum must be considered to facilitate fast removal
of gaseous products from the reaction medium.
3. The kind of reaction medium, i.e. whether it is inert, oxidative, or reductive, deserves
attention because of its substantial effect on the yield and composition of solid, liquid,
and gaseous products.
4. Raw material may need some kind of pretreatment. For example, styrene foam can be
subjected to heat to make it compact before grinding to fine particles.
5. A direct current screw feeder should help to deliver under control the feed at the
precalculated rate. This rate depends on the size and speed of the feeder.
6. It is essential to centralize the feed and keep it away from the reactor walls. Sticking of
particles to the inner surface of the walls turns rapid pyrolysis into fixed-bed pyrolysis.
The growth of the stuck mass leads to blocking of the reactor. Carbonization on walls
is an impediment to drawing a mass balance.
7. Another important point is the attainment of a smooth temperature profile along the
reactor. Multiple heaters may provide this smoothness.
4 A FREE-FALL REACTOR SYSTEM FOR FLASH PYROLYSIS
4.1 SET-UP
Figure 23.1 depicts the current version of the free-fall reactor developed and used in
a series of pyrolysis researches [23–26] at Ateklab, Ankara University, spanning over
Feed unit
Feed unit
+ -
Inert gas
0 1
Power unit
Vacuum
Temperature
Control unit
120 cm
140 cm
5 cm ID
Quartz reactor
Screw feeder
Furnace
Gas collector
Char
collector
GC Vacuum Condensers
Figure 23.1 The FFR set-up

15 years. The inset shows the specially designed feed unit consisting of a 12 V DC motor,
a bladed shaft, and a single-thread screw feeder connected in this order and housed in a
three-piece Pyrex casing which is about 400 mm high. A power unit (not included in the
drawing) precisely regulates the voltage of the DC motor to vary between 0 and 12 V
which in turn fixes the rotational speed of the screw feeder and thereby the (downward)
feed rate, depending on the particle size fraction. The motor is seated in the top piece
Pyrex. The middle Pyrex has a side entrance (not shown) through which to dump a
preweighed lot of raw material. Two extra blades break up and smoothly deliver the lot
to the screw feeder underneath. The bottom Pyrex extends about 50 mm downward from
the feeder’s tip in order to prevent scattering and direct the feed towards the central axis.
A conical funnel situated between the feed unit and the quartz reactor also helps to centre
the feed particles and thus substantially reduce their sticking at the walls.
A high-temperature furnace jackets the reactor which is connected to a char collector
and two water-cooled condensers in series. Each condenser balloon is in a salt–ice bath.
The reactor’s diameter is 50 mm and height 1400 mm, its heated zone being 1200 mm
long. An inert gas (N2 ) entrance is also incorporated to purge oxygen. Experiments are
carried out under vacuum, the suction being at the exit of the condenser bath series.
Vacuum is also connected to the middle Pyrex of the feed unit in order to balance pressure.
The application of vacuum helps to adjust the retention time of the pyrolysis products and
to remove them from the reaction medium, thereby reducing unwanted further reactions.
A possible alternative to achieve these would be the use of a carrier gas, as mentioned
above. This is not opted for here because of its undesirable dilution of the products.
Two Ni–CrNi thermocouples measure the reactor temperature at 400 and 800 mm from
the top, the upper thermocouple being harnessed for the temperature control by a personal
computer.
Free fall time through the reactor is an important factor influencing the reaction extent.
The reactor length must match the particle size range to render a suitable retention
time. This is exemplified by an Ateklab investigation as follows. Raw material particles
(LDPE) were separated by ISO 3310-1 standard sieves into (three) size ranges, namely
150–212 µm, 75–150 µm, and >75 µm diameter. After calibration for each of these
ranges, the voltage of the DC motor driving the feeder was appropriately set to render an
approximate feed rate of 2 g/min.
4.2 EXPERIMENTAL PROCEDURE
The feed unit is dismounted, charged with a weighed amount of feed particles in the
selected size range, and remounted after heating the reactor to the preset temperature with
a stopcock in its place. Oxygen is purged out of the system by nitrogen. The vacuum
pump is operated until a preset reduced total pressure. The motor of the feeder is started.
The reaction causes the pressure to rise. The vacuum connection is shut off and the system
is allowed to cool when the feed is completely exhausted. The temperature varied along
the reactor’s heated zone as depicted in Figure 23.2.
The gases from the vacuum pump are either directed to a gas chromatograph (GC)
through an automatic injection valve whose inside loop was 0.250 mL or discharged to
gas collection burettes. The GC is a Varian 3400 with a flame ionization detector (FID)
1000
900
800
700
Temperature, °C 600
500
400
300
200
100
0
0 20 40 60 80 100 120
Distance from the reactor base, cm
Figure 23.2 A typical temperature profile of the reactor
and a Porapac Q column. It is employed to analyse both the vacuum pump effluent and
the gas in the collection burettes. The results are averaged for each run. The liquid product
is analysed harnessing a HP5890 Plus GC/MS with an OV-101 column.
The residue in the char collector and the liquid total in the condenser balloons were,
respectively, taken to be the solid and the liquid yields based on the feeder charge. The
gas yield was then found by taking the difference. The sum of the gas and liquid yield
was defined as the total conversion.
5 PLASTIC WASTE RECYCLING
Plastic wastes are generated in Europe at the rate of 15 million tons per annum [28]. Their
minimization and recycling are encouraged [28] and legislated [29–30] for economic and
ecological reasons. Recycling also serves to conserve natural resources. This is indicated
for example by the statement [31] that each ton of polyethylene (PE) and polyvinyl
chloride (PVC) respectively requires for its production 18.7 and 8 tons of crude oil.
The 1973 petroleum crisis intensified research on coal liquefaction and conversion pro-
cesses. The technology developed in this field was later harnessed in chemical recycling
of plastics. Mastral et al. [32], for example, employed two different batch reaction sys-
tems (tubing bomb reactors and magnetically stirred autoclave) and a continuous reactor
(swept fixed bed reactor). Chemical recycling techniques such as pyrolysis [28, 33–38]
or coliquefaction with coal [39, 40] convert plastic wastes into hydrocarbons that are
valuable industrial raw materials.
Generally included in the chemical recycling literature are details such as the plastic
waste treated [41], the reactor type [28, 36, 42], the catalyst [33, 35, 43], the operation
and its conditions [28, 36, 42], the product constituents [28, 33, 44, 45], the liquid and
gas yields and the solid residue [28, 42–44] and kinetics [45, 46]. The most frequently
employed type of reactor in polymer pyrolysis is the fluidized bed, despite its inherent
disadvantages that a fraction of the products is lost to the inert stream and that substantial
extra heat is necessary for the fresh and/or recycled inert gas feed which has to be cooled
on exit so as to separate the condensable products.
PE is the overwhelming majority of post-consumer plastic wastes resulting from agri-
culture, automotive, construction, distribution and domestic use. Polypropylene (PP),
polystyrene (PS), PVC and polyethylene terephthalate (PET) are the other significant com-
ponents. Many workers have studied PE pyrolysis. Scott et al. [33] operated a fluidized-
bed reactor at atmospheric pressure, with difficulty in the calculation of product phase
yields. The situation improved at higher temperatures. At 725◦ C about 12% of the feed
was unaccounted for, the gas yield reaching 42.2% whose ethylene content was 19.3%.
In another flash pyrolysis research on PE Williams and Williams [28] also harnessed a
fluidized bed. They obtained 10.8% gas, 43.9% oil, and 45.3% wax at 500◦ C, and 71.4,
24.6, and 4.0% respectively at 700◦ C. The number average molecular weight of the wax
was 494 at 500◦ C. Moreover, the analysis of the combined wax and oil output at this
temperature showed mainly aliphatic hydrocarbons in the range C18 –C57 with a mean
around C33 . The monomer content of the gas was 2.19% at 500◦ C and 26.86% at 700◦ C.
Milne et al. [42] used an internally circulating fluidized bed to study pyrolysis of low-
density PE (LDPE) at temperatures ranging from 780 to 860◦ C and residence times of
400–600 ms. They achieved gas yields in excess of 90 wt% with total alkene yields as
high as 75 wt%, demonstrating a waste treatment potential for processes such as flash
pyrolysis, distinguished from classical pyrolysis by its high heating rates and low retention
times, where these conditions can be maintained.
LDPE was catalytically depolymerized in solution in an autoclave by Scott et al. [47]
who observed, as expected, that increasing the temperature or decreasing the reaction time
resulted in higher liquid yield. At a plastic waste:catalyst ratio of 20:1 and a maximum
temperature of 420◦ C, they reported 52.6% liquid and 47.4% gas yield. The majority of
the gas was C3 and C4 , the monomer being about 5%.
Polystyrene was flash pyrolyzed in a free-fall reactor under vacuum [49, 50] giving
yields at the level of fluidized-bed figures [33, 51]. Also investigated [49] was flash vac-
uum pyrolysis of LDPE whose results are now presented here in this manuscript with an
additional experiment using the same system.
6 RESULTS FROM ATEKLAB FREE-FALL REACTOR
6.1 LDPE RESULTS
Additive-free granular LDPE was PETKİM Commercial Code Number F12, obtained
from PETKİM Petrochemical in Aliaĝa, Turkey. The particles were separated by ISO
3310-1 standard sieves into three size ranges, namely 150–212 µm, 75–150 µm, and
less than 75 µm diameter. After calibration for each of these ranges, the voltage of the
DC motor driving the feeder was appropriately set to render an approximate feed rate
of 2 g/min.
The first set of experiments used LDPE particles in the 150–75 µm size range and
varied the reactor temperature between 750 and 875◦ C. As seen in Figure 23.3, both
100
Solid residue
Liquid
80 Gasous matter
Total
60
Yield, %
40
20
0
750 775 800 825 850 875 900
Temperature, °C
Figure 23.3 Temperature effects on product phase yields for the feed size range
150–75 µm. (Copyright 2003 from Polymer-Plastics Technology and Engineering by
A Karaduman, M. C. Kocak and A. Y. Bilgesu. Reproduced by permission of Taylor &
Francis, Inc., http://www.taylorandfrancis.com)
Table 23.1 Temperature effects on gaseous output

composition (feed size 150–75 µm). (Copyright 2003
from Polymer-Plastics Technology and Engineering
by A Karaduman, M. C. Kocak and A. Y. Bilgesu.
Reproduced by permission of Taylor & Francis, Inc.,
http://www.taylorandfrancis.com)
Gas products (%) Temperature (◦ C)

750 850 875
Methane 11.09 19.92 21.84
C2 67.20 66.29 64.28
C3 1.10 4.92 8.58
C4 20.61 8.87 5.30
the liquid and the gas yield (i.e. wt% of feed) rise monotonically with temperature at the
expense of the (unwanted) solid residue, the total conversion gain reaching about 43%. The
gas yield alone changes from 22 to 37%. The overwhelming majority (over 99%) of the
gaseous product is C1 –C4 . Table 23.1 indicates that high temperature reactions involv-
ing C4 (mainly butene) and C2 (mainly ethylene) almost double the methane fraction,
accompanied by an increase in propene. Milne et al. [42] reported a similar temperature
effect for an internally circulating fluidized-bed reactor. Williams and Williams [28] also
harnessed a fluidized bed at lower temperatures (700◦ C maximum) and observed a similar
trend with some fluctuation in butene fraction.
The substantial increase (more than 50%) in the gas yield more than compensates for
the slight drop (from 67.2 to 64.3%) in its ethylene monomer content. Thus operation at
higher temperatures is desirable. This work is eminently superior in respect of ethylene
yield; the highest literature value given in Milne et al. [42] is about 33%. Fluidized bed
rendered 2.19–26.86% [28], circulating fluidized bed 27–37% [42], autoclave 5% [47]
and steam cracker fluidized bed 8.1–30% [44].
The gas chromatogram of the liquid product at 875◦ C is depicted in Figure 23.4. The
bulk of the liquid product is paraffinic. Derived from Figure 23.4, Figure 23.5 shows that
96% of the liquid product is below C40 while over 55% of it is C12 –C20 . As is known
C12 –C20 hydrocarbons are essential raw materials for the production of fatty acids, fatty
alcohols and detergents. In contrast, the liquid output of Williams and Williams [28], as
mentioned above, comprised alkadienes, alkenes, and alkanes in the range C11 –C57 with
a mean of C33 at 700◦ C. They observed that, at higher pyrolysis temperatures, the total
concentration of aliphatic species above about C30 was greatly reduced. This is further
evidence that the temperatures employed in the present work are appropriate for LDPE
pyrolysis.
Kiran et al. [48] pyrolyzed PE in a fixed-bed reactor (Gray–King apparatus) obtaining
a gaseous mixture and a green wax whose melting point was about 80◦ C. (This wax
apparently plugged their product lines and condenser tubes.) They heated PE samples
up to 600◦ C at the rate of 5◦ C/min despite the TGA indication that degradation finished
between 440 and 475◦ C. The batch time was about 4 h. In comparison, the present work
is a continuous process whereby approximately half of the LDPE waste is converted to
liquid and gaseous products within seconds, albeit at about 875◦ C.
As portrayed in Figure 23.6, at 875◦ C, increase in particle size adversely influences the
liquid and gas yields and hence the total conversion. In going from <75 to 212–150 µm
2.00 4.00 6.00 8.00 10.00

Time, min
Figure 23.4 The GC/MS analysis of the liquid products at 875◦ C for the feed size range
150–75 µm
70
60 56.64, %
50
Weight, %
40
30
21.97, %
20 15.54, %
10
4.35, %
1.5, %
0
< 12 12-20 21-30 31-40 41<
Carbon Number
Figure 23.5 The carbon number distribution of the liquid product
70
60
50
40
Conversion, %
30 Solid residue
Liquid
20 Gaseous matter
Total conversion
10
0
75-receiver 150-75 212-150
Particle size, micrometer
Figure 23.6 The effect of the feed size on the product phase yields at 875◦ C. (Copy-
right 2003 from Polymer-Plastics Technology and Engineering by A Karaduman, M.
C. Kocak and A. Y. Bilgesu. Reproduced by permission of Taylor & Francis, Inc.,
http://www.taylorandfrancis.com)
range, they respectively change from 8 to 4%, from 47 to 34%, and from 55 to 38%.
Thus the smaller the particles size the better.
The free-fall reactor operating under vacuum has the added advantage over both the
sweeping fixed bed and fluidized-bed reactor types that it does not dilute the gaseous
products with an inert.
It is interesting to compare flash vacuum pyrolysis of LDPE and PS in a free-fall
reactor. Temperature rise causes the solid residues to fall and the liquid and gas yields to
increase. The LDPE figures exceed the corresponding PS values in the case of the solid
residue and gas yield by about 50 and 10% respectively. In contrast, the liquid yield of
LDPE is about one-fifth of PS. These findings are in harmony with the activation energies:
270–331 kJ/mol for LDPE and 126–151 kJ/mol for PS [34].
The most common reactors in polymer pyrolysis are fluidized-bed types, which inher-
ently have the disadvantages that a fraction of the products is lost to the inert stream and
that substantial extra heat is necessary for the fresh and/or recycle inert gas feed which
has to be cooled on exit so as to separate the condensable products. Free-fall reactors are
of course without these disadvantages. This waste treatment study has shown furthermore
that flash pyrolysis of low-density polyethylene (LDPE) in a free-fall reactor under vac-
uum is a promising continuous recycling technique superior to other techniques as regards
product quality. The solid, liquid, and gas yield are respectively 60, 4, and 36% at 875◦ C
when the feed is 150–75 µm LDPE particles. The overwhelming majority (over 99%) of
the gaseous product is C1 –C4 . Over 64% of this is the ethylene monomer. The bulk of the
liquid product is paraffinic; 96% of it is below C40 while over 55% of it is C12 –C20 . As is
known, C12 –C20 hydrocarbons are essential raw materials for the production of fatty acids,
fatty alcohols and detergents. Reduction in operation temperature, down to 750◦ C causes
the total conversion (i.e. the sum of liquid and gas yield) to fall from 40 to 25%. This is
accompanied by a slight increase (from about 64 to 67%) in the ethylene monomer yield.
Thus higher temperatures should be preferred. On the other hand, lowering the particle
size down to <75 µm favourably influences the total conversion raising it by about 20%.
6.1 POLYSTYRENE RESULTS
Plastic wastes may be the remains of production or post-consumer wastes, the latter
being classified as municipal, packaging, agricultural, automotive and electrical. Packaging
wastes are the major category [33, 52–54]. These are mainly thermoplastics such as
polyethylene, polypropylene, polystyrene and polyvinyl chloride [28, 33, 55–56].
Plastic waste minimization and recycling are encouraged [28] and even legislated [30,
57–58] for both economic and environmental reasons. Using properly labelled plastics
aids separation of mixed wastes prior to recycling either immediately or after remoulding
or a chemical treatment, e.g. pyrolysis, rendering various products which may include
monomers. Chemical recycling of plastics is an important and challenging task and has
led to intensive research. Generally included in the relevant literature are details such as
the plastic waste treated [35, 59], the reactor type [33, 36, 42, 51], the catalyst [35], the
operation [41] and its conditions [41], the product constituents [33, 51, 60], and phase
yields [33, 60]. Information on kinetic and process parameters are scarce, however.
Highly reactive radicals form in pyrolysis due to bond scission. These decompose or
react with each other or the polymer giving gaseous, liquid, and solid products [61]. Flash
pyrolysis is distinguished from the classical slow pyrolysis by its relatively higher heating
rate and lower retention time [23–24]. As in other kinds of thermal degradation, other
products such as benzene, toluene, ethyl benzene, and naphthalene accrue in polystyrene
pyrolysis when the primaries, namely styrene and its oligomers, are not immediately
removed from the reaction medium. Liu et al. [51] detected a wider variety of products.
In a study by Sato et al. [62], the primaries dissolved in the melted PS or the solvent
where the low mass transfer rate lead to significant secondary products. Ohtani et al. [61]
avoided secondary products by employing helium carrier. They reported monomer, dimer,
and trimer of styrene. Flash pyrolysis of PS in a fluidized bed under atmospheric conditions
rendered liquid products, mainly containing styrene monomer, toluene, ethyl benzene, and
naphthalene [33].
In this study [25], waste polystyrene was flash pyrolyzed in a free-fall reactor under
vacuum with the aim to assess the effects of both the operating temperature and the feed
particle size on the kinds and relative distributions of products.
While falling in the reactor due to gravity, polymer particles degraded into smaller
molecules in a series of reactions, including bond scission. Investigated in this study were
the effects of the waste particle size fed and the operating temperature on the type and
extent of these reactions. Two sets experiments were carried out. One set employed the
150–75 µm size range at different temperatures, namely 700, 750, 775, 800, 825, and
875◦ C. The other set harnessed all of the four size ranges mentioned above at 825◦ C.
Figure 23.7 indicates the temperature effects on the yields in the first set of runs. The
gas yield increased throughout the temperature range studied. Up to about 750◦ C, the
operating temperature increase rapidly lowered the solid yield and raised both the liquid
yield and the total conversion. Beyond this point, the solid yield continued to decrease,
but at a highly diminished rate. The liquid yield, on the other hand, began to fall slowly.
This may be due to partial decomposition of the expected product styrene. At 750◦ C the
solid, liquid, and gas yields were 47, 32, and 21%, respectively.
The GC analysis results of the liquid product (Figure 23.8) were focused on styrene,
benzene, toluene, and naphthalene components, the often quoted compounds in polystyrene
degradation [33, 51, 62–64,]. The run at 750◦ C showed 48% benzene, 18% styrene, 8%
toluene. The benzene content decreased steadily with increasing operating temperature,
100
Solid residue
Liquid yield
80 Gas yield
Total conversion
60
Yield, %
40
20
0
700 750 775 800 825 875
Temperature, °C
Figure 23.7 The temperature effects on product phase yields of PS. (Reproduced from
Journal of Analytical and Applied Pyrolysis, 60 (2), A. Karaduman, Flash pyrolysis of
polystyrene wastes in a free-fall reactor under vacuum, 179–186 (2001), with permission
from Elsevier)
60
Benzene
Toluene
50 Styrene
Naphthalene
Concentration, %
40
30
20
10
0
750 775 800 825 850 875 900
Temperature, °C
Figure 23.8 The temperature effect on liquid product composition. (Reproduced from
Journal of Analytical and Applied Pyrolysis, 60 (2), A. Karaduman, Flash pyrolysis of
from Elsevier)
vanishing at 875◦ C. Toluene rose initially up to 18%, began to fall at 825◦ C disappearing
at 875◦ C. The styrene curve resembles in shape that of toluene, reaching a maximum of
34% at 825◦ C and declining to 30% at 875◦ C. While negligible at lower temperatures, a
little (about 1%) naphthalene appeared at this final temperature.
The C1 –C4 contents of the gas products are shown in Figure 23.9 for various operat-
ing temperatures, disregarding H2 which the FID detector is known to miss. Apparently
generated were about 21–28% methane, 60–70% C2, 5% C3 , and 4% C4 .
How the waste feed particle size influenced the yields were investigated in runs at
825◦ C, the temperature giving the maximum styrene yield in the first set of experiments.
As depicted in Figure 23.10, the coarsest size (300–212 µm) rendered respectively 42%
solid, 29% liquid, and 29% gas yields. As the particles became finer the solid yield
diminished steadily to about 34% at less than 75 µm. In contrast the gas yield increased
monotonically to 38%. The liquid yield seemed little affected by the feed particle size.
The total conversion rose from 58 to 66% because of its gas contribution.
In polystyrene degradation, it is desired to maximize the styrene monomer output and
hence the liquid yield. The rather low figures of this study were probably related to
residence time problems. The generated species and the high gas yield indicate that the
primary products decomposed significantly because they remained too long in the reactor.
The pressure rise observed after the reaction start certainly reduced the suction and slowed
down their removal which may be substantially improved by a continuous N2 stream
throughout the run and/or exploiting a reactor with intermediary exits. In view of the
second set of experiments, employment of finer waste feed is advisable since this reduced
the solid yield and boosted the total conversion, possibly by increasing the polystyrene
residence and hence degradation time as reported in two other free-fall reactor studies [23,
24]. Another alternative is to harness a reactor with a longer heated zone.
80
70
60
C1
Mole fraction, %
50 C2
C3
40 C4
30
20
10
0
800 825 850 875
Temperature, °C
Figure 23.9 The temperature effect on C1 –C4 contents of the gas products. (Reproduced
from Journal of Analytical and Applied Pyrolysis, 60 (2), A. Karaduman, Flash pyrolysis of
from Elsevier)
70
60
Solid residue
Liquid yield
50
Yeild, %
Gas yield
Total conversion
40
30
20
75-reciever 150-75 212-150 300-212
Particle size, micrometer
Figure 23.10 The effect of PS particle size on phase yields. (Reproduced from Journal
of Analytical and Applied Pyrolysis, 60 (2), A. Karaduman, Flash pyrolysis of polystyrene
wastes in a free-fall reactor under vacuum, 179–186 (2001), with permission from
Elsevier)
GPC analysis of the solid products is needed to elucidate whether or not they contain
partially degraded styrene oligomers.
This study showed that polystyrene pyrolysis in a free-fall reactor under vacuum is
a promising technique to obtain important liquid chemicals such as benzene, toluene,
and naphthalene besides styrene monomer and valuable gaseous output. The liquid yield
maximized around 750◦ C and the styrene yield at 825◦ C. In general, the higher the
operating temperature the lower the solid yield and the higher the gaseous yield and
the total conversion. The latter two were also helped by lowering the particle size of
the waste feed. Connecting the rather low liquid and styrene yields to residence time
problems, suggestions are suggested for improvement and for future work.
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PART V
Monomer Recovery
24
Monomer Recovery of Plastic

Waste in a Fluidized Bed Process
WALTER KAMINSKY
Institute for Technical and Macromolecular Chemistry, University of Hamburg,
Bundesstr. 45, 20146 Hamburg, Germany
1 INTRODUCTION
The pyrolysis of poly(methylmethacrylate) (PMMA) waste is one of the few technical
processes for feedstock recycling of plastics which has been working economically for
the last 30 years [1]. The reason for this is the relatively high price of PMMA compared
with standard plastics and the possibility to recover up to 95% of the monomer methyl-
methacrylate (MMA) [2–4]. Feedstock recycling of polyolefins, for example, produces
a component-rich mixture of gas and oil and only if the price for crude oil is high, is
the economy of such processes viable [5–12]. Other plastics which can be pyrolyzed to
high yields of the monomers are polystyrene (PS), polytetrafluoroethylene (PTFE), and
polyethyleneterephthalate (PET) [13–17]. The amounts of the monomers with these poly-
mers as feedstock are smaller than using PMMA. If PMMA is heated to a temperature
of more than 400◦ C, it will decompose almost completely into the monomer [18].
For the depolymerization of PMMA, molten metal bath, dry distillation, extruder pro-
cesses and fluidized-bed processes are used [19]. The depolymerization reactor of a molten
metal bath consists essentially of a gas- or oil-heated metal bath. The metals used are
those which have a low melting point such as tin and lead. The PMMA regrind is fed
from the storage silos onto the stirred metal bath. Bath temperature and a residence time
of some minutes are important for good yield and quality of the MMA.
In contrast to this, the residence time of the products in a fluidized bed lies between
1 and 5 s [20]. Buekens [21] studied the influence of the residence times in technical
fluidized-bed processes. One of the main advantages in using a fluidized bed reactor for
depolymerization is that it involves no contamination of organometallic compounds in
the products and less environmental problems [1]. Therefore, companies are looking to
use fluidized-bed processes especially for filled PMMA. The filler will contaminate the
molten metal bath while in a fluidized bed the often expensive fillers can be recovered.
628 W. KAMINSKY
Today, PMMA is mainly filled by silica, quartz, aluminium hydroxide and other inorganic
fillers. For special uses, the polymer is cross-linked. This, together with the high molecular
weight, makes regeneration as a raw material in reprocessing impossible. The feedstock
recycling by pyrolysis to recover the monomer is therefore a practical way.
2 FLUIDIZED-BED PROCESS
The experiments for the pyrolysis of PMMA, PS, and PTFE were carried out in a lab-
oratory plant with throughputs of 300 g h−1 to 3 kg h−1 using the Hamburg process of
an indirect heated fluidized-bed reactor. Figure 24.1 shows the scheme of the laboratory
plant [22]. The fluidized bed with a diameter (Figure 24.1) of 154 mm and a length of
770 mm, consisting of fine quartz sand with a particle size of 0.3–0.5 mm is heated
indirectly from outside by electricity. The gas distributor is a steel plate with 108 tubes
(3.2 × 0.75 mm) which were moulded into hooks, thus ensuring that no sand could fall
through the plate. Nitrogen was used as a fluidizing medium, but during the experiments
it was slowly displaced by gaseous PMMA products. An auxiliary gas stream was led
through the feeding system to prevent hot gases and sand from entering the input system.
The feeding system consists of two conveyors, the first for a constant feed rate and the
Water
PIR TIR
5003 5007 Ethanol
Storage TIR
Cyclone
PIR TIR
5006 5004 5009
vessel
TIR
5005
PIR
5002 TIR
Electrostatic
5008 precipitator
Reactor
TIR
5004 TIR PIR
TIR 5010 5005
5003
TIR
5002
PIR PI
5001 5001
TIR
5001
PI
FQI 5006
WG TIR
Compressor PIR
5006
5011
Fluidized FQI
gas meter PIR TIR ÜG
Overflow 5007 5012
vessel
Flare
Exhaust gas meter
Vacuum pump
Nitrogen
Gas samples
Figure 24.1 Scheme of a fluidized bed process for feedstock recycling of plastics
MONOMER RECOVERY IN A FLUIDIZED-BED PROCESS 629
second for a quick transport into the reactor. In case of filled polymers an overflow vessel
is used. The products left the reactor and passed a combined cooling and condensation
unit. Fillers and fine sand were precipitated in a cyclone. The gas was cleaned up in an
electrostatic precipitator. By a membrane compressor, part of the gas is cycled and used
as fluidizing gas for the bed reactor. The oil product is collected below the coolers.
In all experiments, gases, liquids, water fraction as well as solid residue were obtained
as products and analyzed on different capillary GC columns and registered with TCD-
and FID-detectors. The reactor sand used and the fillers in the overflow and cyclone were
combusted in a furnace at 810◦ C to constant weight. The loss in weight was balanced as
carbon black.
Elementary analysis of the feed materials was made with a Carlo Erba Strumentazione
CE 1106 CHNS-O. Gases were analyzed with GC-TCD (Chrompack CP 9001; Carboplot
P7) and GC-FID (Chrompack CP 9002; Chrompack Al2 O3 /KCl Plot-capillary column).
Correlation was based on the methane peak.
After oil distillation, three fractions were obtained. Water and organic fractions were
analyzed quantitatively with GC-FID (HP 5890; Macherey & Nagel SE-52). Qualitative
analysis of the organic fraction took place by GC-MS (HP 5890; Macherey & Nagel SE-
52; Fisons Instrument VG 70 SE). Water was determined by the method of Karl Fischer
(Methrom Karl-Fischer-Titrierautomat E547). The third fraction contained high boiling
(fluorine cut: bp>295◦ C) and inorganic components. Like the other solid products it was
heated at 815◦ C to constant weight to determine the organic part. All results of the analysis
of the organic product fraction were combined to give a total mass balance.
3 PYROLYSIS OF PMMA
3.1 PURE PMMA
The PMMA pellets were milled to a size of 0.5–1.5 mm. Table 24.1 shows the results of
three runs in the fluidized bed with new material, one with tinted product from automobile
rear lights.
Raising the temperature increases the amount of gas. At temperatures beyond 550◦ C,
the gas fraction increases rapidly, reaching 42 wt% at 590◦ C. The gas consists of methane,
ethene, propene, carbon monoxide and carbon dioxide (Table 24.2).
Only small amounts of carbon black are formed. The main component in the liquid
is methylmethacrylate (MMA). At a pyrolysis temperature of 450◦ C it is 98.6%, and at
490◦ C it is 98.3% pure. Even coloured waste PMMA materials such as rear lights gave
Table 24.1 Pyrolysis of polymethylmethacrylate in a fluidized bed

(products in wt%)
Pure pellets Waste

◦ ◦ ◦
450 C 490 C 590 C 490◦ C
Gas 0.37 2.63 42.46 7.36
Liquid 98.48 97.08 57.27 92.13
(MMA) (97.16) (95.48) (54.88) (90.99)
Carbon black 0.15 0.29 0.27 0.51
630 W. KAMINSKY
Table 24.2 Gas products of the pyrolysis of PMMA in
a fluidized bed: dependence on temperature (components
in wt%)
Temperature 450◦ C 490◦ C 590◦ C

Hydrogen 0.47 0.30 0.021
Methane 11.8 10.3 9.2
Ethene 4.7 4.4 5.87
Ethane 3.4 2.6 1.6
Propene 1.3 6.8 16.3
Propane 0.78 1.3 1.9
Propadiene 0.009 0.02 0.09
Propyne 0.014 0.05 0.24
Dimethylether 0.024 0.031
iso-Butane 0.009 0.075 0.088
iso-Butene 0.21 1.85 4.9
1,3-Butadiene 0.19 0.10 0.15
trans-2-Butene 0.05 0.18 0.34
cis-2-Butene 0.03 0.11 0.24
2-Pentene 0.05 0.10 0.46
Carbon dioxide 75.8 55.0 20.4
Carbon monoxide 0.78 14.3 31.9
a really clean monomer with 98.6 wt%. The liquid contains small amounts of methyl
isobutyrate (MA), methylacrylate (MA), 1,4-cyclohexane dicarboxylic acid dimethyl ester
(dimeric MMA), and methanol (MeOH) as side products. The concentration increases with
increasing temperature, but these concentrations are still so low that the liquid could be
polymerized to new PMMA after distillation without any further purification. The polymer
is totally colourless.
The detailed pyrolysis products are listed in Table 24.3. The influence of temperature
on MMA is small between 450 and 500◦ C, but is drastically increased in the temperature
range 500–600◦ C. The MMA concentration decreases from 97 to 54%.
At the same time there is an increase of carbon dioxide, carbon monoxide, methane,
propene, and other gaseous components. The low-boiling components are carbon oxides
and hydrocarbon while the higher-boiling components are esters. Mechanistically, the
pyrolytic conversion of PMMA to its monomer is a radical process [24]. Two radicals are
formed by the action of heat of the polymer chain (Scheme 24.1).
H CH3 H CH3
R C C R' R C C· + · R'
H COOCH3 H COOCH3
H CH3 H CH3 H CH3

Rn C C° C C + Rn−1 C C·
H COOCH3 H COOCH3 H COOCH3
Scheme 24.1
Table 24.3 Products of PMMA pyrolysis at different temperatures (components in wt%)
Pure pellets Waste

◦ ◦ ◦
450 C 490 C 590 C 490◦ C
Carbon monoxide 0.01 0.38 13.55 1.05
Carbon dioxide 1.04 1.45 8.67 4.05
Methane 0.16 0.27 3.91 0.76
Ethene 0.064 0.12 2.49 0.33
Ethane 0.047 0.71 0.71 0.20
Propene 0.018 0.18 6.95 0.51
Propane 0.011 0.36 0.82 0.10
Propadiene <0.001 <0.001 0.038 0.002
Propyne <0.001 0.001 0.102 0.004
iso-Butene 0.019 0.087 2.10 0.142
1,3-Butadiene 0.003 0.003 0.064 0.007
Butene 0.033 0.068 0.29 0.045
Pentene 0.011 0.031 0.33 0.022
Pentadiene 0.007 0.02 0.063 0.009
Cyclopentene 0.001 0.007 0.053 0.001
Methanol 0.03 0.07 0.06 0.05
Methyl propionate 0.01 0.02 0.03 0.02
Methyl isobutyrate 0.11 0.13 0.31 0.12
Methyl acrylate 0.28 0.33 1.25 0.22
Methyl methacrylate 97.16 95.47 54.88 90.98
3-Methyl-2-butenoic acid methyl ester 0.01 0.03 0.05 0.03
2-Methylene butanoic acid methyl ester 0.03 0.06 0.05 0.07
2-Pentenoic acid methyl ester 0.01 0.06 0.10 0.08
3-Methyl-3-pentenoic acid methyl ester 0.01 0.03 0.05 0.03
1,4-Cyclohexane dicer-boxylic acid dimethyl ester 0.14 0.25 0.29 0.14
Carbon black 0.15 0.29 0.27 0.51
Each of the radicals is then degraded by the repeated elimination of monomeric units.
The activation energy of the depolymerization was found to be 105 J/mol at 400◦ C. The
excellent heat transfer in a fluidized bed, the low residence time of the monomers, and
the low temperature gradient in the bed explain why so few side products and so little
carbon black is formed. After distillation the recovered liquid can be polymerized to new
PMMA without any other purification.
3.2 FILLED PMMA

Three different filled PMMA were used. One contains 62 wt% of silica (SiO2 , 10–100 µm),
the other 71 wt% of granite (100–1000 µm) and the third contains 67% of aluminium trihy-
droxide (Al(OH)3 , ATH). For the pyrolysis, the laboratory-scale fluidized plant (Figure 25.1)
was used and for two runs the pilot plant with a capacity of 10–50 kg/h feeding rate (Ham-
burg Process)
Silica- and ATH-filled PMMA is an often-used material, for example in bathrooms
and kitchens. ATH-filled PMMA is less flammable because the ATH produces water at
high temperatures which kills the flame. The question was whether such highly filled
PMMA gives similar amounts of MMA and if there is a catalytic effect of the ATH on
the pyrolysis process.
632 W. KAMINSKY
The parameters of the pyrolysis experiments are shown in Table 24.4. In the exper-
iments, the pyrolysis temperature was 450◦ C which was found in previous experiment
with pure PMMA to be the optimal temperature. Total mass balances are calculated to the
organic content even for the filled PMMA to allow a comparison. The losses (1–2%) cal-
culated to 100% were determined on all product fractions proportionately. The following
results should be noted.
The monomer recovery is the highest by feeding pure PMMA pellets (98.4 wt%) in the
laboratory plant. But highly filled PMMA yielded monomer concentrations of 83–90 wt%.
A short residence time is preferred. The good results of the laboratory-scale experiments
were confirmed by the experiments in the technical-scale plant yielding 97% MMA for
pure PMMA pellets and 83.5% for silica-filled PMMA.
In all experiments the gas fraction is small. Only 0.4–4.9 wt% of gas molecules are
produced. Other ligand compounds were found in a range of 1–95%; filled PMMA affords
the higher amounts of oily compounds. In the case of ATH-filled PMMA water is formed
as a main product by drying
2Al(OH)3 → Al2 O3 + 3H2 O.
Up to 4.3% of water was found on feeding silica-filled PMMA, mostly deriving from
hygroscopic PMMA. For unfilled PMMA in the laboratory plant the carbon black forma-
tion is very low (0.01%). This value increased to 1.3% for filled PMMA as feedstock.
Fillers and cross-linking in the PMMA increased the amount of gas, other liquids
and carbon black significantly. More detailed information on the product composition is
shown in Tables 24.5 and 24.6 in the composition of gas and liquid fractions. The main
components in the gas fraction are hydrogen, CO, CO2 , and methane. They are degradation
products from PMMA and MMA. All other products appear in low concentration and
increase with the pyrolysis temperature and by fillers.
Table 24.4 Process conditions and product fractions for the pyrolysis of filled and pure PMMA
in laboratory and mini pilot plants of fluidized beds at 450◦ C
Plant Lab Lab Lab Lab Pilot Pilot

Fillers (wt%) 71 SiO2 62 SiO2 67 ATH 71 SiO2
Throughput (kg/h) 2.0 1.9 0.9 3 34 16
Feed (kg) 5.8 2.8 4.2 12 389 575
Reaction time (h) 2.9 1 1.5 4 11.5 37
Sand in reactor (kg) 8 8 8 9 200 160
Gas flow (m3 /h) 3.9 5.2 3.4 3.9 50 65
Residence time in fluidized bed (s) 1.2 1.0 1.3 1.4 2.9 1.6
Products (wt% of the organic input):
Gas 2.6 2.0 0.4 4.9 1.6 0.5

MMA 86.6 90.5 98.4 57.9 83.5 96.7
Other liquids 8.1 5.7 0.8 35.2 9.4 1.6
Water 1.4 0.6 0.4 (24) 4.3 0.8
Fillers (71) (62) (44) (71) 0.3
Carbon black 1.3 1.2 0.01 0.01 1.2 0.1
Table 24.5 Product gases of the pyrolysis of pure and filled poly(methacrylate) (PMMA) (vol%
in relation to the organic input; + = traces) a 450◦ C pyrolysis temperature

Hydrogen 4.1 7.7 15 7.6 12 9.6
Carbon monoxide 23 27 27 25.5 22 28
Carbon dioxide 54 45 36 52.4 43 33
Methane 11 11 17 7.4 11 18
Ethane 0.6 0.6 0.2 0.4 1.0 1.6
Ethene 1.8 1.8 0.6 2.1 4.0 2.3
Propane 0.3 0.2 0.1 0.5 0.6 0.9
Propene 3.3 3.8 1.6 2.3 4.2 3.3
iso-Butane 0.04 0.04 + 0.2 0.05 0.02
n-Butane 0.03 0.04 0.01 0.2 0.04 0.03
trans-2-Butene 0.1 0.2 0.1 0.3 0.2 0.2
1-Butene 0.2 0.6 0.4 0.3 0.3 0.7
iso-Butene 1.2 1.4 0.4 0.2 1.4 0.9
cis-2-Butene 0.1 0.2 0.1 0.2 0.1 0.1
1,3-Butadiene 0.02 0.1 + 0.2 0.05 0.03
1-Pentene + 0.04 0.01 0.1 0.03 0.02
Other compounds 0.3 0.3 1.5 0.6 0.1 1.3
Table 24.6 Liquids of the pyrolysis of pure and filled poly (methylmethacrylate) (PMMA) (wt%
in relation to the organic input; + = traces, − = not detectable, temperature 450◦ C)

Dimethylether 0.02 0.03 − − 0.03 −
Methanol 0.01 0.01 0.2 8.4 0.02 0.01
Acetone + + + 1.3 0.5 +
Methylacrylate 0.1 0.2 + 1.0 0.2 0.03
Methylpropionate 0.1 0.1 0.02 1.2 0.1 0.1
Methylisobutyrate 0.2 0.2 0.05 1.7 0.4 0.2
Ethylacrylate 0.2 0.1 0.1
Methylmethacrylate 92 96 99 60.8 92 98
Cyclopentanone + + + 22.4 0.02 +
2-Methylbutanoic acid methylester 0.03 + + 1.0 0.1 +
Methacrylic acid 1.0 0.9 0.1 11.9 0.9 +
Butylacrylate + + − 1.2 + 0.02
Phenol − − − + 0.2 −
Dimethylethylcyclohexene 1.0 0.9 0.1 + 0.9 +
Trimethoxymethylbenzene 0.1 + − + + −
Dodecanoic methyl ester 0.1 + − + 0.1 −
Terephthalic dimethyl ester 0.1 + + + 0.2 +
TRIM-H2 − + − − 0.02 −
TRIM − + − − 0.2 −
Water 1.3 0.6 0.4 1.2 0.8 0.8
Other compounds 4.4 1.9 0.2 7.9 4.2 0.8
634 W. KAMINSKY
The liquids contain mainly the monomer MMA in the range 92–99% for silica-filled
PMMA and 58% for ATH-filled PMMA. Other liquid compounds in higher concentration
are methacrylic acid and dimethylethylcyclohexene. After distillation, the MMA is pure
enough for new polymerization. Filled PMMA yielded more by-products such as long-
chain methyl esters and Diels–Alder products. The reason for their formation could be
the higher residence time and some catalytic effect of the filler.
The excellent heat transfer in a fluidized bed, the low residence time of the monomers,
and the low temperature gradient in the bed is a reason so few side products and so little
carbon black is formed.
The highly filled PMMA (71% SiO2 ) was cross-linked. For the cross-linking trimethyl-
(3-propane)trimethacrylate (TRIM) and trimethylol-(3-propane)-isobutyrate-dimethacry-
late (TRIM-H2) were used. These compounds were detected in small amounts up to
0.2 wt% in the liquid fraction.
O O O O O O
O O O O
O O
TRIM: Trimethylol-(3-propane)- TRIM-H2: Trimethylol-(3-propane)-

trimethacrylate isobutyrate-dimethacrylate
They also reduce monomer recovery as well as recovery of other comonomers during
pyrolysis because of the disturbance of the step-by-step radical degradation process [29].
It was found that the pyrolysis of the ATH-filled PMMA yielded only 58% MMA
monomer instead of 97% found with a pure PMMA feed. Hydrolysis products from
MMA such as methacrylic acid, methanol and isobutyric acid were found to be the other
main by-products from the thermal decomposition of this composite material. Pyrolysis-
GC-MS experiments showed that the yield of the monomer MMA can be increased to
65 wt% by lowering the process temperature to 400◦ C. Water released during pyrolysis
of ATH and the chemical starter/stabilizer in the composite material were found to be
responsible for the low monomer yield. The high amount of the aluminium components
in this material has almost no catalytic influence on the hydrolysis reaction because the
same result was found if steam was used as fluidizing medium instead of nitrogen.
For the pyrolysis, an energy balance was made, too. Between 0.92 and 1.50 kW h kg−1
PMMA were needed for heating up the fluidizing gas and for delivering the degrada-
tion energy.
The following values were measured for the pilot plant: melting and depolymerization
energy (450◦ C) of pure PMMA: 0.60 kW h kg−1 ; heating up the fluidizing gas on pyrolysis
temperature 0.20–0.40 kW h kg−1 , losses of heat by reactor isolation: 0.50 kW h kg−1 .
The losses can be reduced in a technical plant.
4 PYROLYSIS OF POLYSTYRENE
Polystyrene (PS) is another polymer which can be degradated to the monomer. The
required pyrolysis temperature is higher than in the case of PMMA as feedstock. The
experiments were carried out in the fluidized-bed reactor (see Figure 24.1) between 515
and 540◦ C and with different fluidizing gas flows (Table 24.7). The molecular weight of
the unfilled PS was 225 000.
The main product is in all cases the liquid. Up to 99.7% can be obtained. The gas
fraction is very low and contains mainly methane, ethene, ethane, and propene. The gas
content is higher with increasing pyrolysis temperature.
The oil content decreases with increasing pyrolysis temperature and decreasing resi-
dence time represented by the fluidizing gas flow rate. A higher gas flow rate gives a
shorter residence time of the gases in the fluidized bed.
The whole product composition is shown in Table 24.8. The styrene content decrease
with increasing temperature and reaches 74.85 wt% by 519◦ C and shorter residence time
(gas flow rate 6.8 m3 /h). In a pilot plant experiment the pyrolysis temperature was 520◦ C
resulting in a styrene content of 76.8%.
Other main liquid components are dimeric, trimeric, and other oligomeric styrene com-
ponents. The content reaches 14 wt% of these oligomers. Other components formed by
the pyrolysis of polystyrene are toluene, α-methylstyrene, diphenylethane/propane, and
other aromatics. The styrene oligomers show secondary isomerization reactions. These
make it difficult to pyrolyze them in a following step into higher amounts of styrene.
Mainly, other aromatics are obtained by the degradation of the styrene oligomers. This
means that the optimum recovery of styrene from PS is about 77 wt% in an uncatalyzed
fluidized-bed process.
5 PYROLYSIS OF PTFE
Fluoropolymers are technical polymers with very special properties and applications.
Their properties are derived mainly from the strong carbon–fluorine bond energy of
507 kJ mol−1 , compared with typical energies of 415 kJ mol−1 for C–H or 348 kJ mol−1
for C–C bonds. The most important fluoropolymer is polytetrafluoroethylene (PTFE). In
Table 24.7 Reaction parameters for the pyrolysis of PS and the prod-
uct fractions obtained
Temperature (◦ C) 515 540 540 515

Gas flow (m3 /h) 3.7 3.7 6.8 6.8
Reaction time (h) 2.0 4.0 2.75 2.0
Throughput (kg/h) 1.25 1.30 1.10 1.05
Feed (kg) 2.5 5.2 3.0 2.1
Products
Gas (wt%) 0.90 1.88 0.82 0.14
Oil (wt%) 98.87 97.75 99.04 99.71
Soot (wt%) 0.23 0.37 0.14 0.15
636 W. KAMINSKY
Table 24.8 Products formed by the pyrolysis of PS in a fluidized-bed reactor in wt%, + = traces
Temperature (◦ C) 515 540 540 515

Flow gas (m3 /h) 3.7 3.7 6.8 6.8
Hydrogen 0.03 0.05 0.02 +
Methane 0.20 0.52 0.16 0.03
Ethene 0.28 0.63 0.35 0.06
Ethane 0.07 0.24 0.07 0.01
Propene 0.19 0.30 0.15 0.03
Propane 0.02 0.03 0.02 +
Butenes 0.09 0.09 0.06 +
Other aliphatics 0.19 0.34 0.10 0.05
Benzene 0.30 0.12 0.07 0.13
Toluene 2.23 2.91 2.31 2.01
Ethylbenzene 0.66 0.86 0.34 0.36
Styrene 71.94 68.73 73.41 74.85
α-Methylstyrene 2.33 3.19 2.22 2.30
Propylbenzene 0.03 0.06 0.03 0.01
Indene 0.39 0.56 0.50 0.32
Methylindene 0.14 0.08 0.02 0.04
Naphthene 0.06 0.11 0.02 0.05
Diphenylmethane 0.06 0.09 0.06 0.04
Diphenylethane 1.32 2.19 1.66 0.87
Diphenylpropane 1.97 3.07 2.46 1.36
Styrene dimer 6.64 4.28 6.11 4.85
Phenylnaphthaline 1.12 0.67 0.24 0.22
Higher styrene oligomers 4.75 9.08 7.25 9.25
Other components 4.76 1.43 2.23 3.01
Soot 0.23 0.37 0.14 0.15
order to improve the properties of PTFE it is often compounded with glass fibres, carbon
fibres, coal/soot, bronze, steel, molybdenum sulphide or polymers such as polyimides or
poly(phenylene sulphide).
Slow decomposition of PTFE occurs above the application temperature of 260◦ C. How-
ever, for a noticeable decomposition to occur, temperatures above 400◦ C are needed.
The primary decomposition products are tetrafluoroethylene (TFE) and difluorocarbon
diradicals (CF2 ). Further products are formed by secondary reactions, depending on tem-
perature, reaction pressure and reaction atmosphere. The typical main products are TFE,
hexafluoropropene (HFP), cyclo-perfluorobutane (c-C4 F8 ) and other fluorocarbons. Most
of these substances are nontoxic, but highly toxic substances such as perfluoroisobutene
or fluorophosgene are also formed under some reaction conditions.
Lewis and Naylor reported the first results on the pyrolysis of PTFE in 1947 [26]. At a
temperature of 600◦ C yields of up to 97% TFE were obtained under vacuum (7 × 102 Pa).
Under an atmospheric pressure of 1.103 × 105 Pa this yield dropped to only 16%, whereas
the yields of HFP and c-C4 F8 were increased.
Miesowicz [27] used a tube reactor for the depolymerization of PTFE under a nitrogen
or steam atmosphere. We have carried out PTFE decomposition in a fluidized-bed reactor
using nitrogen as fluidizing gas at different temperatures (Table 24.9).
Table 24.9 Main products of the pyrolysis of PTFE
in a fluidized bed
Temperature (◦ C) 605 650 700

Duration (min) 81 91 55
Feed rate (g h−1 ) 90 83 104
Products (wt%)
TFE 78.5 75.9 60.2
HFP 4.6 5.2 6.0
c-C4 F8 3.7 5.9 16.1
Pyrolysis products were mainly TFE, c-C4 F8 , and HFP. Other fluorocarbons and carbon
oxides were found only in traces. Reactions of decomposition products with the bed
material increase from 5% at 605◦ C to 9% at 650◦ C and 13% at 700◦ C.
Other experiments were carried out with filled PTFE material, using steam as fluidiz-
ing gas. Fillers were carbon black, glass fibres, and bronze. Important parameters are
listed in Table 24.10. In the first three experiments, the influence of the temperature was
investigated, in the following were other fillers used.
The PTFE compounds were production wastes ground down to a diameter around 2 mm.
The mass fraction of filler was 25 wt% for carbon black and glass fibres and 60 wt%
for bronze. The length and diameter of the glass fibres are 30–70 µm and 10–20 µm,
respectively. Carbon particles are 5–150 µm in diameter with an average of 20 µm.
Bronze particles were of irregular shape and reached a maximum diameter of 60 µm. All
experiments yielded gases, a water fraction, and solid residues as product fractions. Mass
balances of all fractions and substances are given in Table 24.11. They are referred to
PTFE input. The main products were TFE, HFP, c-C4 F8 , and fluoride (F− ).
The highest yields of monomers such as TFE, HFP and c-C4 F8 of around 90 wt% were
obtained at pyrolysis temperatures of between 645 and 600◦ C. Formation of oligomeric
PTFE waxes can be explained by repolymerization of TFE in the cooling steps where
the steam is condensed. The same phenomena occur during industrial production of TFE.
Carbon black and glass fibres have nearly no influence on the product composition (com-
pare Table 24.9). For the bronze-filled PTFE the yields of TFE, HFP and c-C4 F8 were
Table 24.10 Parameters of the main pyrolysis experiments of filled PTFE pyrolysis
Fluidized bed temperature (◦ C) 505 545 600 600 600

Compound material Carbon black Carbon black Carbon black Glass fibre Bronze
Input (kg) 5.0 4.8 4.8 3.2 7.1
Duration (min) 145 130 155 225 180
Feed rate (kg h−1 ) 2.1 2.2 1.9 0.9 2.4
Water throughput (kg h−1 ) 3.5 5.5 3.3 3.3 2.9
Steam flow (m3 h−1 ) 12.6 20.7 12.7 12.5 11.7
Auxiliary nitrogen flow (m3 h−1 ) 0.6 1.1 0.8 0.8 0.8
Fluidized bed residence time (s) 0.6 0.4 0.6 0.6 0.6
Freeboard residence time (s) 2.4 1.4 2.3 2.4 2.5
Water/PTFE ratio 2.3 3.3 2.4 5.1 3.1
638 W. KAMINSKY
Table 24.11 Mass balance for the pyrolysis of different PTFE compounds
Fluidized bed temperature (◦ C) 505 545 600 600 600

Compound material Carbon black Carbon black Carbon black Glass fibre Bronze
Productsa (wt%)
Soot 4.7 + 0.18 1.0 +
Fluoride 2.4 6.7 5.9 5.1 16.0
Oligomeric PTFE 11.0 1.9 1.9 0.64 +
Carbon in CO and CO2 0.51 2.0 1.8 1.4 3.5
Trifluoromethane 0.01 0.18 0.05 0.04 0.24
Difluoroethylene 0.01 0.07 0.07 0.03 0.47
Trifluoroethylene 0.01 0.09 0.05 0.03 0.14
Tetrafluoroethylene 71.0 68.0 71.0 75.0 51.0
Pentafluoroethane + + 0.05 0.03 +
Hexafluoropropene 6.3 7.8 7.5 6.6 7.3
Heptafluoropropane + + + + +
Cyclo-octafluorobutane 3.9 12.0 11.0 9.9 21.0
Octafluorobutane + + 0.03 0.01 +
Hexafluorobutane + + 0.16 0.05 +
Not identified 0.42 1.0 0.26 0.12 0.72
TFE + c-C4 F8 75.0 80.0 82.0 85.0 72.0
TFE + c-C4 F8 + HFP 81.0 88.0 89.0 91.0 79.0
a
Referring to PTFE input, + = traces
significantly reduced at the same temperature. There is a catalytic influence, mainly for
the formation of fluoride (HF) by reaction with water. The amount of CO2 and CO
also increased.
6 CONCLUSIONS
It can be shown that it is possible to recover high amounts of monomers from special
polymers by pyrolysis in a fluidized-bed process. Up to 98 wt% of MMA can be recovered
from filled or coloured PMMA wastes. In the case of polystyrene the rate of recovered
styrene is limited to about 77 wt%; the rest is oligomers. The high yields of TFE, HFP and
c-C4 F8 obtained from PTFE compounds in the experiments described show that fluidized-
bed pyrolysis of pure PTFE or PTFE compounds is a feasible and interesting opportunity
for the chemical recycling of this polymer.
In contrast to other recycling processes (mechanical recycling, vacuum pyrolysis),
fluidized-bed pyrolysis has a number of advantages. Different kinds of plastics can be
degradated into monomers in higher yields than with other methods and without needing
to mill wastes into small particle sizes. The most important advantages are that monomers
produced can be purified before repolymerization which allows production of a more
valuable product and that the process allows continuous operation.
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(1976).
16. T. Masuda, Y. Niwa, A. Tamagawa, S. R. Mukai, K. Hashimoto and Y. Ikeda,
Degradation of waste poly(ethylene terephthalate) in a steam atmosphere to recover
terephthalic acid and to minimize carbonaceous residue, Polym. Degrad. Stab., 58,
315–320 (1997).
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of PET and PBT, Polym. Degrad. Stab., 42, 13–28 (1993).
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DGMK Symposium, Essen, 6–8 September, 1989.
640 W. KAMINSKY
22. C.M. Simon and W. Kaminsky, Chemical recycling of poly(tetrafluoroethylene) by
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25
Feedstock Recycling of PET

TOSHIAKI YOSHIOKA AND GUIDO GRAUSE
Graduate School for Environmental Conservation, Department of Applied Chemistry,
Tohoku University, Aramaki Aza 07 Aoba-ku, Sendai 980-8579, Japan
1 INTRODUCTION
PET is one of the most versatile plastics in use today. It can be used for one-dimensional
(fibers), two-dimensional (films) and three-dimensional (bottles) applications (Table 25.1).
Two-thirds of the PET production is used for filament and staple fibers. These fibers are
used for textiles, carpets, tyre cords, safety belts or tent squares. According to the broad
range of applications for fibers their properties differ very strongly. Their molar weights
range from 10 000 g/mol for low-pilling fibers to 42.000 g/mol for tire cord. Furthermore,
these are long term applications and the task of recycling these materials will become
urgent in the future. Especially collecting and sorting will be a challenge of increasing
interest.
Films and bottles are mainly used as packaging materials in the food industry. Their
amounts are increasing rapidly. PET bottles have replaced glass-bottles in many cases.
These materials usually have a short lifetime and they are collected by several systems,
depending on local conditions. In many countries bottles are separately collected, in
Europe as bottles returned to the merchant, in Japan separately collected additional to
the municipal waste (Table 25.2). Films used for food packaging are usually mixed with
other plastics and wastes. For recycling, mechanical or manual separation is necessary. The
effectiveness of recycling depends strongly on the waste management. Countries with large
landfill possibilities show a smaller tendency for recycling than other countries. Collected
plastics are not always recycled. Often they are used for thermal energy production.
According to the wide range of applications PET consumption is increasing rapidly. From
2000 to 2010 a doubling of PET demand from 27.6 million tons to 56.0 million tons is
estimated (Table 25.3). While in Europe and America the raise of the PET consumption
is mainly maintained by PET bottle production, in Asia the expansion of PET use is
correlated to a higher production of fibers, due to the shift of fiber production from the
industrialized countries to low-wage countries (Table 25.4).
642 T. YOSHIOKA AND GUIDO GRAUSE
Table 25.1 Demand of polyester worldwide according to application, and future prediction [1]
1990 1995 2000 2005 2010

Fiber 8 900 11 700 18 800 24 200 33 300
PET resin (for bottles) 1 100 3 100 7 100 11 900 18 900
Film 1 000 1 100 1 400 1 400 1 700
Others 700 800 1 100 1 900 2 200
Total 11 700 16 700 28 400 39 400 56 100
Unit : thousand tons in 2000
Table 25.2 Recycling of PET bottles worldwide (2000) [2]
Continent Country Recovery Consumption Ratio

Asia Japan 125 362 34.5
Korea 39 85 46.0
Taiwan 11.3 91 12.4
China 6.3 363 1.7
Indonesia 3.0 26 11.5
Thailand 38
India 15 70 21.4
Oceania Australia 28 88 31.8
New Zealand 1.0 9 11.1
Europe Austria 12 34 35.6
Belgium 22 80.9 27.2
Czech 0.1 8 1.2
Denmark 0.3 5.2 5.8
Ireland 0.5 10.8 4.6
Finland 2 8.1 24.7
France 55.5 254 21.8
Germany 48 100 48.0
Greece 1.1 34.5 2.9
Hungary 0.2 9 2.2
Iceland 1.0 1.0 100
Italy 75 420 17.8
The Netherlands 1.5 67 2.2
Norway 1.5 4.8 31.2
Poland 0.5 65 0.8
Portugal 1.5 32 4.7
Spain 8.9 159 5.6
Sweden 7 19.4 36.1
Switzerland 24 24 100
Britain 7 227.5 3.1
Turkey 7.3 35 20.8
North America Canada 30 76 39.5
Mexico 20 91 22.0
USA 356 1 597 22.3
South America Brazil 20 110 20.0
Chile 1.0 16 6.2
Total 944.5 4 621 20.4
FEEDSTOCK RECYCLING OF PET 643
Table 25.3 Demand for polyester in different regions, and future prediction [1]
Area 1985 1990 1995 2000 2005 2010

North and South America 2 400 2 800 4 300 6 600 9 000 12 000
Europe, Middle and Near East, Africa 1 900 2 800 3 300 4 300 7 000 9 000
Asia 3 300 5 700 9 000 16 700 24 000 35 000
Total 7 600 11 300 16 600 27 600 40 000 56 000
Table 25.4 Consumption of PET resin for bottles worldwide, and future prediction [3]
Area 1995 2000 2005 2010

North and South America 1 500 3 000 4 800 6 400
Europe, Middle and Near East, Africa 900 2 400 4 200 6 800
Asia 600 1 600 3 000 5 600
Total 3 600 7 000 12 000 18 800
2 PHYSICAL RECYCLING (MECHANICAL RECYCLING)
The collection of PET bottles leads to a pure PET material. After cleaning from conta-
mination and separation of paper labels and polyethylene caps the PET is used to make
pellets or flakes. The starting PET material has to be free from polyvinylchloride, because
released HCl catalyzes the saponification of PET.
This PET recyclate is used mainly in the nonfood sector, because of hygienic concerns.
Small amounts of recyclate are used in bottle-to-bottle applications. In the sandwich
process a core of recyclate is coated inside and outside by virgin PET. In this case up to
40% recyclate can be used.
Another possibility to use PET recyclate for food applications is the URRC process
(United Resource Recovery Corporation). In this method the cleaned PET flakes are
covered with concentrated caustic soda. After evaporation of the water in a rotary kiln
the sodium hydroxide etches the surface of the PET at a temperature of more than 200◦ C.
The resulting sodium terephthalate is removed by washing. The remaining flakes are
used for the production of bottle preforms. Since 2000 several plants in Switzerland and
Germany have been established [1].
3 SOLVOLYSIS (CHEMOLYSIS)
PET is manufactured in a two-step process. In the first step terephthalic acid (TPA) is
esterified with ethylene glycol (EG) to form bis-2-hydroxyethylene terephthalate (BHET)
and oligomers up to a molar mass of 2000 g/mol. Older plants use the transesterification
of dimethylterephthalate (DMT) with EG, because for a long time it was difficult and
O O + HOCH2CH2OH O O
O C C O CH2CH2
n HOH2CH2C O O CH2CH2OH
Figure 25.1 Glycolysis of PET
expensive to obtain the necessary purity for TPA. In the second step BHET is polycon-
densed at temperatures between 270 and 300◦ C and a vacuum of less than 100 kPa to
remove the released EG.
Solvolysis (chemolysis) is defined as a technique which obtains the raw materials, such
as TPA, DMT, EG monomers and oligomers as the reverse process of PET production
by saponification or transesterification with water, methanol or EG. For the process of
PET production raw materials of high purity are obligatory. Polycondensation is not a
chain reaction, but a step reaction. Impurities can stop the polycondensation at low molar
masses, so high-purity standards are also required for the solvolysis products. The choice
of process depends on the starting material and the demand for solvolysis products.
3.1 GLYCOLYSIS
The most important solvolysis process today is the glycolysis of PET with EG, forming
BHET as the simplest oligomer of PET. This reaction is performed at 190–200◦ C and
3.0–4.0 MPa using glycol as solvent as shown in Figure 25.1.
Since, during the production and the glycolysis process diethylene glycol is formed,
diethylene glycol is accumulated in the BHET. This diethylene glycol has a negative
influence on the properties of PET. Hence, the contribution of glycolysis BHET is limited
to 20–30% in the production of new PET.
This process also generates higher oligomers as impurities in BHET. In many cases
metal acetic acid salts are used as catalysts in this reaction. Baliga and Wong [5] examined
the catalytic effect of acetic acid salts of zinc, lead, cobalt, and magnesium in order to
raise the generation of BHET, and reported a catalytic effect in the order Zn2+ > Pb2+ >
Mn2+ > Co2+ . This ranking is in agreement with the effect during polycondensation [6].
Transesterification performed at 170–200◦ C in the presence of aliphatic carboxylic
acids, such as adipic acid, after the depolymerization of PET in EG and propylene glycol
leads to unsaturated polyesters. These materials are used in foam production or for the
production of polyurethanes and polyester polyol copolymers [7–9].
Since 2003, AIES Co., Ltd. operates a glycolysis and polycondensation plant
(Figure 25.2) with a capacity of 27 500 t/y. After a sorting and cleaning process, which
is used to separate PET from glass, metal, caps and paper, the PET is depolymerised by
ethylene glycol in continuous stirring reactors at a temperature between 200 and 220◦ C.
The resulting BHET is purified by filtration, adsorption on activated carbon, crystallization
and vacuum distillation steps. After purification it is directly depolymerised to produce
virgin PET.
3.2 METHANOLYSIS
Alcoholysis with methanol (Figure 25.3) is the most general method of manufacturing
DMT and EG from waste PET. When PET is treated with an excess of methanol at
PET bottle (Bale) Waste PET bottle precutting process Flake storing process
Wet type crusher
Water washing
CAP, STEEL GLASS, CAN PET flake silo
CAP, LABEL
Bale dismantling Decolorization and
Floatation
Depolymerization deionaization
E-11
processes Purification processes
process
Purification machine BHET flaking
E-24
processes
Crystallizer
Solid/Liquid separator
Melting vessel EG purification
process
Depolymerization vessel
Crystallizer
Melt state polymerization process Hopper
reactor
Pure
E-59
E-57 PET
Final-polymerization Pre-heater Pellet cooler PET resin silo

vessel Pelletizer pellet chamber
Solid state polymerization PET resin shipping process

Pre-polymerization vessel Middle-polymerization vessel
Figure 25.2 AIST glycolysis process
O O O O
O C C O CH2CH2 + 2 CH3OH + HOCH2CH2OH
n H3CO OCH3
O O O O
+ CH3OH + HOCH2CH2OH
H3CO O CH2CH2OH H3CO OCH3
Figure 25.3 Methanolysis of PET
about 200◦ C and 2.5–4.5 MPa, DMT and EG are produced stoichiometrically. In the
methanolysis the same catalysts are used as in glycolysis. The yield of DMT varies
between 80 and 85%.
The methanolysis process was patented in 1957 by DuPont [10]. Since 1960 several
processes have been developed [11, 12]. The methanolysis process makes use of several
steps. At first the PET is dissolved and partially glycolyzed. By this first step the pressure
of the subsequent methanolysis can be reduced. The resulting DMT and EG are purified
by crystallization and distillation (Figure 25.4).
The methanolysis process can be performed batchwise (Figure 25.4) or continuously
(Figure 25.5). In both cases the PET is molten. After that the melt is treated with methanol
(2)
(3)
PET MeOH (5)
DMT
(1)
(4)
(6)
MeOH
for distillation
Figure 25.4 High-pressure methanolysis (batch process). (1) Autoclave; (2) reflux con-
denser; (3) crystallizer; (4) centrifuge; (5) melter; (6) distillation column
PET
(1) (2)
PET Melt
melter storage
MeOH
(3)
(4)
(5)
(6)
(7)
MeOH DMT
Figure 25.5 Continuous methanolysis. (1) Melter; (2) melt storage; (3) first autoclave;
(4) second autoclave; (5) mixer; (6) crystallizer; (7) centrifuge
O O O O
+ H2O
O C C O CH2CH2
n − HOCH2CH2OH HO OH
Figure 25.6 Hydrolysis of PET
under pressure and elevated temperature to obtain DMT. For purification of the DMT
vacuum distillation columns and crystallizers are used. The purified DMT is usually used
for the production of PET in the transesterification process.
Teijin Fiber Ltd introduced a process using the combination of glycolysis and methanol-
ysis. In recent years, this technology has been developed to recycle PET bottles to obtain
DMT and purified TPA. The products are used for the production of PET fibers and
films. In 2003 Teijin Fiber Ltd. opened a methanolysis plant for the production of 50 000
t/y DMT.
3.3 HYDROLYSIS
Hydrolysis is the saponification of PET with water to TPA and EG as shown in Figure 25.6.
Campanelli et al. [13] obtained the initial hydrolysis rate constant of molten PET around
250◦ C from the concentrations of carboxyl groups, ester bonds and water after the reac-
tion. The results are shown in Table 25.5, together with the results at 100◦ C [14] and
186◦ C [15] for solid PET.
Since the hydrolysis rate is small at low temperatures, it is important to raise the
rate by increasing the temperature and pressure. Using a temperature higher than the
melting point of PET at about 250◦ C leads to a better distribution of the reactants. At this
temperature no catalyst is necessary. At 265◦ C the reaction leads to a complete conversion
in 30 min, with yields for TPA of 97% and EG of 91%. The TPA produced (solubility in
water at 270◦ C = 28.5 wt%) can be obtained by cooling down the solution and following
crystallization, because of the almost insoluble character of TPA at room temperature.
3.3.1 Acid-catalyzed Hydrolysis

Pusztaseri [16] and Yoshioka et al. [17] describe an improved hydrolysis process using
strong sulfuric acid with a good yield of TPA and EG. In this process, it is necessary to
purify the EG from sulfuric acid.
Table 25.5 Initial hydrolysis rate constants for PET

at different temperatures
Temperature (◦ C) Rate constant

(g PET mol−1 min−1 )
100 3.0 × 10−7
186 2.0 × 10−4
250 0.244
265 0.352
280 0.487
Yoshioka et al. [18] describe a process using nitric acid at 70–100◦ C and atmospheric
pressure. The resulting products are TPA and EG. The EG is simultaneously partially
oxidized to oxalic acid by the nitric acid:
3 HOCH2 CH2 OH + 8 HNO3 → 3(COOH)2 + 8 NO + 10 H2 O
The nitric acid acts as a catalyst. The NO formed in this reaction is regenerated by the
addition of water and oxygen:
3
2 NO + O2 + H2 O → 2 HNO3
2
3.3.2 Base-catalyzed Hydrolysis

Base-catalyzed hydrolysis of PET can be used to obtain TPA and oxalic acid [19]. PET is
completely hydrolyzed to TPA and EG at 250◦ C in concentrated aqueous NaOH solution.
Then EG is converted to oxalic acid and CO2 by the introduction of oxygen. Since the
sodium terephthalate formed is stable to oxidation, the yield of TPA reaches 100%. EG
is converted to oxalic acid by base-catalyzed oxidation with a maximum yield of 61%:
HOCH2 CH2 OH + 2 O2 → (COOH)2 + 2 H2 O
Oxalic acid is a more valuable product than EG. The final product mixture is a colorless
liquid, even when green PET bottles are used as feedstock, indicating that the green
dyestuff is effectively oxidized.
Oku et al. [20] described an interesting process using a solution of NaOH in EG. PET
is completely saponified by the base. The EG formed can be reused as new solvent. EG
does not participate in this reaction directly as in the glycolysis process:
O O
O O NaO
+ NaOH ONa
O C C O CH2CH2 +
HOCH2CH2OH
n HOCH2CH2OH
The UnPET-process of the United Resource Recovery Cooperation [21] uses a con-
centrated alkaline solution for the saponification of finely grounded PET. In this process
a preceding cleaning treatment is not necessary. The alkaline/PET mixture is heated to
230–290◦ C in a rotary kiln. After vaporizing the water the PET is saponified. Also EG is
vaporized and collected. Impurities such as paper and polyethylene are oxidized by air.
Base-catalyzed hydrolysis always leads to the TPA salt of the cation used. Releasing
the salt by neutralization leads to large amounts of waste salts such as NaCl or Na2 SO4 or
a complicated treatment of the sodium terephthalate. Figure 25.7 shows the neutralization
scheme for sodium terephthalate with CO2 for the UnPET process. All components run
in cycles. Just TPA, EG, CO2 and water are released. This product treatment needs five
PET + Contaminations
NaOHaq
EG + CO2 + H2O
Na2Tp + By-products
By-products
CaCO3 H2O
NaCO3 CaO
CO2 Na2Tpaq Na2Tp
TPA
H2O
NaHCO3(aq)
NaHTp
Figure 25.7 UnPET process and neutralization of Na2 Tp (sodium terephthalate) with
CO2 avoiding the production of salts
single steps and is especially energy intensive. After the saponification of the PET in a
rotary kiln the products are dissolved in water. Insoluble products return to the rotary kiln.
Na2 Tp is neutralized with CO2 and NaHTp (monosodium terephthalate) precipitates. The
NaHTp is heated in water, Na2 Tp dissolves and TPA remains as a precipitate. The solution
of Na2 Tp is used to dissolve the products from the rotary kiln. After the neutralization
process the NaHCO3 solution is heated to vaporize water and CO2 to form NaCO3 . The
NaCO3 is dissolved in water again and treated with CaO. The resulting NaOH solution is
used for the saponification of the PET. The precipitated CaCO3 is thermally decomposed
to CaO and CO2 . The CaO is used for the recovery of NaOH and the CO2 for the
neutralization of the Na2 Tp solution.
3.4 OTHER PROCESSES
Fundamentally, solvolysis of PET is separated into methanolysis, glycolysis, and hydroly-

sis. Recently, many processes have been developed, which combine two or three of these
techniques, such as the neutral hydrolysis process [22], hydrolysis by reactive extru-
sion [23], glycolysis–hydrolysis [24], etc.
4 PYROLYSIS AND OTHER HOT PROCESSES
Besides low temperature processes such as solvolysis and alkaline or acid saponification
described above, which are usually accomplished in a liquid media at high pressure,
there are also high-temperature processes from 300◦ C to more than 1000◦ C, at fairly low
pressure. In this temperature range products leave the hot reactor zone in a gaseous state.
High-boiling products can be condensed. Sublimable products such as TPA or benzoic
acid can block pipes and cause corrosion. Especially TPA with a sublimation point of
more than 400◦ C has to be considered as a severe problem in the construction of PET-
using facilities. It is necessary to find a safe way to remove them from the gas stream
by decomposition, if these products are unwanted or by appropriate filtration methods, if
these products are wanted. A special advantage of these processes is that they are carried
out under atmospheric pressure in simple reactors.
4.1 DECOMPOSITION MECHANISM OF PET
In contrast to polymerisates, polycondensates can not be depolymerized under inert con-

ditions. Decomposition usually leads to the destruction of the chemical structure and the
monomers. The thermal decomposition of PET starts at about 300◦ C in an inert atmo-
sphere [25]. Between 320 and 380◦ C the main products are acetaldehyde, terephthalic
acid, and carbon oxides under liquefaction conditions. The amounts of benzene, benzoic
acid, acetophenone, C1 –C4 hydrocarbons, and carbon oxides increase with the tempera-
ture. This led to the conclusion that a β-CH hydrogen transfer takes place as shown in
Figure 25.8 [26]. Today the β-CH-hydrogen transfer is replaced as a main reaction in PET
degradation by several analytic methods to be described in the following sections. The
most important are thermogravimetry (TG) and differential scanning calorimetry (DSC)
coupled with mass spectroscopy and infrared spectroscopy.
4.1.1 Analysis by Negative Chemical Ionization (NCI) Mass Spectrometry

For a long time electron ionization (EI) at 70 eV was the most used method for the
identification of pyrolysis products. Unfortunately, in the case of oligomers EI leads to a
strong fragmentation, and the molecular ions are difficult to observe. Negative ionization
is a softer kind of ionization. The use of negatively charged molecular ions from methane
or ammonia leads just to a small fragmentation and to a good observation of the molecular
mass of the target molecule.
H O
O
O
O
O O
+
OH O
Figure 25.8 β-CH hydrogen transfer

100
192
165
314 340
50
384
100 200 300
100 352
50 576
506
400 500 600
100
50
768
916
700 800 900
Figure 25.9 Negative chemical ionization mass spectrum of the pyrolysis products of
PET at 350◦ C
Adams [27] and others analyzed the products of the thermal decomposition at 350◦ C
by NCI at 10–15 eV. They found strong peaks for the dimer, trimer and tetramer of
ethylene terephthalate (Figure 25.9). It was considered that an intermolecular backbiting
process is favored at this temperature and that β-CH hydrogen transfer is not a dominant
reaction, because the intensities of β-CH hydrogen transfer products were smaller than
those of the oligomers. Montaudo et al. [28] found that cyclic oligomers are preferred.
They are formed by ionic intramolecular exchange reactions. In a second step the cyclic
oligomers decompose by a β-CH hydrogen transfer and form open-chain oligomers with
olefin and carboxylic end-groups.
4.1.2 Analysis by Collision-induced Dissociation Tandem Mass Spectrometry

(CID-MS/MS)
Montaudo et al. [28] used CID-MS/MS to obtain information on the original molecular
structure from the cleavage pattern of the molecular ion. In this procedure the ion with
Linear ion 476 576

100
532
I% 50
505
0
400 500 m/z 600
53 57
10 Cyclic ion
47
I 5 54 55
48
46
0
40 50 m /z 60
ion at m/z = 576 from PET 53 57

10
47
I 5
50
46 48 54
0
40 50 m /z 60
Figure 25.10 CID-MS/MS shows the existence of both linear and cyclic oligomers in the
product spectrum of PET pyrolysis. (Reprinted from Polymer Degradation and Stability,
Vol. 42, G. Montaudo et al., pp 13–28, 1993, with permission from Elseveir)
m/z 576 was chosen to be analyzed by a second MS. The cyclic and the linear trimer
were used as comparison in this experiment. According to Figure 25.10, both peaks of
the cyclic trimer (m/z 460, 488, 546) and the linear trimer (m/z 505) were detected. This
suggests that both cyclic and linear trimers are formed during the pyrolysis of PET.
4.1.3 Analysis by Fourier Transform Infrared Spectroscopy (FT-IR)

Holland [29] followed the thermal degradation of PET at 370◦ C in an argon atmo-
sphere using FT-IR. This method allows one to follow the changes of several functional
groups during the decomposition process. The absorbance of three wavenumbers corre-
sponding to the C–H stretching vibration (2960 cm−1 ), the carbonyl stretching vibration
(1730 cm−1 ), and the ester C–O stretching vibration (1250 cm−1 ) decreased simultane-
ously (Figure 25.11) due to the degradation of the material. It was suggested that the
main reaction is an intramolecular backbiting mechanism, leading to cyclic oligomers
(Figure 25.12).
1250 cm−1
C – O stretching
0.8 1560cm−1C C
Absorbance 0.6
2960 cm−1
C–H stretching
0.4
0.2
1730cm−1
1200 C=O stretching
2400
3600
4800
6000
Time(sec)
Figure 25.11 Time dependence of FT-IR spectra of PET pyrolysis at 370◦ C. (Reprinted
from Polymer, Vol. 43, B. J. Holland et al., 2002, pp. 1835–1847, with permission from
Elsevier)
O O
O
O O
Cyclic oligomers
O O
O
HO O
Intramoleclar transfer
Figure 25.12 Intramolecular backbiting process for the formation of cyclic oligomers
from PET pyrolysis. (Reprinted from Polymer, Vol. 43, B. J. Holland et al., 2002, pp.
1835–1847, with permission from Elsevier)
4.2 PYROLYSIS PROCESSES
Pyrolysis can be performed for many different reactors. The product distribution varies
markedly between the different reactor types and the reaction conditions, such as temper-
ature, bed materials or catalyst. The aim of the pyrolysis is the reduction of wastes for
landfilling and the production of fuels. Especially fuel oil with a high calorific value is an
interesting product. Char can be used as a fuel, but is also seen as a precursor for other
carboneous materials such as activated carbon. The best way to obtain these products is
decarboxylation of the polymer. In this way carbon oxide-rich gas is produced.
4.2.1 Pyrolysis
Most work has focused on the use of fixed–and fluidized-bed reactors. Fixed-bed reactors
are commonly used as batch reactors with the disadvantage of long ramp times. The choice
of temperature and heating rate leads to strong differences in the product distribution.
Table 25.6 Comparison of different pyrolysis methods for PET
Williams and Williams [30] de Marco et al. [31] Yoshioka et al. [32]
Reactor type Fixed-bed Fixed-bed Fluidized-bed
Temperature 25◦ C/min → 700◦ C 500◦ C 510–730◦ C
Gas (%) 34.0 73.4 38–49
Oil (%) and 41.3 9.1 14–56
organic solids
Char (%) 15.6 18.5 5–41
Total (%) 90.8 100 100
More than 40% oil can be achieved by heating the polymer at 25 K min−1 to a final
temperature of 700◦ C [30]. The oil obtained is rich in aldehydes, ketones, carboxylic
acids, alcohols and aromatic compounds; 34% gas and 16% char were also produced.
Pyrolysis at 500◦ C for 30 min leads to 73% gases, 19% solids and 9% liquids [31].
In this case a large amount of sublimed products are observed, which can cause prob-
lems by blocking pipes. Table 25.6 shows a comparison of different pyrolysis methods
for PET.
The fluidized-bed process shown in Figure 25.13 is a continuous waste treatment pro-
cess [32]. The polymer can be fed directly into the fluidized bed. Volatile products leave
the reactor with the gas stream. Solid products such as fillers and char can be removed
by exchanging the bed material. In a temperature range between 510 and 730◦ C 38–49%
Storage Vessel
Electrostatic
precipitator
Steel cooler Glass cooler
cyclone Water
Precipitator
Cooling
ethanol
N2
Fluidized bed Vacuum pump
reactor
Pre-heater Compressor Fluidized-gas Exhaust-gas Flare

gas meter gas meter
Figure 25.13 Fluidized-bed plant for the pyrolysis of PET with a feed rate of 1 kg
PET/h [32]. (Reprinted from Polymer Degradation and Stability, Vol. 86, T. Yoshioka
et al., pp. 499, 2004, with permission from Elseveir)
SOFTENING
of the polymer surface
ADHESION of sand particles

of the polymer surface
ELUTRIATON REDUCTION
of fines of conversion
CRUMBLING
efficiency
of the aggregate
and, in the case of a
persistent carbon residue,
VOLATILE RELEASE carbon fines formation by
and polymer flowing attrition of bridges or
throughout the sand particles detachement of carbon layers
SINTERING
of the sand particles covered
by a layer of adhesive residue
SEGREGATION WORSENING
FORMATION of an AGGREGATE
of the aggregates having of fluidization quality
made of several layers of sand
a sufficient long life-time and risk of bed
kept together by the polymer
defluidization
not yet devolatilised (PE) or
by the carbon residue (PET)
POSSIBLE GROWING
of the aggregates
with the consequent
formation of a size
and density distribution
of the aggregates
Figure 25.14 Mechanism of the defluidization during the pyrolysis of PE and PET [33]
(Reprinted from Chemical Engineering Science, Vol. 55, U Arena et al., 2000, pp. 2849,
gases (mainly carbon oxides) are produced. At low temperatures high amounts of ben-
zoic acid and TPA are observed. Their yields decrease at higher temperatures in favor of
carboneous residues in the reactor. Over the whole temperature range only a little oil was
observed.
Indeed, PET shows an effect of defluidization, as shown in Figure 25.14 [33]. Sticky
carbon residues formed by PET are covered by layers of sand. In this way larger particles
are formed which can not be fluidized by the gas stream. The defluidization time can be
increased by reducing the feed rate of the polymer and increasing the reactor temperature.
4.2.2 Catalytic Processes

In most cases the yield of oil produced during PET pyrolysis is very low. But some
catalysts can increase the amount of oil and decrease the amount of char. Additionally
they show a selectivity for special products.
Calcium hydroxide shows a strong selectivity for benzene [34]. In a steam atmosphere
the PET is hydrolyzed and after that the resulting TPA is decarboxylated by the catalyst.
At 700◦ C 36% of the PET can be converted into benzene. This corresponds to a benzene
yield of 88% based on PET. Other main products are carbon oxides and char. Organic
acids are not observed (Figure 25.15).
One possibility to reduce solid products and obtain hydrocarbons is the pyrolysis of
PET together with PP in order to increase the hydrogen content [35]. Pyrolysis at 425◦ C
over a TiO2 /SiO2 catalyst leads to a high amount of oil with a high C18+ hydrocarbon
content (Figure 25.16).
Figure 25.15 GC-MS chromatogram of the liquid products of PET pyrolysis with
Ca(OH)2 [34]. (Reproduced by permission of the Chemical Society of Japan)
Figure 25.16 Comparison of the product distribution from a mixture of PP and PET over
different weights of catalyst at 698 K and the carbon number fractions of the resulting
oil [35]. (Reproduced with kind permission of Springer Science and Business Media)
Also copper(II) chloride shows a positive effect on the weight loss of PET during
pyrolysis [36]. Between 450 and 500◦ C the amount of residue can be reduced by half.
But the interaction between chloride and polymer leads to chloroorganic compounds,
which makes the usage of this method difficult from the point of view of health and
environment.
In different processes TPA is an undesired side product. It causes blocking and cor-
rosion problems. It can be decomposed by several catalysts such as CaO/ZnO [37] at
temperatures above 300◦ C. Resulting products are benzene, benzoic acid and carbon
dioxide.
4.2.3 Carbonaceous Materials from PET

PET can also be used as a source of activated carbon. The properties of the products are
dependent on the process parameters. Surface area, pore size distribution and adsorption
behavior are influenced by the heating method and the atmosphere composition. A heating
rate of 50 K h−1 with a final temperature of 500◦ C maintained for 2 h leads in different
atmospheres to surface areas between 402 and 123 m2 /g [38]. A nitrogen atmosphere gives
the best result, while carbon dioxide and steam show lower surface areas. Oxygenated
atmospheres show a tendency to increase the pore size. In all these cases a yield of
activated carbon of about 17% can be obtained related to PET. Higher temperatures under
a nitrogen atmosphere lead to worse results. The surface area decreases from 242 m2 /g
at 750◦ C to 14.7 m2 /g at 1200◦ C [39] during a stepwise heating process.
The activation of char, obtained from the pyrolysis of post-consumer PET bottles, with
carbon dioxide at 925◦ C leads to highly porous materials. After a burn-off of 76% a BET
area of 2500 m2 is reached. This material shows similar or better hydrogen adsorption
properties than high-tech carbon materials such as nanotubes [40]. It was possible to
charge the carbon with 2.3 wt% hydrogen at −196◦ C. This fact opens the way for the
use of this low-cost material as hydrogen storage.
4.2.4 Oxidative Pyrolysis and Combustion

Another way of using plastics as fuels is their direct combustion. The oxidative pyrolysis
of PET has been investigated in several cases. Oxidative pyrolysis means that instead
of an inert atmosphere an oxygen-containing gas was used. In this case pyrolysis can
occur, if oxygen can not reach the particle surface due to efflux of volatiles or diffusional
resistances at boundary layers, or if oxidative conditions do not affect the kinetics and
mechanism of the pyrolytic processes [41].
Senneca et al. [41] investigated the oxidative pyrolysis of PET and other materials
using a thermobalance. The samples were heated to 800◦ C at different heating rates and
different oxygen contents of the atmosphere. Pyrolysis took place up to a temperature
of 415–450◦ C. A higher oxygen concentration led to a shift of the weight loss to lower
temperatures due to the overheating by the combustion of volatile products. At higher
temperatures weight loss was generated by char combustion (Figure 25.17).
In fact the oxygen content of the atmosphere has little influence on the pyrolysis [42].
Of course there is more carbon dioxide produced, but the emission of the most products,
hydrocarbons and aromatics, remains similar. The combustion reduces primarily the amount
PET
O2 5% N2
O2 10%
O2 21%
5°C/min
O2 5% N2
(dm/dT)/mo, K−1
O2 10%
O2 21%
10°C/min
O2 5% N2
O2 10%
O2 21%
20°C/min
200 300 400 500 600 700

T, °C
Figure 25.17 DTG curves of PET at different heating rates and oxygen concentra-
tions [41]. (Reprinted from Journal Of Analytical And Applied Pyrolysis, Vol. 71, O.
Senneca et al., 2004, pp. 959, with permission from Elsevier)
of residue. However, at 850◦ C the emission of dibenzofuran increases drastically from

30 µg/g PET during pyrolysis to more than 5000 µg/g PET under oxidative conditions.
4.2.5 Hydrolysis
Another possibility is the saponification with steam to obtain monomers from PET, similar
to the hydrolysis in liquid water under pressure. In this way TPA can be obtained, on
water
input vessel water Electrostatic

reactor cyclone precipitator
gas samples
desublimator coolers
ethanol
steam generator flare
nitrogen
Figure 25.18 Fluidized-bed reactor for hydrolysis of PET [44]. (Reprinted from Polymer
Degradation and Stability, Vol. 85, G. Grause et al., pp. 571, 2004, with permission from
Elseveir)
the contrary ethylene glycol is usually decomposed. The temperature range of this high-
pressure hydrolysis is limited at the bottom by the sublimation point of TPA at 400◦ C
and at the top to 500◦ C by increasing pyrolytic decomposition of the PET.
Masuda et al. [43] have shown that hydrolysis of PET in a fixed-bed reactor at 450◦ C
in an atmosphere of 70% steam and 30% nitrogen led to a yield of 87% TPA and less
than 1% carbonaceous residue.
Using a fluidized-bed reactor (Figure 25.18) the results are very similar [44]. For virgin
PET with an optimal temperature of 450◦ C a yield of 72% TPA can be achieved. An
additional 24% is fixed in two oligomers. The TPA yield using real bottle materials is
still about 61%, and between 17 and 23% TPA remains as oligomers. Fe2 O3 and NiO
fillers in the material reduce the oligomer content rapidly. In this case a yield of 69%
TPA can be obtained. Char production is negligible.
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PART VI
Asian Developments
26
The Liquefaction of Plastic

Containers and Packaging in Japan
A. OKUWAKI
Tohoku University, 31-9 Hagurodai, Taihaku-ku, Sendai 982-0817, Japan
T. YOSHIOKA
Graduate School of Environmental Studies, Tohoku University, Aramaki Aza Aoba
6-6-07, Aoba-ku, Sendai 980-8579, Japan
M. ASAI
Rekisei Kouyu Co. Ltd, Niigata Plastic Liquefaction Center, 3-1 Heiwa, Niigata, Japan
H. TACHIBANA
2879-52 Kikuma, Ichihara, Chiba 290-0007, Japan
K. WAKAI
Sapporo Plastics Recycling Co. Ltd, 45–57 Nakanuma-chou, Higashi-ku, Sapporo
007-0890, Japan
and
K. TADA
Kubota Corporation, 3-1-3 Muromachi, Nihonbashi, Chuo-ku, Tokyo 103-8310, Japan
1 INTRODUCTION
A. Okuwaki and T. Yoshioka
1.1 BRIEF HISTORY OF PLASTICS LIQUEFACTION IN JAPAN
Feedstock recycling of waste plastic is an established method for recycling post-use

plastics. Typically, waste plastics are recycled to naphtha, their raw material. This is
666 A. OKUWAKI ET AL.
because of the high crude oil price, crude oil price of West Texas Intermediate (WTI) is
the highest in the oil market.
The liquefaction of waste plastics is not an entirely new technique, but the challenge
to operate commercial plants has been tried in Germany by pyrolysis and hydrogenation.
However, the former, operated by BASF was stopped in 1996, and the latter by Veba Oel
GmbH in 1999 [1]. It is well known that the reason is not a technical problem, but an
economic one; the cost is higher than those of competitive techniques, such as mechanical
recycling or blast furnace application.
Economic conditions in Japan are quite similar to those in Germany. Although the
feedstock recycling of waste plastics in household waste has progressed since 1997,
economic problems still exist in collection, baling, transportation, and feedstock recycling,
compared with incineration of household waste that is treated locally on site. The main
reason why various feedstock technologies have been commercialized in Japan is that the
Plastic Containers and Packaging Recycling Law (abbreviated as Plastic Recycling Law,
below) came into effect in 2000. Especially, there is a long history of the liquefaction of
mixed waste plastics, as shown in Table 26.1, supported by the Government [2].
The first generation supported by the Government started just after the oil crisis in
the 1970s. However, it took a long time for commercialization of liquefaction; until
environmental awareness developed in Japan on issues such as problems of the shortage
of landfill site and excessive CO2 emission by simple incineration of huge amount of
waste plastics. The Plastic Recycling Law had a big impact.
However, several tens of millions of people’s efforts sorting waste plastics in every-
day life support the recycling system as well as the financial support of municipalities
together with businesses that manufacture or use the containers and businesses that use
the packaging.
This section describes the recycling law, the amount of recycled waste plastics, some
operating information on three liquefaction processes, and the scope of liquefaction of
post-use plastic containers and packaging in Japan.
1.2 THE LAW FOR PROMOTION OF SORTED COLLECTION AND RECYCLING

OF CONTAINERS AND PACKAGING [3]
This is simply called the Containers and Packaging Recycling Law, applying to glass
bottles, steel and aluminum cans, and plastic containers and packaging. In this law,
Table 26.1 Brief history of liquefaction of waste plastics in Japan
1972 Start of the development of liquefaction (PWMI)a

1973 Evaluation of melting, microwave heating, and fluidized bed processes. (PWMI)
1990 Test plant (400t/y) at Okegawa city (SMERI)b
1991 Liquefaction of industrial waste plastics (5,000t/y) at Aioi City (CJC)c
1995 Pilot plant test for containers and packaging plastics at Kawasaki city. (PWMI)
1997 Liquefaction (6,000t/y) at Niigata city supported by MITI.(Rekisei) Liquefaction
(3,000t/y) at Tachikawa city supported by MHW.(JWRF)d
a
Plastic Waste Management Institute;
b
Organization for Small and Medium Enterprises and Region Innovation, Japan.;
c
Clean Japan Center.;
d
Japan Waste Research Foundation
LIQUEFACTION OF PLASTIC WASTES IN JAPAN 667
the respective roles of, consumers, businesses, and municipalities, concerned with the
recycling system for container and packaging waste are as follows.
Consumers must assume the role of separating waste on discharge, as well as sup-
pressing the generation of waste through the rational use of containers and packaging as
described above.
Businesses that manufacture or use the relevant containers and businesses that use
the relevant packaging, bear the obligation to recycle. Businesses may also transfer the
exercise of the obligation to recycle to the Japan Container and Package Recycling Asso-
ciation (JCPRA), the designated corporate body. Ultimately, they have to pay to recycle
their plastic waste.
Municipalities must draw up selective collection plans and devise necessary measures
for selective collection of container and packaging waste in their local areas. Thus, they
have to collect the plastic waste and to bale it, removing foreign materials, on their budget.
The ratios of recycling for these materials are the highest in the world, especially for
plastic containers such as PET bottles. The recycling of PET bottles was started earlier in
the USA and EU, but the ratio has decreased in the USA, since enough economic support
has not been obtained. However, in the EU, the recycling ratio has increased gradually,
supported by the environmental awareness of European people. The increasing ratio in
Japan is predominant, since the law became effective in 1997, preceding the other plastic
containers and packaging [4].
1.3 FEEDSTOCK RECYCLING OF PLASTIC CONTAINERS AND PACKAGING
The amount and rate of plastic waste and resource recovery is shown in Table 26.2 [5].
Total plastic waste discharged reached 9900 000 t in 2002. The amount of municipal solid
waste exceeded that of industrial waste in 2001 and the difference between them tends to
increase. Although the amount of feedstock recycling reached 450 000 t in 2002, it still
accounts for only 8.9% of municipal solid waste (MSW). Large amounts of waste plastics
are treated by incineration with or without energy recovery both in MSW and industrial
waste.
In the recycling of plastic containers and packaging, mechanical recycling occupies a
major role. Mechanical recycling and feedstock recycling are authorized by the guidelines
from JCPRA, but energy recycling is not permitted by the Plastic Recycling Law.
The minimum recycling ratio for each recycling method designated is shown in
Table 26.3. A standard method for treatment of bales prepared by municipality is also
given there and the ratio is calculated by the designated equation for each method.
All the bales prepared by municipalities according to the guidelines are controlled by
JCPRA, and every enterprise permitted by JCPRA having various techniques is able to
apply for the tender.
Mechanical recycling has a predominant bidding right over feedstock recycling, since it
has an advantage with Life Cycle Analysis (LCA). Practically, however, the mechanical
recycling of PE, PP, and PS (3P) needs careful separation by specific gravity separation
processes, and only 45% of the minimum recycling degree is permitted. The remaining
55%, composed of PET material, PVC material and PVDC film and accompanying 3P
are discarded as industrial waste, though they have been collected, baled, and transported
to the recycling sites from various municipalities in Japan.
668
Table 26.2 Amount and rate of plastic waste and resource recovery in 2002
Material recycling 260 Material recycling

Municipal Liquefaction/gasification/Blast furnace 190 1520 (15%)
solid waste Densified-refuse-derived fuel 50 Liquefaction, Gasification,
Incineration with power generation 1,830 Blast furnace Utilized
5080 Incineration with heat utilization facility 330 250 (3%) plastic
Total plastic Incineration without power generation 1,520 Densified-refuse-derived fuel waste
waste discharge or heat utilization facility 320 (3%)
Landfilling 910 Incineration with power generation 5420
Material recycling 1,270 2050 (21%) (55%)
Liquefaction/blast furnace 70 Incineration with heat
9900 Densified-refuse-derived fuel 270 utilization facility
(100%) Industrial Incineration with power generation 210 1270 (13%)
waste Incineration with heat utilization facility 950 Incineration without power Non-utilized
generation or heat utilization facility plastic waste
4820 Incineration without power generation 210 1730 (18%)
or heat utilization facility Landfilling 4490
Landfilling 1,850 2760 (28%) (45%)
[Unit; thousand tons]
A. OKUWAKI ET AL.
Table 26.3 Guidelines for minimum recycling
ratio for each method (wt%)
Year
Method 2002 2004
Mechanical ≥40 ≥45∗
Liquefaction ≥35 ≥45
Blast furnace ≥50 ≥75
Coke oven ≥50 ≥85
Gasification∗∗ ≥50 ≥65
∗
For Types I, II, III;
∗∗
energy base
Table 26.4 Large-scale feedstock recycling facilities of plastic containers and packaging in 2003
Method Company Location Municipal mixed Remarks

plastic waste
(t/yr)
JFE Steel Kawasaki 40 000

Fukuyama 40 000
Blast furnace
Kobe Steel Kakogawa 10 000
Nippon Kimitsu 50 000
Coke oven Steel Nagoya 50 000
Mixed Corp. Muroran 20 000
plastics Yahata 20 000
Ube-Ebara Ube 30 000 EUP
Gasification JFE Steel Chiba 20 000 Thermo select
Showa Denko Kawasaki 60 000 EUP
Sapporo Yuka Sapporo 13 000 Toshiba
Liquefaction Douo Yuka Mikasa 6 000∗ Kubota, March 2004.
Rekisei Koyu Niigata 6 000 PWMI
∗
Stopped.
Liquefaction, iron and steel industry applications, and gasification are authorized as
the feedstock techniques. The capacities of recycling via these techniques are shown in
Table 26.4.
The capacity of liquefaction is less than that of other techniques since its tender price
has been the highest in these as shown in Section 5. However, liquefaction has come into
effect in the Plastic Recycling Law, since the Niigata liquefaction plant has demonstrated
for the first time in these feedstock techniques, that such mixed and complicated household
waste plastics were recyclable as pyrolysis oil.
The liquefaction plant encountered a fire problem towards the end of 1996 under test
operation, but it attained commercial operation in April 1998 due to the enthusiastic
contribution by Niigata city, PWMI, MITI, and others. Then, the Sapporo Plastic Recycle
Co. Ltd (SPR) was founded to recycle the waste plastics collected in Sapporo city, where
13 500 t has been baled every year. This system has received excellent support by Sapporo
city. However, only half of the baled plastics is used in the SPR liquefaction plant located
just next to the baling plant due to the tender system controlled by JCPRA. Thus, the
operating ratio of the SPR plant is not so high, and this also raises the treatment cost
of waste plastics, as does the small scale. The remaining half is used for the iron and
steel industry, far from Sapporo. The third liquefaction plant constructed at Mikasa city,
Hokkaido stopped this March, since sufficient raw plastic waste could not be obtained.
REFERENCES
1. PWMI Report, Present Status of Niigata Plastics Liquefaction Center, p. 17 (2000).

(In Japanese).
2. M. Kaji, Presentation at the 6th General Meetings of FSRJ , Tokyo, 2004.
3. Clean Japan Center, Recycling-Oriented Society, p. 17, (2001).
4. A. Okuwaki, Polym. Deg. Stab, 85, 981–988, (2004).
5. PWMI, Fundamental Information for Plastic Recycling 2004 (In Japanese). http://
www. pwmi.or.jp.
6. The Association for Containers and Packaging Recycling, Japan, Guidelines for the
Facilities of Recycling of Plastic Containers and Packaging in 2002 Fiscal Year, p. 9,
(2001) (In Japanese).
7. The Association for Containers and Packaging Recycling, Japan, Guidelines for the
Facilities of Recycling of Plastic Containers and Packaging in 2004 Fiscal Year, p. 8,
(2003). (In Japanese).
2 NIIGATA WASTE PLASTIC LIQUEFACTION PROCESS
A. Okuwaki, T. Yoshioka and M. Asai

The Plastic Wastes Management Institute (PWMI) has started to develop liquefaction
technology using plastic containers and packaging, with cooperation among the companies
operating original unit processes in the 1994 fiscal year, supported by MITI. As a result
of this development, Rekisei Kouyu Co. Ltd started construction of a liquefaction plant
that consists of pretreatment and liquefaction processes at Niigata city in 1995, and the
test operation started in September 1996.
2.1 PLANT OUTLINE
The plant is shown in Figure 26.1. The official capacity reaches 6000 t/y for sorted
bales. Rekisei Kouyu, commissioned by Niigata city, accepts the waste plastics separated
domestically and collected in Niigata city (population ∼500 000). The waste plastic is
pretreated to remove PET bottles and foreign material and to make fluff for liquefaction,
Figure 26.1 The Niigata liquefaction plant (Reproduced by permission of Plastic Waste
Management Institute)
then liquefied by pyrolysis of dehydrochlorinated plastic melt. The product oil is used as
fuel in the utilities of Niigata city.
2.2 PROCESS DESCRIPTION
The process is composed of a pretreatment process and a liquefaction process, using

pyrolysis of melted dehydrochlorinated plastic, similar to other liquefaction processes.
2.2.1 Pretreatment Process

The separated plastic containers and packaging wastes are collected by 30 packer trucks,
capable of carrying 700 kg/truck, and thrown in a pit. The collected waste in the pit is
treated by a bag-breaking machine and iron is removed by a magnetic separator, PET
bottles by hand picking, grinding, removal of foreign materials such as glass, sand, etc., a
continuous feeder, and compacting machine to prepare fluff and stored in a silo. Separation
of foreign materials is very important for stable operation, to minimize plugging in the
plastic melt line. PET bottles are compacted to a bale of 18 kg.
2.2.2 Liquefaction Process

The flow sheet of this process is shown in Figure 26.2. Prepared plastic fluff is sent to
a bag filter set on the top deck (Figure 26.1) by a pneumatic conveyer after treatment
by a second magnetic separator and an aluminum separator. Then, the plastic fluff is
sent to two series of dehydrochlorinators, specially designed, reciprocally rotating twin-
screw-type extruders, through a vertical screw conveyer. This equipment is composed of
a melter of plastic fluff and circulator of waste plastic melt. Each is a horizontal type
Mixed plastics HCI gas Incinerator Recovered

HCI
De-gassing
Waste gas
Plastic melt
Pretreatment
Product Distillation Oils
Residue
De-hydrochlorination
Furnace
Pyrolysis
Energy
recovery
Figure 26.2 Process flow sheet of the Niigata liquefaction plant
Table 26.5 Composition of melted

dehydrochlorinated plastic
Total chlorine 1.67 wt%

Inorganic chlorine 1.29 wt%
Organic chlorine 0.23 wt%
Softening point >180◦ C
Specific gravity (25◦ C) 1.04
with an impeller. These are heated at 340◦ C by a jacket in which thermal medium is
circulated.
The evolving gas, composed of HCl and light hydrocarbon, is incinerated at 1000◦ C
or higher and quenched by a water spray to make a 10% HCl solution as well as
to control dioxins. The composition of melted dehydrochlorinated plastic is shown in
Table 26.5.
The total chlorine consists mainly of inorganic chlorides, which are formed by reaction
of HCl gas from PVC and PVDC materials, and metallic materials in the fluff during
the dehydrochlorination. This has been reported already from IKV [2]. The degree of
dehydrochlorination was almost 95% [3].
The melted dehydrochlorinated plastic is then sent to a vertical tank pyrolyzer, fit-
ted with a scraper for removing carbonaceous material on the reactor wall. Energy
for pyrolysis is fed from a jacket heater and a high-temperature gas heater in a cir-
culating furnace, and blown into the bottom of the reactor, holding the temperature
at 420◦ C.
Table 26.6 Composition of plastic
containers and packaging (wt%)
Accepted Plastic fluff

PE 32.34 21.15
PP 12.98 23.40
PS 18.33 37.40
PVC 7.66 5.23
PET 15,43 5.78
Other 12.77 7.04
Note Dry basis Dry basis
June 1996
The carbonaceous material and foreign materials for liquefaction are intermittently
extracted from the bottom of the reactor with a part of the reaction mixture and cooled
as residue. The pyrolysis gas emerging is carried to a distillation column and condensed
as light, medium and heavy fractions.
The light oil from the top is a slightly lighter than kerosene, and the noncondensable
light fraction is burned in a waste gas incinerator. The medium oil, corresponding to heavy
oil A, is stored as product oil, and partly recycled to the pyrolyzer as a heat source, and
heated in a tubular heater of the furnace at 420◦ C. Initially, plugging with carbonaceous
material caused the plant to stop frequently to remove it. However, since October 2002
this problem has been resolved by addition of Ca(OH)2 powder to the fluff. After this
improvement, the operation is quite smooth.
The heavy fraction, solid at ambient temperature, has a slightly higher pour point, and
requires heating equipment.
2.3 QUALITY OF WASTE PLASTICS
One example of waste plastics accepted is shown in Table 26.6. The composition of waste
plastic fluff varies enormously and the accepted value is an average of three samples. PET
and PVC materials are predominant, though PET bottles are removed by hand-picking in
the pretreatment by Niigata city.
2.4 PROPERTIES OF OUTPUTS
2.4.1 Properties of Oils

The properties of light, medium, and heavy oils distilled from pyrolysis oil. are shown
in Table 26.7.
The light oil originally contained relatively high amounts of chlorine, but recently
the content has decreased to the 10–40 ppm level. Thus, a packing tower for removing
hydrogen chloride from organic chlorine compounds is no longer in use, since the product
oil now meets the quality requirement directly. Thus, after addition of Ca(OH)2 , the
chlorine content dropped to 10 ppm level as shown in Table 26.7.
Table 26.7 Properties of light, medium and heavy oils distilled pyrolysis oil
Reactivity Light oil Medium oil Heavy oil

Date of sampling ‘98/10 ‘04/3 ‘98/10 ‘03/12 ‘98/10 ‘03/12
◦ 3
Density (at 15 C) (g/cm ) 0.8083 0.8019 0.8362 0.8473 0.8634 0.8926
Kinetic viscosity (15◦ C) (CSt) 0.64 0 1.74 2.712
Viscosity (50◦ C) (CP) 44
Pour point (◦ C) <−50 0.0 52.5
Moisture (ppm) 200 111 72
Flash point (◦ C) <−30 46.0 92.0
High heating value (cal/g) 10000 10720 10880
Elemental Analysis
C (wt%) 88.5 86.5 86.7
H (wt%) 11.3 11.8 12.1
O (wt%) <0.1 0.2 <0.1
N (wt%) 0.085 0.092 0.12 0.114 0.11 0.112
S (wt%) 0.0012 0.0043 0.0251 0.006 0.0294
Total Cl (wt ppm) 550 11 45 13 43 65.6
Inorganic Cl (wt ppm) 380 15 17
Organic Cl (wt ppm) 200 33 25
Bromine value (Br-g/100 g) 42 35.0 25 13.5 16 8.9
Residual C (wt%) <0.01 0.02 0.45
Ash (wt%) <0.01 0.01> 0.04
pH 2.7 3.4 3.3
Terephthalic acid (wt ppm) <10 100 50
Phthalic acid (wt ppm) <10 110 70
Benzoic acid (wt ppm) 1100
Cetane number 46.0
Oxidative stability (mgKOH/g) 93.8 0.09 1.90 0.05 0.49
Type analysis
Aromatic (wt%) 56.2 32.0
Unsaturated (wt%) 26.3 27.0
Saturated (wt%) 17.5 41.0
Diene value (g/100g) 1.1 1.8 1.0 2.5 0.9
The medium oil contains quite low sulfur, but has a slightly lower pour point compared
with commercial heavy oil A. It is used as a boiler fuel for the sewage treatment plant in
Niigata city. The heavy fraction contains quite low sulfur and is used in a paper and pulp
factory in Niigata city. The distillation properties of the oils are shown in Figure 26.3.
2.4.2 Hydrochloric Acid

A chlorine balance in the raw fluff has been reported [2] and chlorine recovery had reached
94.95% as 9.6% hydrochloric acid. Recently, calcium hydroxide is added to the fluff as
in the Sapporo Plastic Recycling Center to stabilize the operation. The recovery of HCl
decreased greatly from 5.4 to 1.2%, as shown in the material balance in Figure 26.3 and
is discarded after neutralization.
700
600
Heavy oil
500
Temperature (°C)
400
Medium oil
300
200
Light oil
100
0
IBP 20 40 60 80 EP
Degree of distillation (%)
Figure 26.3 Distillation curves for light, medium, and heavy oils
2.4.3 Pyrolysis Residue

In Table 26.8, the properties of the residue are also shown. It is notable that aluminum
arising from laminated material and foil, and terephthalic acid from PET materials are
dominant. The chlorine in the raw fluff transferred some 2.4% or so to the residue [3].
2.5 MATERIAL BALANCE AND CONSUMPTION FIGURES
In Figure 26.4, total material balance is shown, including the pretreatment process, as at
22, October 1998. At that time, since the Plastic Recycling Law had not come into effect
yet, large amounts of discharge of the pretreatment was observed. Inflammable residue
indicates foreign material, and flammable residue corresponds to paper material.
Pyrolysis oil is produced at 380 kg from 1000 kg of waste plastics. The oil for sale
externally amounts to 125 kg, with 255 kg self-consumed as process fuel. After opera-
tional, improvements these values improved remarkably, as shown in the following energy
balance.
2.6 HEAT BALANCE
Figure 26.5 shows an energy balance on the same date as for the material balance. The
product oil for external sale is 167 kg from 1000 kg of waste plastic fluff. The net weight
Table 26.8 Analytical data for residue
Reactivity
Density (g/cm3 ) 1.08 (at 25◦ C)
Viscosity (CP) 1900
Softening point (◦ C) 138.5
High heating value (cal/g) 8810
Ash (wt%) 10.3
Elemental analysis
C (wt %) 75.0
H (wt %) 9.5
O (wt %) 5.0
N (wt %) 0.20
S (wt %) 0.043
Total Cl (wt ppm) 1.08
Inorganic Cl (wt ppm) 0.70
Organic Cl (wt ppm) 0.35
Terephthalic acid (wt ppm) 23 000
Phthalic acid (wt ppm) <10
Pb (mg/kg) 410
Cd (mg/kg) 13
Cu (mg/kg) 270
Hg (mg/kg) <0.05
As (mg/kg) <1
Cr (mg/kg) 24
Sb (mg/kg) <1
K (mg/kg) 1300
Na (mg/kg) 3700
Al (mg/kg) 16 400
Zn (mg/kg) 300
Fe (mg/kg) 3300
22 October 1998
of pyrolysis oil is 56 kg for sale, since 109 kg of fuel comprises 98 kg of pyrolysis oil
and 11 kg of LPG is consumed. These values are greatly improved, as shown in the lower
columns, to yield an increased amount of external sale.
The reason for the poor energy balance is that all the residue was landfilled at first
and pyrolysis gas was not utilized at all, as well as due to the stoppages of the plant for
cleaning the plugging. At present, the energy balance has improved remarkably due to
the improvement of oil yield from 501 to 551 kg and the residue has begun to be used
partly as fuel.
2.7 APPLICATION OF THE OUTPUTS
The product oil corresponding to heavy oil A, is used as fuel in the sewage plant of
Niigata city as well as in a test application for a diesel engine in the Niigata Tekko Co.
Ltd (applicable for power plant using diesel engines). The NOx content in exhaust gas is
of similar level to that for heavy oil A, and DXNs contents were 0.0055 ng TEQ/N m3 .
Waste plastics
1,000
PET bottle 55
Inflammable
(Pre-treatment process) Discharge
residue 55
250
Flammable
residue 140
Plastic fluff
750
HCl 40
(Liquefaction process) Discharge Gases 120
Residue 210
Light oil Medium*Heavy oils

250 130
Product oil
380
Fuel
255
For sale
125 (Unit : kg)
Figure 26.4 Material balance in the Niigata liquefaction plant
Plastic fluff
Electricity
1,000 Discharge
399 kWh
377 kWh
HCl Exhaust gases Residue
(Liquefaction process)
53 160 280
12 214 223
Light oil Medium*Heavy oils

333 174
Product oil
507
551
Fuel LPG Fuel

(Unit : kg)
98 11 340 Light oil Medium*Heavy oil
For sale
77 11 225 Date ‘98.10.22 333 174
167
04.6.- 265 286 new data
283
Figure 26.5 Initial and latest energy balances in the Niigata liquefaction plant
A residue used for analysis contained 47% oil. The residue has a higher heating value
than that of coal and is suitable for energy recovery. However, it contains chlorine and
heavy metals as shown in Table 26.8. Any exhaust gas and fly ash treatment must be
carefully considered in its application. Recently, it has been used in a furnace, and has
contributed to the improvement of heat balance, as described above.
2.8 ENVIRONMENTAL MEASUREMENT
Exhaust gases from the incinerator, thermal medium furnace, and absorption tower using
light oil as fuel, have all met the regulation determined by the law and ordinance for
air pollution. Wastewater from two effluents have also met the water pollution law and
ordinance [3]. Naturally, the latest values meet these regulations [1].
REFERENCES
1. PWMI Report, The Present Status of Niigata Plastic Liquefaction Center, May, 2000.
(In Japanese).
2. V. Lackner, Diploma Thesis at IKV, RWTH Aachen, 1991.
3. PWMI Report, The Performance Summary in Test Operation of Niigata Plastic Liq-
uefaction Center, p.13, March, 1999. (In Japanese).
3 SAPPORO WASTE PLASTICS LIQUEFACTION PROCESS

H. Tachibana and K. Wakai
3.1 PLANT OUTLINE
This waste plastics pyrolysis process has been developed by Toshiba Corporation, and
a plant with 14 800 tons annual capacity of household waste plastics was constructed
in Sapporo by Toshiba Corporation (Figure 26.6). The plant has been in operation since
April 2000 by Sapporo Plastics Recycling Co., Ltd (hereinafter SPR) with investment
by TERM Corporation, Toshiba Corporation, MITSUI & Co., Ltd. and Sapporo City
Government.
The waste plastics utilized at the SPR plant are the household waste plastics specified
by the Containers & Packaging Recycling Law and marked as ‘recyclable’ on the each of
the products. The waste plastics are discharged at curbside by residents once per week, and
collected, sorted, compacted in bale form by the local government, which then supplies
the SPR plant.
The SPR plant handles of 43 tons/day on a two-line pretreatment section, 40 tons/day
on a two-line pyrolysis and oil distillation section, and operates a 2000 kW × 2 line
cogeneration facilities (Figure 26.7) that uses pyrolysis heavy oil as fuel. The pretreatment
section is operated by two operators and three forklift operators for 10 hours per day, and
the pyrolysis and oil distillation section is continuously operated for 24 hours per day,
Figure 26.6 SPR plant view
Figure 26.7 Cogeneration system
by four operators per shift. The Whole plant is automatically operated by a distributed
control system (DCS). All of the products and by-products obtained from pyrolysis are
utilized for feedstock recycling or energy recovery, except for hydrochloric acid obtained
from PVC.
The system flow diagram of waste plastics discharged by Sapporo citizens to conversion
to oils at SPR plant is shown in Figure 26.8.
Houses in Sapporo city Bulk waste plastics

packed in PE bags.
(discharged by citizen)
Curve side
(collected by city)
City sorting center Bale

(transported by forklift)
SPR pretreatment plant Pellets

(transported by conveyor)
SPR pyrolysis plant Pyrolysis oil

(transported by pump)
SPR oil distillation plant 3 kinds of Distilled oils

Light/Medium/Heavy
(stored for shipment)
Figure 26.8 Sapporo system flow diagram
Figure 26.9 Waste plastics bale
The waste plastics bales (Figure 26.9) which are 1 × 1 × 1.3 m and weigh 200 kg are
transported by forklift in the warehouse of the pretreatment section of the plant and
weighed, stored and then continuously shredded, dried, sorted, and pelletized to 6 mm
diameter × 20 mm length pellets that are stored in a pellet silo.
The flow sheet of the pyrolysis and oil distillation section is shown in Figure 26.10.
The waste plastics pellets are conveyed from the pellet silo to the pellet hopper located on
Pyrolysis Oil Distillation Application
Waste plastics pellets inlet Vent

Steam
De-HCI gas incinerator to oil refinery
Pellets hopper
HCI absorber Waste gas Incinerator
Fuel
Off gas scrubber
De-hydrochlorinator Light oil tank
(for plant)
Distillation column
Medium oil tank Electric power
LIQUEFACTION OF PLASTIC WASTES IN JAPAN
Molten Polymer vessel

Co–generator Steam
Oil drum Heavy oil tank
Pyrolysis reactor
Residue cooling conveyor
Pump
Residue
Hydrochloric acid tank
Figure 26.10 SPR process flow for pyrolysis and distillation

681
the top elevation of the pyrolysis plant and stored. Calcium hydroxide (Ca(OH)2 ) powder
is added to the pellets. Pellets containing Ca(OH)2 are fed into the dehydrochlorinator,
which has electric heaters on the cylinder and a specially designed single-axis screw.
The waste plastics are melted and thermally degraded in the machine. PVC contained in
the waste plastics, is dehydrochlorinated at 300–330◦ C and ∼5 kPa overpressure. The
dehydrochlorinated molten polymer and the evolved gases are moved into the molten
polymer vessel.
The mixed gas, composed of hydrogen chloride and hydrocarbons, which are separated
in the molten polymer vessel, goes into dehydrogen chloride gas incinerator and the
hydrocarbons are burnt out at 1300◦ C. The incinerator and the operating conditions are
designed and operated to prevent the generation of dioxin. The hydrocarbon-free exhaust
gas from the incinerator is quenched and absorbed into water in the HCl absorber to give
20 wt% hydrochloric acid.
The dehydrochlorinated molten polymer in the molten polymer vessel is quantitatively
fed into the pyrolysis reactor (Figure 26.11), which is of rotary kiln type. It has a hot air
jacket and ceramic balls inside to prevent coking problems, as shown on the Figure 26.12.
Thermal degradation is at 400◦ C and ∼5 kPa overpressure.
The thermally degraded gas discharged from the reactor is liquefied by quenching and
is stored in the oil drum. The residue generated in the reactor, which is a dry, fine particle
size powder, is periodically discharged from the bottom of the reactor and transferred to
the residue hopper through a cooling jacket chain-conveyer. One of the characteristics of
the plant design is to move the materials by gravity flow from the waste plastics pellet
hopper to residue discharge from the pyrolysis reactor.
The pyrolysis oil stored in the oil drum is fed into the distillation column with reboiler
and separated into three fractions; light oil from the top, medium oil from the middle and
heavy oil from the bottom of the column. These three types of oils are stored in separate
oil tanks and sent to the furnaces and cogeneration system in the plant as fuel through
piping, or loaded onto a tank lorry for shipment.
The off-gas, composed of hydrogen and C1 –C4 hydrocarbons generated in the pyrolysis
reactor, goes to waste gas incinerator, in which the hydrocarbons are burnt out and only
inert gas is vented to atmosphere through the exhaust gas boiler, where the energy is
recovered as steam.
3.3 QUALITY OF WASTE PLASTICS
Figure 26.13 shows the analytical results of waste plastics bales from Sapporo city, as
sent to the SPR pyrolysis plant. The content of polyethylene (PE), polypropylene (PP) and
polystyrene (PS) which are suitable for the pyrolysis is 71%. Although the consumption of
polyvinylchloride (PVC) products is decreasing, PVC content of household waste plastics
is still 3.1%. The content of polyvinylidenechloride (PVDC) is relatively high, because
PVDC film is used as food wrap in Japan. Polyethyleneterephthalate (PET) bottles used
for drinks and soy sauce are collected separately and recycled to feedstock recycling or
mechanical recycling according to the Container and Packaging Recycling Low. However,
PET waste from nonfood sources is collected together with other plastics and supplied
to the SPR plant for pyrolysis treatment. The PET content of household waste plastics
Figure 26.11 Part of the pyrolysis plant
Pyrolysis gas outlet

Hot air inlet
Dehydrochlorinated
molten polymer inlet
Ceramic balls
Hot air outlet

Residue outlet
Figure 26.12 Pyrolysis reactor

Foreign matters
Other plastics
2.1%
9.9%
ABS
0.4%
Polyethylene –
terephthalate(PET) Polyethylene(PE)
12.2% 38.0%
Polyvinylidenechloride
(PVDC)
1.4%
Polyvinylchloride(PVC)
3.1%
Polystyrene(PS)
16.8% Polypropylene(PP)
16.1%
Figure 26.13 Composition of waste plastics bale
is more than 10% and is likely to increase. The amount of foreign matter is relatively
low, since foreign materials are previously separated in the city’s sorting facilities. The
moisture content of the bale is approximately 6%.
3.4 PROPERTIES OF OUTPUTS
3.4.1 Properties of Oils

Table 26.9 shows the properties of pyrolysis oil and distilled oils. The pyrolysis oil is the
fully condensed oil before distillation. The distillation characteristics of product oils are
shown in Figure 26.14. Figure 26.15 shows the carbon number distribution (NP gram) of
the pyrolysis oil and distilled oils. Table 26.10 shows the standard specifications TS Z
0025, that will apply to the waste plastics pyrolysis oils in energy recovery applications,
effective in 2005 in Japan. The analysis results shown in Table 26.9 indicate that all
distilled oils satisfy the specifications of Table 26.10.
The physical properties of distilled oils corresponded to a mixture of gasoline and
kerosene for light oil, diesel oil for medium oil, and crude oil for heavy oil. Light oils
contains a high concentration of C9 aromatic compounds, primarily a styrene monomer
and ethyl benzene. Styrene dimer and trimer are not found that much. Medium oils offer
the best qualities for fuel application, because of higher flash points and lower pour points.
Heavy oils are solid at ambient temperature and must be kept above 60◦ C for handling in
liquid form. Pyrolysis oils contain much ash, including Cl, Ca, Si and other metals, which
accumulate in heavy oil and are separated by a centrifuge in the plant. Medium and heavy
oils indicate the high cetane index that is suitable for cogeneration fuel (a diesel-driven
power generator). Compared with the standard petroleum oils used as fuel, the distilled
oil has the same heating value and less sulfur content.
Table 26.9 Analytical results of pyrolysis and distilled oils
Property Analytical Pyrolysis Distilled Distil. Distil.

method oil light medium heavy
Appearance Black solid Yellow liquid Amber liquid Black solid
Density (15◦ C) JIS K 2249 0.8545 0.8310 0.8377 0.8626
Flash point (◦ C) JIS K 2265 92 117
Pour point (◦ C) JIS K 2269 35.0 <−50 −25.0 47.5
Carbon residue (wt%) JIS K 2270 4.18∗ 0.05
Carbon residue (10%) (wt%) JIS K 2270 0.08 0.3
Reactivity JIS K 2252 Natural Natural Natural Natural
Viscosity (30◦ C) (mm2 s−1 ) JIS K 2283 0.681 2.615
Viscosity (50◦ C) (mm2 s−1 ) JIS K 2283 2.458 19.27
Water content (wt%) JIS K 2275 0.005 0.031 0.02 0.0085
Ash content (wt%) JIS K 2272 2.69∗ <0.01 <0.01 0.04
Total heating value (kJ kg−1 ) JIS K 2279 44,750 43,750 44,290 45,800
Dry sludge (mg 100 ml−1 ) Hot filter 6.9∗ <0.01 0.02 0.2
Cetane index JIS K 2280.0 42.3 7.9 48.6 56.6
Total chlorine (mg kg−1 ) TS Z 0025 3,800∗ 90 47 71

Inorganic chlorine (mg kg−1 ) TS Z 0025 <5 3 38
Organic chlorine (mg kg−1 ) (balance) 90 44 24
Terephthalic acid (mg kg−1 ) GC/MS 100 <10 300
Benzoic acid (mg kg−1 ) GC/MS <100 42 100
C (wt%) TCD 85.6
H (wt%) TCD 12.6
O (wt%) (balance) 1.58
N (wt%) JIS K 2609 0.11 0.044 0.191 0.08
S (wt%) JIS K 2541 0.01 <0.01 <0.01 0.04
Ca (mg kg−1 ) JIS K 0102 50.3 8,200∗ 17.0 2.2 82
Fe (mg kg−1 ) JIS K 0102 57.4 99 <0.2 7.3 33
Na (mg kg−1 ) AAS 200∗ 0.8 ND 2.8
Al (mg kg−1 ) JIS K 0102 58.4 150∗ <0.2 ND 17
Si (mg kg−1 ) ICPAES 2,000∗ <100 4.0 <50
Cu (mg kg−1 ) JIS K 0102 52.4 84∗ 0.6 0.1 2.3
Zn (mg kg−1 ) JIS K 0102 53.3 18∗ 0.6 ND 2.1
Mn (mg kg−1 ) JIS K 0102 56.4 13∗ <0.2 ND <0.5
T-Hg (mg kg−1 ) Govern.guide line <0.01 <0.01 ND <0.01

R-Hg (mg kg−1 ) Govern.guide line ND ND ND ND
Cd (mg kg−1 ) JIS K 0102 55.3 0.8 <0.2 ND <0.5
Pb (mg kg−1 ) JIS K 0102 54.3 37∗ <0.2 ND 2.6
T-Cr (mg kg−1 ) JIS K 0102 65.1.4 37∗ <0.2 ND 8.2
Cr+6 (mg kg−1 ) JIS K 0102 65.2.4 <0.1 <0.1 ND <0.1
As (mg kg−1 ) JIS K 0102 61.3 <0.1 <0.1 ND <0.1
Aromatic (vol%) UOP 501-71 70.7 27.5
Saturated (vol%) UOP 501-71 9.3 20.6
Olefin (vol%) UOP 501-71 20.0 51.9
∗
The ash containing Ca,Cl,Si and other metals is transferred to heavy oil, and separated by centrifuge
ND: not detected
3.4.2 Hydrochloric Acid

Table 26.11 shows the analytical results of hydrochloric acid. The recovered hydrochloric
acid shows a 20 wt% concentration and has a good appearance, however, to date it has not
been used in a product application because Hg and As content do not meet to customer
600
Pyrolysis oil
Distilled light
500 Distilled medium

Distilled heavy
400
Temperature (°C)
300
200
100
0
t
10
20
30
40
50
60
70
80
90
95
t
in
in
po
po
wt.%
al
d
En
iti
In
Figure 26.14 Distillation characteristics
specifications. Therefore, the recovered hydrochloric acid is now neutralized by NaOH

in the plant and then transferred to city sewage treatment facilities together with other
wastewater. Contaminated containers in the waste plastics may contribute the Hg, while
As is thought to come from the additives and paints of the waste plastics.
3.4.3 Pyrolysis Residue

Table 26.12 shows the results of pyrolysis residue analysis. The pyrolysis residue is a
fine dry powder, black in color. Total Cl and organic Cl contents are 1.4 and 0.1 wt%,
respectively. Dioxin content is negligibly small. The higher content of Ca, inorganic Cl
and oxygen is due to the presence of CaCl2 and Ca salts of organic acids produced by
the addition of Ca(OH)2 . SiO2 and Al from raw materials contained in waste plastics.
Although some heavy metals, such as Cd and Pb, are detected, dissolving test results are
satisfactory. Therefore, landfill of the residue is possible. The high heating value and high
C and H content indicate that fuel application is possible. Recently, the residue has been
used as supplementary fuel for the city sludge incinerator at sewage treatment facilities,
utilizing the higher heating value.
60
50 Pyrolysis oil
Distilled light
Distilled medium
40 Distilled heavy
wt.%
30
20
10
0
1
3
5
7
9
11
13
15
17
19
21
23
25
27
29
31
33
35
37
39
41
43
45
Carbon number
Figure 26.15 Carbon number distribution
Table 26.10 Standard specifications of the pyrolysis oils from waste plastics
Property Method Specifications

1st category 2nd category 3rd category
Flash point (◦ C) JIS K 2265 <21 ≥21 to <70 ≥70 to <200
Ash content (wt%) JIS K 2272 ≤0.05 ≤0.05
S content (wt%) JIS K 2541 ≤0.2
T-Cl content (wt ppm) Specified∗ ≤100
N content (wt%) JIS K 2609 ≤0.2
Water content Observation No free water contained
∗
Specified in TS Z 0025
3.5 MATERIAL BALANCE AND CONSUMPTION FIGURES
Table 26.13 shows the material balance of the pretreatment section based on 100 kg bales,
the pyrolysis and distillation section based on 100 kg pellets, and whole plant based on
100 kg bales. The material balance of the whole plant is illustrated in Figure 26.16.
The material balance based on pellets shows a total oil yield of 62.0 wt% for household
waste plastics, the composition of which is indicated in Figure 26.13. The light/medium
/heavy ratio is 50/7/43(wt%). The yield of medium oil, most suitable for energy recovery,
is low. Hydrochloric acid yield is only 1.0 wt%. PVC content in household waste plastics
is only 3.1 wt%, and more than 50 wt% of HCl is fixed as CaCl2 by Ca(OH)2 addition.
Pyrolysis residue generation was originally 9 wt% and has now increased to 17.5 wt% due
to the increase in CaCl2 and Ca salts of organic acids in the residue through the addition
Table 26.11 Analytical results for hydrochloric acid
Property Analytical method Analysis data Specification∗

Appearance Transparent
light yellow
HCl concentration (wt%) JIS K 8180 20.2
Ignition residue (wt%) Weighing after ignition 0.06
SO4 2− (wt%) Turbidimetry 0.29
SS (mg l−1 ) Filtration 89
Oil (mg l−1 ) n-C6 extraction <1 <50
Fe (mg l−1 ) JIS K 0102-57.2 2.6
Cd (mg l−1 ) JIS K 0102-55.2 <0.005 <0.01
Pb (mg l−1 ) JIS K 0102-54.1 0.032 <0.1
Cu (mg l−1 ) JIS K 0102-52.2 0.04 <0.2
Zn (mg l−1 ) JIS K 0102-53.1 0.25 <1.0
Ni (mg l−1 ) JIS K 0102-59.2 <1 <1.0
Mn (mg l−1 ) JIS K 0102-56.2 0.05 <1.0
T-Cr (mg l−1 ) JIS K 0102-65.1 0.02 <5.0
As (mg l−1 ) JIS K 0102-61.2 0.39 <0.01
T-Hg (mg l−1 ) Govern.guide line 0.018 <0.001
R-Hg (mg l−1 ) Govern.guide line <0.0005
Cr6+ (mg l−1 ) JIS K 0102 65.2.4 <0.04
∗
Specification by HCl customer
of Ca(OH)2 . The off-gas comprises the volatile products under the operating conditions,
composed of hydrogen and C1 –C4 hydrocarbons, which are generated in pyrolysis and
separated in the distillation column.
As all the pyrolysis and distillation plant outputs are mechanically or thermally recycled
except for hydrochloric acid, the total recycle ratio in the pyrolysis process is calculated
as 99.0%.
Table 26.14 shows the consumption figures of energy and chemicals necessary for
operation of the plant. From the operation cost point of view, electrical power and fuel
are the most expensive. In this plant, product oils are used for these purposes: light oil
for fuel, and heavy oil for electrical power through the cogeneration system.
3.6 HEAT BALANCE
Table 26.15 shows the heat balance in the plant based on the material balance and con-
sumption figures shown in Tables 26.13 and 26.14, under following conditions:
1. All electrical power and fuel required for operation are calculated assuming an external
supply;
2. Enthalpies are 33.5 MJ kg−1 for waste plastics bales, 44.0 MJ kg−1 for pyrolysis
distilled oils, off-gas and fuel, and 18.0 MJ kg−1 for residue;
3. Power generation efficiency is 38%.
Table 26.12 Analytical results for pyrolysis residue
Property Analytical method Residue Dissolving test

Appearance dry powder
C (wt%) TCD 46.5
H (wt%) TCD 3.3
O (wt%) IS 18.2
N (wt%) TCD 0.37
S (wt%) JIS K 2541 0.08
Ca (wt%) JIS K 0102 50.3 10.0
SiO2 (wt%) CIP 4.5
Al (wt%) JIS K 0102 58.4 1.5
Na (wt%) AAS 0.33
Fe (wt%) JIS K 0102 57.4 0.32
K (wt%) AAS 0.11
T-Cl (wt%) TS Z 0025 1.4
Org.Cl (wt%) (T-Cl)-(Inorg.Cl) 0.1
Inorg.Cl (wt%) TS Z 0025 1.3
Terephthalic acid (wt%) HPLC 0.049
Benzoic acid (wt%) HPLC 0.021
Oil content (mg kg−1 ) N-C6 extraction 490
T-Hg (mg kg−1 ) Government guide lines ND ND (<0.005)
R-Hg (mg kg−1 ) Government guide lines ND ND
Cd (mg kg−1 ) JIS K 0102 55.3 3.3 ND (<0.01)
Pb (mg kg−1 ) JIS K 0102 55.4 33 ND (<0.01)
Cr+6 (mg kg−1 ) JIS K 0102 65.2.4 ND ND (<0.01)
As (mg kg−1 ) JIS K 0102 63.1 ND ND (<0.01)
Se (mg kg−1 ) JIS K 0102 67.3 ND ND (<0.01)
T-Cr (mg kg−1 ) JIS K 0102 65.1.4 28
Zn (mg kg−1 ) JIS K 0102 53.3 350
Mn (mg kg−1 ) JIS K 0102 56.4 160
Ni (mg kg−1 ) JIS K 0102 59.3 32
Total heating value (kJ kg−1 ) JIS K 2279 17,830
Incandescence loss (wt%) Government guide lines 58.5
Flash point (◦ C) ASTM E659 >510
Bulk density 0.38
Mean particle size (Nm) 6.0
DXN (pg TEQ g−1 ) 0.0033
ND: not detected

Table 26.13 Material balance
Pretreatment Pyrolysis Whole plant (wt%)

Waste plastics bale 100.0 100.0
Residue in pretreatment 2.0 2.0
Water in the bale 6.0 6.0
Pretreated plastics pellet 92.0 100.0 (92.0)
Distilled light oil (31.0) (28.5)
Distilled medium oil (4.5) (4.1)
Distilled heavy oil (26.5) (24.4)
Whole pyrolysis oil 62.0 57.0
Hydrochloric acid as HCl 1.0 0.9
Pyrolysis residue 17.5 16.1
Off-gas 19.5 18.0
Water in waste plastics

Sorted materials 6.0%
2.0%
Hydrochloric acid
0.9% Pyrolysis oil
57.0%
Distilled light oil
Off gas 28.5% (50)
18.0%
Distilled medium oil
4.1% (7)
Distilled heavy oil

24.4% (43)
Pyrolysis residue
16.1% based on waste plastics bale
wt.%,
Figure 26.16 Material balance
Table 26.14 Consumption figures
Pretreatment Pyrolysis Whole plant

per bale per pellet per bale
Electric power (kWh t−1 ) 230 1200 1334
Fuel (kg t−1 ) 200 184
NaOH (kg t−1 ) 8.5 7.8
Ca(OH)2 (kg t−1 ) 40 36.8
Water (t t−1 ) 10 9.2
LPG (Nm 3 t−1 ) 0.1 0.09
Wastewater (t t−1 ) 2.5 2.3
Table 26.15 Heat balance
Input (MJ/kg bale)

Enthalpy of waste plastics 33.5
Electric power 11.3
Fuel 8.8
Total 53.6
Output
Heating value of oils 27.2
Heating value of off gas 8.6
Heating value of residue 3.1
Total 38.9
Input total/output total = 72.6%
Table 26.16 Output applications
Yield (wt%)∗ Applications

Distilled light oil 20.0 Fuel for furnaces and incinerators in ER
plant
Distilled light oil, remainder 11.0 Feedstock recycling in petroleum FSR
refinery plant
Distilled medium oil 4.5 Fuel for boiler in outside factory ER
Distilled heavy oil 21.0 Fuel for cogeneration in plant ER
Distilled heavy oil, remainder 5.5 Fuel for boiler in outside factory ER
Hydrochloric acid 1.0 Wastewater after neutralization W
Pyrolysis residue 17.5 Supplementary fuel for outside sludge ER
incinerator
Off-gas 19.5 Burnt in incinerator and recovered as ER
steam in the exhaust gas boiler
Total 100.0
ER energy recovery; FSR feedstock recycling; W waste

∗
Yield per waste plastics pellet
The total energy efficiency of the plant, which is determined by the total available output
energy and total input energy, reaches 72.6%. These heat balance data are available for
LCA (life-cycle assessment).
3.7 APPLICATION OF THE OUTPUTS
Table 26.16 shows the applications of outputs in the pyrolysis and distillation sections.
Recently, a portion of light oil is being sent to a petroleum refinery plant as feedstock recy-
cling. All other outputs, such as oils, off gas, residue are used for energy recovery. Only
hydrochloric acid is not recycled because of the conditions described in Section 3.4.2.
Table 26.16. indicates that 11.0% of output is applied for feedstock recycling, 88% is for
energy recovery and 1% is for waste. On the other hand, 60.5% of output is thermally
used in plant, 38.5% is shipped outside, and 1.0% is waste.
3.8 ENVIRONMENTAL ASPECTS
3.8.1 Wastewater
All plant wastewater, including the neutralized hydrochloric acid, is transferred to city
sewage treatment facilities. The results of the wastewater analysis at the border between
the plant and its surroundings, and the city regulation data are shown in Table 26.17. The
table shows that all city regulations are met.
3.8.2 Waste Gas

All waste gases from the pyrolysis plant and distillation section generated by burning
the off-gas and distilled light oil in furnaces and incinerators are finally vented to the
Table 26.17 Analytical results for wastewater
Property Analytical method Analytical data Regulation∗

pH JIS K 0102 12.1 7.7 5–9
SS (mg l−1 ) JIS K 0102 14.1 11 <600
BOD (mg l−1 ) JIS K 0102 21 & 32.3 38 <600
n-C6 extraction
Mineral oil (mg l−1 ) JIS K 0102 20 <1 <5
Other oils (mg l−1 ) JIS K 0102 17 <1 <30
I2 consumption (mg l−1 ) Government guide lines <220
Cd (mg l−1 ) JIS K 0102 55.3 <0.005 <0.1
CN (mg l−1 ) JIS K 0102 38,1.2,3 <0.1 <1
Pb (mg l−1 ) JIS K 0102 54.3 <0.005 <0.1
Cr+6 (mg l−1 ) JIS K 0102 65.1.4,2.1 <0.04 <0.5
As (mg l−1 ) JIS K 0102 61.3 <0.005 <0.1
T-Hg (mg l−1 ) Government guide lines <0.0005 <0.005
Cu (mg l−1 ) JIS K 0102 52.4 0.01 <3
Zn (mg l−1 ) JIS K 0102 53.3 0.07 <5
Soluble Fe (mg l−1 ) JIS K 0102 57.4 0.05 <10
Soluble Mn (mg l−1 ) JIS K 0102 56.4 0.45 <10
T-Cr (mg l−1 ) JIS K 0102 65.1.4 <0.01 <2
F compound (mg l−1 ) JIS K 0102 34.1 <0.1 <8
Dichloromethane (mg l−1 ) JIS K 0125 5.1,2 <0.002 <0.2
CCl4 (mg l−1 ) JIS K 0125 5.1,2 <0.0005 <0.02
1,2-Dichloroethane (mg l−1 ) JIS K 0125 5.1,2 <0.0005 <0.04
1,1-Dichloroethylene (mg l−1 ) JIS K 0125 5.1,2 <0.002 <0.2
cis-1,2-Dichloroethylene (mg l−1 ) JIS K 0125 5.1,2 <0.004 <0.4
1,1,1-Trichloroethane (mg l−1 ) JIS K 0125 5.1,2 <0.1 <3
1,1,2-Trichloroethane (mg l−1 ) JIS K 0125 5.1,2 <0.0006 <0.06
Trichloroethylene (mg l−1 ) JIS K 0125 5.1,2 <0.003 <0.3
Tetrachloroethylene (mg l−1 ) JIS K 0125 5.1,2 <0.001 <0.1
1,3-Dichloropropene (mg l−1 ) JIS K 0125 5.1,2 <0.0005 <0.02
Benzene (mg l−1 ) JIS K 0125 5.1,2 <0.001 <0.1
Seren (mg l−1 ) JIS K 0102 67.3 <0.005 <0.1
Phenols (mg l−1 ) JIS K 0102 28.1.2 <0.1 <5
∗
According to Sapporo city regulation
Table 26.18 Analytical results for waste gas
Property Analytical Waste gas from plant Waste gas from CG

method
Analysis data Regulation∗ Analysis data Regulation∗
Fuel used Distilled light oil and off-gas Distilled heavy oil
Dust(6%O2 ) (g/N m3 ) JIS Z8808 <0.001 <0.15
Dust(13%O2 ) (g/N m3 ) JIS Z8808 0.02 <0.10
SOx (ppm) JIS K0103 <14 <322 2 <98
NOx (6%O2 ) (ppm) JIS B7982 111 <150
NOx (13%O2 ) (ppm) JIS B7982 850 <950
HCl (12%O2 ) (mg/N m3 ) JIS K0107 <3 <49
HCl (13%O2 ) (mg/N m3 ) JIS K0107 1.3
DXN (ng TEQ/N m3 ) WHO-TEF 0.0026 0.023
∗
According to Japanese national regulation
atmosphere through a central vent stack, while the waste gas from the cogeneration
facilities, which burn distilled heavy oil, is vented to a dedicated stack. Table 26.18
shows the analyzed results of both waste gases. All items clear the national regulation,
and dioxin content in the waste gases is below 0.1 ng TEQ/N m3 .
3.9 CHARACTERISTICS OF THE PLANT
3.9.1 Pyrolysis of Waste Plastics Containing PET and PVC

The pyrolysis process for polyolefin wastes only is simple and operation is easy. In
addition, oil yield is high and operation costs are low. However, the SPR plant is designed
to be operated using household waste plastics, which contain PVC, PVDC, PET and many
other kinds of plastics, as shown in Figure 26.13. After plant start-up in 2000, it became
clear that the organic acids, such as terephthalic acid and benzoic acid, generated by the
hydrolysis and pyrolysis of PET, can cause operational instability due to corrosion at
higher temperature ranges and blocking problems in the equipment and pipes.
To overcome these problems, Ca(OH)2 powder was added in waste plastics input [1].
As a result, stable process operation was attained because the organic acids generated in
the dehydrochlorinator and pyrolysis reactor were converted to chemically stable Ca salts.
The problematic terephthalic acid changed to calcium terephthalate, which is a solid and
is stable up to approximately 600◦ C [2]. The HCl separated from PVC is also fixed in
CaCl2 , and the phthalic anhydride generated from the plasticizer contained in flexible PVC
is also stabilized. The blocking problems on dehydrochlorinating gas line by terephthalic
acid due to its sublimation temperature of 300◦ C and crystallization of phthalic anhydride
at 230◦ C have also been solved.
Thus, stable operation of the pyrolysis plant for household plastics was successful,
although the residue volume increased with higher chlorine content and the oil yield
decreased.
In addition, the HCl content of oil decreased, moreover the off-gas scrubbing system, in
which light oil was washed by NaOH aqueous solution, was out of operation; NaOH con-
sumption decreased, and process wastewater also decreased. Reactivity (pH in extracted
water) of the oils was improved from ‘acid’ (pH: below 4.6) to ‘natural’ (pH: above 4.6).
3.9.2 Quality of Oils for Energy Recovery Applications

The three types of distilled oils have a good reputation and have not created problems
in energy recovery applications. The higher pour point and higher viscosity problem of
heavy oil was solved by keeping the heavy oil above 60◦ C using steam tracing. At this
temperature, heavy oil is liquid and has a low viscosity for processing, tank storage,
transportation by truck, or burning in furnaces and incinerators. Therefore, no catalyst is
used for the cracking of heavy oil.
3.9.3 Feedstock Recycling of the Distilled Light Oil

After research and development was conducted with Japan Energy Corporation (JEC), the
remaining distilled light oil has been applied at JEC’s petroleum refinery plant as feedstock
recycling since April 2004. To date, JEC has not reported operational problems.
3.9.4 Utilization of Pyrolysis Residue

The residue consists of mainly carbon and has a high heating value, as shown in
Table 26.12. However, applications could not be found and the residue was landfilled
as waste, after costly packaging in a flexible container because the residue was a fine dry
powder and caused dust problems upon handling. The codevelopment work with Sap-
poro city successfully utilized the residue in the sludge incinerator as supplementary fuel.
However, dust was still a problem in this application. To resolve the problem and to find
better applications, pelletizing facilities for this residue were installed in April 2004. As
a result, the dust problem was solved and better applications are expected.
3.9.5 High Recycling Ratio

As mentioned above, the only wastes discharged from the plant are hydrochloric acid,
pretreatment residue, and moisture contained in the waste plastics. Therefore, the recycling
ratio is calculated as 99.0 wt% in the pyrolysis and distillation sections, and 91.1 wt%
in the whole plant as shown in Table 26.13. The heat balance shown in the Table 26.15
indicates that the total heat recovery ratio is 72.6%.
3.9.6 Low Running Cost

The running costs has been remarkably improved by the following developments:
1. Operating capacity was increased to 110–120% of designed capacity;
2. Energy costs are very low, because the heavy oil is used for the generation of electrical
power supplied by cogenerator, and light oil is used for the furnaces and incinerators;
3. Waste costs are also very low because the only waste requiring disposal is the residue
from the pretreatment section and hydrochloric acid, and these represent only 2 and
0.9% of the waste plastics bales, respectively.
REFERENCES
1. Toshiba Corporation, Japanese Patent, P3435399, 30 May 2003.

2. T. Yoshioka, E. Kitagawa, T. Mizoguchi and A. Okuwaki, Chemistry Letters, 33(3),
282, (2004).
3. Y. Sato, K. Saito and H. Tachibana, Pyrolysis of household waste plastics, The Japan
Society of Waste Management Experts, 13(2), (2002).
4. H. Tachibana, Current situation and future aspect of chemical recycling of waste
plastics, especially for pyrolysis technology, Plastics Age, 49, (2003).
5. H. Tachibana, Current situation of waste plastics pyrolysis technology, 6th FSRJ,
Hokkaido University, 30 September 2003.
4 MIKASA WASTE PLASTIC LIQUEFACTION PLANT [1]
K. Tada
4.1 PLANT OUTLINE
Development of liquefaction of waste plastics via thermal cracking by Kubota Co. Ltd
was started during the oil crisis in the 1970s, but the yield and quality of reclaimed oil
as well as cost were unsatisfactory. At the beginning of the 1990s, a catalytic cracking
process was developed by joint research among IIT, Fuji Recycle Co. Ltd, and Mobil Oil
Co. Ltd, and the output of reclaimed oil has been markedly improved. Kubota, with Fuji
Recycle, has started to operate a liquefaction plant for industrial waste plastics with output
5000 t/yr at Aioi. A test operation has finished at Saga city, pretreating plastic containers
and packaging waste. As a result of such extensive development, the Douo Liquefaction
Center was founded in April 1999 under the leadership of Kubota in Mikasa city. The
capacity is 6000 t/yr of sorted waste plastics, and 3000 kl/yr of product oil. Commercial
operation was began in April 2000, but stopped in the end of March 2004. The plant is
shown in Figure 26.17.
The flow diagram of the pretreatment and liquefaction processes is shown in Figure 26.18.
4.2.1 Pretreatment Process

Foreign materials such as metals, sand, etc., are removed from domestic waste plastics in
the pretreatment process. Mikasa does not have a large population and thus waste plastics
have to be collected from various municipalities in Hokkaido.
Figure 26.17 Liquefaction plant at Mikasa
The waste plastics are put into the receiving hopper and conveyed to pretreatment
machines, i.e. first and second crushers, vibration separator, air separator, dryer, magnetic
separator, aluminum separator, and pelletizers. Plastic pellets having bulk density of 0.35
are obtained.
4.2.2 Liquefaction Process

Plastic pellets conveyed from the pretreatment process are fed into molten plastic tanks by
the feed conveyor. The pellets including PVC are melted and agitated in the tank at 300◦ C
for 2 h. At this stage, the dehydrochlorination reaction is sufficient to remove chlorine in
the fluff. This is a characteristic of this process, since the modification catalyst of ZSM-5,
sensitive to chlorine, is used in the cracking step. The generated gas is collected, and
can be reused to produce hydrochloric acid, but it is currently neutralized with sodium
hydroxide and discarded in the sewage water.
The molten plastic is then sent to a thermal cracking tank from the dehydrochlorina-
tion tanks, and heated to 400◦ C for gasifying. After gasification, hydrocarbons containing
heavy fractions are treated by a neutralization tower to remove hydrogen chloride, com-
pletely. Then, the hydrocarbon gases are sent into a decomposer where they are cracked
and turned into light gas by the catalyst. The decomposed gas is recondensed by the two
condensers so that gas oil and naphtha fractions are obtained. The naphtha and noncon-
densed gases are self-consumed as fuel for furnaces in the plant. The gas oil is sold as
fuel for many uses such as boilers and diesel generators.
Pretreatment process Liquefaction process
Condenser Condenser Mixed oil tank Steam Exhaust gas

Waste plastic Vibration separator (Spray tower)
Treatment facility
Treatment facility
Magnetic separator tower for discharge
Crusher Gas
washing
tank Boiler water Waste heat
Al separator boiler
L.B.P. oil Sublimate Treated
Thickner
Crusher waste water
Waste water treatment
Sublimate
Neutralization tank Gases
for acid gas
Condenser
Thermal
Al separator Hopper cracking tank
Wind
LIQUEFACTION OF PLASTIC WASTES IN JAPAN
separator
Thermal
decomposition
tank Condenser
Dryer
Light oil
Pelletizer Melting
Magnetic
tanks
separator
Pellet silo
Heater for oil
Settler
Heavy oil
Carbon residue1 Carbon residue2 Carbon residue

Deodorizer
Figure 26.18 Flow diagram of the pretreatment and liquefaction processes. (Reproduced by permission of the Kubota Corporation)
697
Table 26.19 Properties of light and heavy oils
Reactivity Light oil Heavy oil

◦
Density (15 C) (g/cm3 ) 0.7816 0.8375
◦
Kinetic viscosity (30 C)(CSt) 0.63
Kinetic viscosity (50◦ C)(CSt) 2.31
Pour point (◦ C) <−45 12.5
Moisture (vol%) 0.00 0.00
Flash point (◦ C) <−20 25
Heating value (cal/g) 9687 10778
pH neutral neutral
Cetane number 27.8
Elemental analysis
N (wt ppm) 820 800
S (wt ppm) 540 1510
Total Cl (wt ppm) 5 23
Inorganic Cl (wt ppm) <1 2
Organic Cl (wt ppm) 5 21
Hydrocarbons
Saturated (vol%) 30.9 54.9
Unsaturated (vol%) 18.0 22.8
Aromatics (vol%) 51.1 22.3
Ash (wt%) <0.01 <0.001
4.3 QUALITY AND APPLICATION OF RECLAIMED OIL
The cracking product oil is condensed to two fractions as light and heavy oils. Their
properties are shown in Table 26.19.
The light fraction of the reclaimed oil has the property of gasoline in its density due to an
effect of the catalytic treatment. In addition, the very low chlorine content both in light and
heavy oils indicate another characteristic, but sulfur content seems to be relatively higher
compared with those for the other pyrolysis oils. Clearly, these low chlorine contents
have been achieved by high removal of chlorine in the dehydrochlorination process and
the gasification process of primary cracking oil. Thus, the oil has the potential to be
fed into refinery plants as a global recycle system. The distillation properties of these
oils are shown in Figure 26.19. The distillation curves of light oil indicate the effect of
modification by the catalytic process.
4.4 MATERIAL BALANCE
The material balance is shown in Figure 26.20. The collected waste plastics are not
satisfactory as fluff raw material, with relatively large amounts of plastics being selected
and removed at the pretreatment process.
Although the residence time of plastic melt in the dehydrochlorination process is very
long, the amount of HCl gas evolved is less than in the liquefaction processes of Niigata
and Sapporo. This may indicate that PVC and PVDC materials are removed effectively
400
Decomposition
350
Heavy oil
300
Temperature (°C)
250
200
150
Light oil
100
50
0
0 20 40 60 80 100
Degree of distillation (%)
Figure 26.19 Distillation curves of light and heavy oils
Waste plastics bale

100
Selection Foreign material + water

+
Drying 19
Pelletizing
81
HCl 1
Residue 1 Melting
Exhaust gas 4
19 81
L. B. oil 18
Residue 2 Cracking
8 49
Heavy oil Light oil Exhaust gas

20 18 3 (Wt%)
Figure 26.20 Material balance

Waste plastics bale

100
Selected plastics
(Pre-treatment)
5
(Liquefaction)
Residues Product oils Exhaust gases

16 56 23
Self consumption For sale

28 28
Steam Cracking Exhaust gas, Cooling water

18 11 22
Figure 26.21 Energy balance
on pretreatment, especially, in the air separation. Practically 19% of foreign materials

including waste plastics is removed during the pretreatment.
4.5 HIGH ENERGY COLLECTION

The energy balance is shown in Figure 26.21. The heating values of removed plastics are
low compared with their weight, 19%. This shows that the quality of collected plastics is
not appropriate for liquefaction since it contains PVC, PVDC, PET, etc., which are low
in heating value.
Conversion performance of reclaimed oil and hydrocarbon gases reaches 70% or higher.
Two kinds of carbon residues are formed in the dehydrochlorination and thermal cracking
processes. They can also used as solid fuel for industries. Their compositions are shown
in Table 26.20.
The heavy metal and chlorine contents seem to be lower in the thermal cracking residue.
They are expected to remain higher in the dehydrochlorination residue, since they are fixed
in it as inorganic chlorides.
4.6 CHARACTERISTICS OF THE PLANT

The process is operated at relatively low working temperature (∼400◦ C) and nearly atmo-
spheric working pressure. Further melting and cracking processes are both heat-absorbing
Table 26.20 Composition of carbon residues
Residue Residue
Hg and/or Hg-compounds (mg/kg) <0.01 <0.01
Cd and/or Cd-compounds (mg/kg) <2.0 2.5
Pb and/or Pb-compounds (mg/kg) <20 <20
As and/or As-compounds (mg/kg) <0.5 <0.5
Cu and/or Cu-compounds (mg/kg) <20 <20
Zn and/or Zn-compounds (mg/kg) 42 91
Fluorine compounds (mg/kg) 8
Fe (mg/kg) 810 640
Mn (mg/kg) 30 71
Cl (wt%) 1.38 0.92
S (wt%) <0.01 0.06
C (wt%) 75 78.6
N (wt%) 0.36 0.5
H (wt%) 9.05 7.8
Ca (mg/kg) 1000 2500
Al (mg/kg) <400 2200
Ignition loss (400◦ C, %) 25.26
(800◦ C, %) 91.6 91.41
(Date) May 2000 September 2000
Table 26.21 Composition of carbon

residue
Total Cl (wt%) 1.38

C (wt%) 75
H (wt%) 9.05
N (wt%) 0.36
S (wt%) <0.01
Ca (wt ppm) 91
Cd (wt ppm)
Pb (wt ppm) 640
Cu (wt ppm) 71
Zn (wt ppm) 0.92
Mn (wt ppm) 0.06
Fe (wt ppm) 78.6
Al (wt ppm) 0.5
Hg (wt ppm) 7.8
As (wt ppm) 2500
Ignition loss (800◦ C, %) 91.6
reactions. This guarantees safer operation of the plant. This is a common advantage with
liquefaction using pyrolysis, but is very important for the municipality and its residents.
4.6.1 De-hydrochlorination Treatment

The chlorine in the fluff is sufficiently removed from the melted plastics in the molten
plastic tanks during the long holding time of 2 h. However, total chlorine in the melt is
present as inorganic chlorides as shown in Table 26.21, and only 0.25% Cl2 remains in
this process. It is well-known that the chlorine in pure PVC is removed easily within a
few minutes at 300◦ C [2]. This chlorine is partly caught as inorganic chlorides by reaction
of HCl gas released and inorganic materials and metals, that stay in the plastic melt. But,
it has been also disclosed that the chlorine in PVDC is removed to only 50–60%, even at
400◦ C [3]. Thus, the remaining organic chlorine in the dehydrochlorination residue may
originate from the residual chlorine in PVDC film, which is one of the major wrapping
films in Japan and is present in the waste plastics.
The removal of foreign plastics and the long heating time on dehydrochlorination
produce a similar effect to Ca(OH)2 addition in the other liquefaction plants. Consequently,
corrosion by hydrogen chloride can be kept to a minimum. This means that maintenance
costs of the plant are remarkably less.
4.6.2 Neutralization of Gas Oil

The capture of HCl gas just before the thermal cracking is another characteristic of this
process. The two tanks are alternatively used to protect the catalyst from HCl attack.
Activated charcoal prepared from palm shell is applied at a loading of 13% K2 CO3 .
4.7 APPLICATION OF THE SYSTEM
Air and water pollution are sufficiently managed according to the law and ordinance, as
in other liquefaction processes. In addition, this process can be applied to treat waste
plastics from households, from industry and from agriculture, since the composition of
plastic containers and packaging is well known (i.e. they contain PVC, PVDC, and ABS,
and sometimes thermosetting plastics).
REFERENCES
1. K. Tada, Kankyou Gijutsu, (2000).(In Japanese).

2. T. Yoshioka, T. Akama, M. Uchida, A. Okuwaki, Chem.Letters, 322–323 (2000).
3. T. Akama, T. Yoshioka, T. Suzuki, M. Uchida, A. Okuwaki, Chem.Letters, 540–541
(2001).
5 THE SCOPE OF LIQUEFACTION IN JAPAN
A. Okuwaki and T. Yoshioka
5.1 PRESENT STATUS OF FEEDSTOCK RECYCLING [1]
The amounts of collection planned by the municipalities, the contracted amount with
municipalities, the amount of acceptance by JCPRA for the recycling of plastics into
(Unit; thoutand tons)
600
Collecting plan by municipality
500 Amount contracted by municipality

Amount accepted by the coorperate body
400
300
200
100
0
2000 2001 2002 2003
Figure 26.22 Collection plan, municipality contract and acceptance by JCPRA
containers and packaging are shown in Figure 26.22, since the Plastic Recycling Law
came into effect in 2000.
The planned amount of collection and sorting by municipalities increased rapidly to
2001, but tended to saturate by 2002 at 487 000 tons, even though the rates of both
numbers of the municipalities and the population engaged in the plastic waste recycling
are projected to increase until 2007, to 82.1 and 83.5%, respectively. This is caused by
the fact that the collection and sorting costs that are payable by the municipality are quite
high, compared with the total incineration cost, composed of collection and incineration
of mixed garbage, with landfill of ash. As a result, many municipalities do not seem to
want to progress the recycling of plastic containers and packaging.
On the other hand, the facilities of feedstock recycling plants have been constructed
corresponding to the planned amount, and the amount accepted has increased sharply.
This indicates that there is competition among the technologies and the recycling plants
and results in the sharp drop in the tender price [2].
Total cost for feedstock recycling of plastic containers and packaging consists of the
collection and baling costs, which are paid by the municipality, and the recycling cost
paid by businesses that manufacture or use the containers and businesses that use the
relevant packaging. The present status and scope for feedstock recycling are discussed
below.
5.1.1 Municipality Expense

In Table 26.22, the costs for collection and baling of post-use plastic containers and
packaging paid by the municipality in 2000 are shown [3]. The recycling cost in the third
column corresponds to the expense paid by the municipality instead of small businesses.
Table 26.22 Municipality expenses for the collection and baling for post-use containers
and packaging plastics in 2000
Collection Baling Recycling∗ Total

Number of municipalities 20 27 27 26
Maximum (×103 Yen/t) 358 679 10 761
Minimum (×103 Yen/t) 19 12 0.3 6
Number average (×103 Yen/t) 84 91 6 196
Weight average (×103 Yen/t) 69 42 5 104
∗
For small businesses
The high total cost has to be paid by municipalities. This high cost is the greatest obstacle
to expanding the feedstock recycling of waste plastics.
Japanese people understand and cooperate significantly with the spirit of the Plastic
Recycling Law and separate the plastics containers and packaging from garbage in every-
day life. But the collection of waste plastics involves quite high initial costs, at least
two to three times that for mixed garbage, since the waste plastics alone are quite light
compared with mixed garbage.
Second, the baling cost add to the collection cost, since the collected waste plastic has
to be baled after removing foreign materials such as metals, glasses, etc. for recycling.
Usually, these total costs, including collection and baling far exceed the total incineration
cost, including collection and incineration of garbage, and landfill of ash. As a result
of these economic conditions, almost all local governments are reluctant to progress the
recycling of waste plastics.
An example of collection and baling costs in 2002 in Sendai city with a population over
one million, is shown in Table 26.23 compared with that for the total incineration cost.
In 2002, about 10 000 tons of bales were prepared from plastic containers and packaging.
The major use was blast furnace application in JFE Steel at Kawasaki.
Evidently, the total incineration cost is much lower than the feedstock recycling cost.
The average waste treatment cost in Japan attained 50 Yen/kg or higher in 2001 [4]. The
old incineration plant and landfill site, of course, contribute significantly to the lower cost.
The total incineration cost in Sendai is lower than the average cost in Japan. Sendai city,
however, has started a new incineration plant, 600 t/d in capacity which should elevate
incineration cost at least 50% over the present one.
Rationalization of the collection system by the municipality may reduce the cost a
little, but the most important way of reducing collection cost is to develop an innovative
Table 26.23 An example of collection and baling cost (Yen/t)
Plastic recycling in 2002 Collection Baling and recycling Total
24 000 33 000 57 000

∗
Garbage incineration in 2001 Collection Incineration Landfill Total
9 024 15 283 8 325 25 519

∗
Ash 14.56%
collection method to densify the light weight plastic containers and packaging in situ
during their collection.
One method available to reduce baling cost is to locate the recycling plant beside the
baling plant. This is absolutely important for every process, especially for liquefaction
operated on a relatively small scale, but does not necessarily harmonize with the Plastic
Recycling Law.
Baling has been introduced according to the bid system by JCPRA to ensure equity for
all enterprises permitted by JCPRA, having material and feedstock recycling techniques.
At present, this equity is preferential, but this system is not always effective or favorable
for reducing the baling cost and progressing feedstock recycling. So, some strange phe-
nomena are associated with the recycling of bales. For example, there is a large baling
plant adjacent to the SPR plant, with only 10 m distance between them. A lot of bales
prepared by Sapporo city have been shared between an iron and steel company and SPR.
The company’s bales are carried a long distance from the baling equipment. On the other
hand, the SPR bales are transferred only 10 m and are broken into plastic fluff to form
pellets. If all the waste plastics collected were liquefied at SRP, the baling cost will be
reduced by half. At Niigata, half of the collection to their baling facility is directly fed to
the liquefaction plant as described in Section 2. This process aids the reduction of cost
for both Niigata city and the company.
5.1.2 Business Expense
The costs of recycling for different feedstock techniques in 2003 are shown in Table 26.24,
which includes the transportation cost from municipality to the recycling plant. These costs
are all paid by businesses, except for small businesses of (paid for by municipalities and
8% in the case of Sendai city).
The high cost for mechanical recycling method is due to the priority for feedstock
recycling. The cost reduction for businesses depends to a great extent on improvement
of feedstock recycling technologies. Another method could easily save the expensive
transportation cost, namely, the light plastic containers and packaging should be recycled
as near as possible to where they are collected.
Table 26.24 Recycling costs∗ for different

techniques
Method Cost (Yen/kg)

Mechanical recycling 108
Liquefaction 98
Blast furnace 83
Coke oven 78
Gasification 80
Average 88
∗
Includes transportation from municipality to plant
5.1.3 Status of Liquefaction in Feedstock Recycling

Feedstock recycling process, other than liquefaction, involve large-scale basic industrial
equipment, blast furnaces and coke ovens for iron and steel applications and ammonia
plants for gasification. Thus, their recycling process can be evaluated as a pretreatment for
such basic industries. Actually, no chemical treatment is performed in the blast furnace
application at present.
However, liquefaction of waste plastics dose not have such a combination with a
petroleum refinery at present. Clearly, small liquefaction plants producing pyrolysis oil
in isolation necessarily incur a high treatment cost. Unfortunately, sufficient quantities of
bales for maintaining a high rate of operation is not feasible under the bid system. This
brings about a vicious circle of high operating cost–low operating rate.
The other issue is the carbon number distribution of pyrolysis oil containing low carbon
number hydrocarbons. This affords a relatively high yield of gasoline component. The
light oil is subject to the expensive gasoline tax for external sale.
The final factors on operational of a liquefaction plant are stoppages and corrosion
problems caused by the decomposition products from pyrolysis of PET material, yielding
terephthalic acid and benzoic acid.
5.2 SCOPE FOR LIQUEFACTION
The characteristic features of liquefaction described above necessarily result in unstable

operation and high cost of liquefaction via pyrolysis. Recently, the operational problems
have been solved by adding calcium hydroxide to control the evaporation and decompo-
sition of terephthalate components such as calcium terephthalate [5].
5.2.1 Cost Reduction

This is a vital problem for liquefaction and has failed in the advanced German trials.
In Japan, liquefaction has first to defeat incineration, the technique that has prevailed in
most municipalities. The rate of incineration in municipalities has reached 80% or so
and 40 million tons of garbage are incinerated every year. From this point of view, the
reduction of collection and baling costs as described above is an easy way to achieve this.
Second is the question of how to reduce the liquefaction cost compared with those for
the other feedstock recycling methods, such as application in the iron and steel industry
and gasification for ammonia synthesis. These methods have the merits discussed above.
On the other hand, liquefaction has many weak points, it is small in scale, complicated
with a mixed raw material for fine technology, and has a low degree of operation, 50%
or so.
Simplification of the present liquefaction processes by removing several pieces of equip-
ment (for example, the distillation column) will be one important solution. The present
complex facilities are necessary to treat chlorine-containing plastics and PET materials
from plastic containers and packaging. They provide only small amounts of oil on pyrol-
ysis, but cause various difficulties. The amount of the former materials tends to decrease
due to the replacement of PVC and PVDC materials with polyolefins, but the latter is
increasing gradually, due to recycled PET sheet which is used, for example in egg cartons.
Removal of such materials is not so difficult by present separation methods, as used in
mechanical recycling, though PE, PP and PS are present to some extent.
Such simplification will make it possible to reduce the high operating cost through
the reduction of investment to the liquefaction plant, to one-half, or to a maximum of
one-third of the present values [6].
5.2.2 A New Recycling Route for Light Oil

The characteristic distribution in the pyrolysis oil is a low yield of medium oil, for diesel
or boiler fuel, but a high yield of light oil. The light oil has similar properties to naphtha
from crude oil. If this is used in the recycling process as fuel, no volatile oil tax (gasoline
tax) is imposed. However, in the case of external sale, the user has to pay the tax. As a
result of regulation by the volatile oil tax law, the light oil is not appropriate for outside
sale at all.
Recently however, a breakthrough has emerged in the cooperative research between
Japan Energy Co. Ltd and the joint group of liquefaction enterprises. The project has run
a trial for introducing the light oil into the pipeline in the equipment (see Section 3). The
results indicate that a small amount of chlorine, several tens of ppm, contained in the
light oil will have no effect on the operation in the main stream.
The result of this trial has been taken into account. In the case of recycling the light
oil to naphtha, the gasoline tax or kerosene tax is not imposed on self-consumption in the
liquefaction process. Light oil produced in Sapporo and Niigata, has been fed 1000 KL
to the Mizushima refinery of Japan Energy Co. Ltd. [7].
5.2.3 Activation for Local Business

The local economy in most districts in Japan has been in a deep recession since the 1990s
and unemployment continues to be problems. The present recycling system well meets
the Plastic Recycling Law. However, from the standpoint of view of the local citizen,
there is a major contradiction. This might lead to a tendency to saturation of the amount
of plastic being recycled.
Many local governments have to pay such high recycling costs, including those of small
businesses, to prepare bales. The company recycling these bales is not always located at
the same municipality; they often have to be transported to the recyclers, far from the
municipalities that prepared the bales. Consumers in a municipality separate the waste
plastics from garbage, and the municipality collects and sorts the material to prepare
bales, but the recycling business is located in another district, or prefecture. This seems
to be one problem in the Plastic Recycling Law that needs to be improved to lower
the environmental load as well as to bring about an activation of local industries and to
provide employment for local citizens. In addition, most local governments have enough
capacity to incinerate their garbage, and waste plastics give no ash on incineration.
Under such considerations of the merits and demerits of recycling plastic containers and
packaging, with the liquefaction plant in the municipality where the bales are prepared
will become an interesting enterprise for many local governments as a tool for activating
the local economy and providing employment opportunities.
The system research division of the Research Association of Feedstock Recycling of
plastics, Japan (FSRJ) has proposed candidate cities, such as Sendai, where there are no
basic industries, such as iron and steel industry and ammonia synthesis [7].
The shortage of plastic containers and packaging should be solved easily by commenc-
ing the collection and baling in mega-cities as Tokyo, Yokohama, Nagoya, Osaka, etc.,
where a lot of factories of big industries are operating. Surely, this will contribute to the
lowering of transportation costs and result in reducing somewhat the load on businesses
having to pay the recycling cost.
ACKNOWLEDGEMENTS
This research was partially supported by the Ministry of Education, Science, Sports and
Culture, Grant-in-Aid for Scientific Research (B), Ministry of Environment, and RISTEX
for JST (Japan Science and Technology Agency).
REFERENCES
1. PWMI: http://www.pwmi.or.jp (in Japanese).

2. A. Okuwaki, Polym,Deg.Stab., 84, 981 (2004).
3. M. Kaji, Presentation at the 6th General Meeting of FSRJ, Waseda University, Tokyo,
6 June 2004.
4. White paper for the Recycling-Orientated Society; 2002 (in Japanese).
5. T.Yoshioka, E.Kitagawa, T.Mizoguchi and, A.Okuwaki, Chem.Lett., 33, 282 (2004).
6. H. Ibe, Presentation at the 6th General Meeting of FSRJ, Waseda University, Tokyo,
6 June 2004.
7. http://www.j-energy.co.jp (in Japanese).
27
Process and Equipment

for Conversions of Waste Plastics
into Fuels
ALKA ZADGAONKAR
Head, Department of Applied Chemistry, G.H. Raisoni College of Engineering.
Res: 9 Buty Layout, RPTS Road, Laxmi Nagar, Nagpur 440016, India
1 INTRODUCTION
Plastic waste is becoming a serious global issue, thanks to extensive plastic usage all over
the world, the treatment of waste plastic has gained the utmost importance. Scientists and
experts all over the world are concerned over this major environmental problem which
is expected to attain mammoth proportions by the year 2010, with an expected annual
increase of global plastic consumption crossing the 5.5% mark.
There are various methods for reutilizing the polymers, each one having its shortcom-
ings or limitations. Yet, thermal and catalytic degradation of plastic into fuel is considered
to be the most effective way of reusing polymers. Of late, experts have begun to pay
attention to pyrolysis, especially thermal or catalytical degradation of plastics.
2 PYROLYSIS
2.1 DEFINITION
Pyrolysis is defined as a chemical degradation reaction that is caused by thermal energy

in the absence of air (oxygen). It is supposed to be one of the most effective methods for
preserving petroleum resources, in addition to preserving the environment by decreasing
the volume of nondegradable waste. Degradation of plastic is achieved by heating at high
temperature, with macromolecules breaking into smaller fragments, consisting valuable
mixtures of hydrocarbons (gas, liquid and solid).
The degradation of different types of waste plastics has been studied in the presence and
absence of a catalyst. It is found that the properties of the products depend significantly on
710 A. ZADGAONKAR
the characteristics of the applied catalyst. A catalyst also reduces the reaction temperature.
The pyrolysis process, requiring high temperatures up to 1 000◦ C can be carried out at
much lower temperature (400–500◦ C) with the use of a proper catalyst. Recycling of
waste plastic by pyrolysis can yield excellent results, even with heterogeneous waste
plastic materials, where segregation is not economic.
2.2 PLASTICS SUITABLE FOR PYROLYSIS
Polymers are structurally made up of carbon atoms linked by single or double bonds.
Hence, each polymer has a specific heat value. For example: Polyethylene and Polypropy-
lene have calorific values of 18 720 BTU/lb and 18 434 BTU/lb, respectively. These
organic molecules have a low decomposition temperature compared with inorganic mat-
ter. Nearly all conventional fuels are organic molecules. The heat content of an organic
molecule depends upon number of carbon atoms in the molecular chain and the complex-
ity of the molecular structure (linear, branched, cyclic, etc.). Thus, when any polymer
decomposes or the polymer structure gets fragmented randomly, each fragment, depend-
ing upon number of carbon atoms, can be classified into various types of fuels. Hence,
pyrolysis of polymers such as PE, PP and PS yield valuable hydrocarbons.
A few polymers such as polyvinyl chloride, ABS, and PET are associated with het-
eroatoms such as Cl, N, and O apart from carbon and hydrogen. During pyrolysis these
heteroatoms get converted into compounds such as HCl, N2 , H2 O etc.
3 PYROLYSIS: MODE OF OPERATION AND APPARATUS
3.1 BATCH PYROLYSIS
The batch-type reactor used for the catalytic pyrolysis of waste plastic is shown in
Figure 27.1. As shown in the figure, the mechanical agitator is installed in the batch-
type reactor wrapped around with an electric heater, to control the pyrolysis temperature
of the waste plastic. The organic vapor generated from waste plastics, is then passed
through the catalytic cracker bed. After that, the vapor is discharged through condensers
I and II, which are maintained at different temperatures for product oil conversion.
The reclaimed oil can be utilized for various applications. In addition, the oil can be
fed into refinery plants as a global recycle system.
3.1.1 Pyrolysis Reactor Configuration

The thermal treatment device for pyrolysis should be properly designed and operated in
order to be more economical in terms of a cost-effective and energy-efficient operation.
The primary driving force for this process is the intraparticle heat conduction. The prin-
ciples of a pyrolyzer design should take the heat transfer and contact mode into account.
Different reactors are used to carry out pyrolysis of the waste plastics. Among them, three
PROCESS AND EQUIPMENT FOR CONVERSIONS OF WASTE PLASTICS 711
Figure 27.1 Batch-type reactor for pyrolysis of waste plastic [1]. 1 uncondensed gas;
2 water outlet for condenser; 3 water inlet for condenser; 4 thermal fluid inlet for
condenser; 5 thermal fluid outlet for condenser; 6 lighter liquid hydrocarbons; 7 liquid
hydrocarbons; 8 agitator
main kinds of reactor: fluidized-bed; rotary kiln; and screw pyrolyzers, are used. A brief
description of these reactors is given below.
3.2 TYPES OF PYROLYZERS
3.2.1 Fluidized-bed Pyrolyzer

The gas fluidized-bed reactor is the most efficient approach to pyrolysis. In this reactor
the waste plastic is suspended around the heating medium and subjected to pyrolysis by
means of immersed heating tubes and gas–solid convective heat transfer. At present the
only difficulty with this reactor is the problem of its structure. Fluidized-bed pyrolyzers
have been designed for pyrolysis of waste tyre rubber in Taiwan and in Hangzou. A
schematic apparatus of a fluidized-bed pyrolyzer is shown in Figure 27.2.
The reactor is constructed with a cylindrical column and an expanded freeboard. The
distributor is a perforated plate. An inert gas matrix composed primary of crystal sand, is
used as the bed material. The blower supplies the inert gas for fluidization or the amount
of air for partial combustion. A cyclone is used to collect fine particles. Scrubbers serve
to quench the off-gases and remove condensables that were withdrawn from reactors.
3.2.2 Rotary Kiln Pyrolyzer

The main advantage of rotary kiln pyrolyzers is that the rotation of the pyrolyzing chamber
guarantees the permanent turning and mixing of the waste plastic, so that the mixture is
continuously homogenized and blended with inert pyrolysis gas. A rotary kiln pyrolyzer
is shown in Figure 27.3.
712 A. ZADGAONKAR
Figure 27.2 Fluidized-bed pyrolyzer [2]. 1 blower; 2 air flowmeter; 3 thermocouples; 4

fluidized-bed reactor; 5 two-stage feeder; 6 cyclone; 7 scrubber; 8 after-burner
Figure 27.3 Rotary kiln pyrolyzer [2]. 1 thermometer; 2 bearing; 3 gear transmission; 4
electric furnace; 5 rotary kiln; 6 temperature controller; 7 seal; 8 two-step condenser; 9
filter; 10 total flowmeter; 11 computer; 12 gas sampler; 13 feed and discharge opening; 14
adjustable-speed motor. (Adapted from Shah, N., Rockwell, J. and Huffman, G.P., Con-
version of Waste Plastic to Oil: Direct Liquefaction versus Pyrolysis and Hydroprocessing,
Energy & Fuels, 13, 832–838 (1999))
The furnace has an adjustable rotation rate of 0.5–10 rpm. The kiln is heated externally.
The sealing of rotary kilns is a difficult task, especially for a pyrolyzer. The internal
pressure of the kiln is higher than atmospheric pressure. A special friction-type seal is
required for a pyrolyzer operating at high temperature. Solid waste with different shapes,
sizes, and heating values can be fed into rotary kilns in batches or continuously.
3.2.3 Screw Pyrolyzer

The screw pyrolyzer, with its lower cost of construction and operation, has great prospects
in the future. A screw pyrolysis conveyer is provided with internal and external heating
modes. It has a special configuration for the removal of the coke formed during the
process, which is a threat to heat transfer, and continuous operation. Figure 27.4 shows
a screw pyrolyzer.
4 PYROLYSIS: THERMAL CRACKING/NONCATALYTIC CRACKING

4.1 OPERATION
The thermal cracking of waste plastic involves breaking of polymeric bonds by the effect
of heat alone. The waste stream may comprise PP, PVC, PET, thermosetting plastic,
2 4 5 8 6 12 1
A
3 11 10 9 7 13 14
Figure 27.4 Screw pyrolyzer [2]. 1 horizontal vessel; 2 gearbox; 3 screw shaft; 4 hopper;
5 mouth for balance; 6 jacket heating; 7 inlet of heating gas; 8 outlet of heating gas; 9–11
drain pipes; 12 outlet of volatile gas; 13 char discharge; 14 baffle
paper, garbage, metals, etc. The heating medium can be sand, thermal fluid or any other
suitable media. The waste plastic is first crushed to 200 mm size and sent to a kiln, which
is maintained at 250–350◦ C. At this temperature, chlorine from the waste is discharged
and the gaseous product is sent to an HCl absorber. The substantially dechlorinated waste
is sent to a mechanically agitated reactor at 350–550◦ C, where pyrolysis occurs. A reflux
tower, which is installed above the thermal cracking reactors, makes it possible to collect
the light oil selectively. The heavy oil fraction, produced by thermal cracking, is condensed
and returned to the thermal cracking reactor for recracking. This enables reduction of the
wax fraction yield.
4.2 PROCESS MECHANISM
All matter has energy stored in its molecular structure and molecules are joined by bonds
with a specific energy that holds them together. If this energy is surpassed it disintegrates
into smaller fragments. Thus, in the pyrolysis process when the heat supplied exceeds
different bond dissociation energies, cleavage of the bonds takes place.
4.3 DEGRADATION OF POLYMERS
When polymers are subjected to elevated temperature in an inert atmosphere they degrade
by different mechanisms, which are described as follows.
4.3.1 Random Depolymerization

This kind of scission is typical of polyethylene (PE). The backbone of the polymer is
broken randomly as all C–C bonds are of the same strength (Figure 27.5). Hence, the
hydrocarbon chain breaks randomly and the resulting products are of the form of alkanes,
alkenes and alkadienes of smaller size. This is a free radical mechanism. The covalent
bond between two carbon atoms is cleaved homolytically to form fragments carrying one
714 A. ZADGAONKAR
H H H H H H H
H C C C … C C C C …
H H H H H H H
Saturated Hydrocarbon Unsaturated Hydrocarbon
Figure 27.5 Random depolymerization
electron each. These fragments with odd electrons are called as free radicals. Random
depolymerization also involves formation of free radicals at some point on polymer back-
bone, producing small fragments of varying chain length.
The structure of polypropylene is similar to PE, except that it possesses branched
methyl groups along its backbone, making every other carbon atom in the chain tertiary
as it holds a methyl group. This leads to scission of the carbon chain, predominantly
between secondary and tertiary carbon atoms.
4.3.2 Side Group Elimination

This involves elimination of side groups attached to the backbone of the polymer, resulting
in the backbone becoming polyunsaturated. In the pyrolysis of polyvinyl chloride, after
elimination of chlorine, a conjugated double bond backbone is obtained (Figure 27.6).
The conjugated chain breaks randomly at the C–C bond, leading to formation of aro-
matic compounds such as benzene, toluene, styrene, etc. The degradation of PVC is
initiated at about 250◦ C with elimination of HCl. Polymers having similar structure, such
as polyvinyl acetate, undergo this type of scission, resulting in formation of a conjugated
double bond backbone.
4.3.3 Chain End Depolymerization

This leads to the formation of monomer. This is a free radical mechanism in which
polymer is degraded to the monomer that makes up the polymer (Figure 27.7). Formation
of a free radical on the backbone of polymer causes the polymer to undergo scission to
form a saturated small molecule and propagate the free radical on the polymer backbone.
In PMMA there are different kinds of bonds since C–H and C=O possess high values
of bond dissociation energy, whereas the bond dissociation energies of C–O and C–C
H Cl H Cl H Cl H Cl H Cl
C C C C C C C C C C
H H H H H H H H H H
−HCl
C C C C C C C C C C
H H H H H H H H H H
cyclization
Aromatics
Figure 27.6 Side group elimination
CH3 CH3 CH
CH2 C CH2 C CH2 C
COOR COOR COOR
Beta
Scission
CH CH CH
CH2 CH + CH2 C + CH2 C
COOR COOR COOR
Monomer
Figure 27.7 Chain end depolymerization of polymethylmethacrylate PMMA (R = CH3 )
are comparable so the C–C bond at the quaternary carbon cleaves first, resulting in the
formation of monomer.
Apart from these three degradation mechanisms, rearrangements of the fractions formed
may take place. A polymer does not undergo only one pyrolysis route always, but multiple
routes may be taken simultaneously. The type of reaction is totally governed by the
strength of bonds in the molecules. The lowest energy path will be favored.
5 PYROLYSIS CATALYST
5.1 ROLE AND EFFECT OF CATALYST
The catalyst plays a vital role in a pyrolysis process. Pyrolysis in the presence of catalyst
requires less energy than a noncatalytic process and results in formation of more branched
716 A. ZADGAONKAR
Si Si Si Si
O O O O O
δ−
H H H H H H H
R C C C H
C C C δ+ C
H H H H H H H H
Polyethylenic fragment
or molecule
Figure 27.8 Mode of fragmentation
hydrocarbons (Figure 27.8). The use of an acid catalyst allows the pyrolysis temperature
to be reduced. A catalyst reduces the pyrolysis initiation reaction time, and improves
output quality and quantity of the product. The catalysts employed are silica–alumina,
synthetic or natural zeolite, synthesized fly ash catalyst (treated with NaOH), which may
be impregnated with NiO, HZSH-5, FeCl2 , etc.
A typical catalyst comprises 20–25% zeolite, 30–35% clay and matrix bound by about
20–30% silica or alumina binder.
Among all varieties of zeolites, the zeolites with 10-membered oxygen rings in their
structure and medium pore size, ZSM-5 and ZSM-11 are remarkably stable as acidic
catalysts.
In the presence of the silica formation of a carbanion ion takes place easily, thus
enhancing the fragmentation reaction at lower temperature.
5.2 PROPERTIES OF CATALYST
The catalyst is an important factor in the pyrolysis process. Various properties of catalysts
also govern the output product in pyrolysis.
5.2.1 Chemical Properties

• Micro activity test (MAT). This test was developed and standardized by ASTM (ASTM-
D-3907). In the MAT test, a sample of cracking catalyst is contacted with gas oil
in a fixed-bed reactor. Gas chromatographic analysis on gas and liquid products
is used to determine the yield structure. Recently, the MAT conditions have been
adapted to simulate commercial units more accurately in terms of contact times.
A higher catalyst activity results in improved conversion and higher regenerator
temperature.
• Hydrogen factor. This is a relative number proportional to the specific hydrogen yield,
defined as specific H2 = H2 yield (100-conversion)/conversion. The hydrogen factor
depends on the catalyst quality and is affected by nickel deposited on an equilibrium
catalyst. The trend of the hydrogen factor is of importance and this can be correlated
with the H2 /CH4 ratio in the unit.
• Zeolite are porous sodium aluminosilicates. Among them only Y zeolites are used
in catalytic cracking. They are preferred because of appropriate pore size (6.5–13.5
Å), high thermal and hydrothermal stability and good acidity. They can be further
tailored into ultrastable Y (USY) zeolites by varying the SiO2 /Al2 O3 ratio and rare
earth content.
• Alumina (Al2 O3 ). Alumina is present in several components of the catalyst such
as zeolite, clay (kaolin) and active matrices. The alumina content of catalyst can
often be used to calculate the degree of exchange when switching to a different
catalyst.
• Rare earth RE2 O3 wt%. The rare earth content of a zeolite indicates the hydro-
gen transfer activity. Higher rare earth content results in more hydrogen transfer
and consequently reduces the product olefinity and research octane level liquid fuel.
Hydrogen transfer terminates the cracking reaction. Thus, reducing cracking from
gasoline to LPG. The specific activity increases in general with rare earth
content.
• Sodium. Sodium acts as a catalyst poison, it neutralizes acid cites. High sodium level
in a catalyst destroys the zeolite. Such catalyst is more sensitive to high temperature
due to increased rates of sintering and surface area destruction; eventually plugging of
cyclone diplegs may occur due to formation of low-melting eutectics.Cyclone diplegs
are the means used to return catalyst collected in cyclones to the reactor. Large addi-
tions of fresh catalyst are required to cope with sodium poisoning.
• Nickel. Nickel is introduced with feed and deposited on the equilibrium catalyst.
Nickel enhances nonselective cracking reactions, particularly those producing more
hydrogen.
5.2.2 Physical Properties

• Surface Area (SA, m2 /g). The surface area is the measure of the catalyst activity
(as long as the same catalyst types are compared) and has a strong effect on the
performance of an Fluidized Catalytic Cracking Unit (FCCU). High surface area
also results in increased adsorption of hydrocarbons, and a higher steam rate in
the stripper may be required. The zeolite and matrix surface areas of a catalyst
can be analysed separately. Matrix pores provide access of the hydrocarbons to
the active zeolite sites and matrix surface area often correlates with the bottoms
conversion activity of the catalyst or the Light Cycle Oil (LCO) yield at constant
conversion.
• Apparent bulk density (ABD, g/ml). ABD is determined by measuring the mass as a
known volume of catalyst settles freely under its own weight. A higher ABD improves
cyclone efficiency, in general. Its effect on catalyst circulation depends on the unit
design and operation, as well as the particle size distribution.
• Particle size distribution (PSD). The PSD is an indicator of the fluidization properties
of the catalyst. In general, fluidization improves as the fraction of 0–40 µm particles
is increased. However, a higher percentage of 0–40 µm particles will also result in
718 A. ZADGAONKAR
greater catalyst losses. The catalyst manufacturers control the PSD of the fresh catalyst,
mainly through the spray drying cycle. In the spray dryer, the catalyst slurry must be
effectively atomized to achieve proper distribution from the particle size distribution;
the average particle size (APS) is calculated. It is not actually the average size of the
catalyst particles, but rather the median value.
• Pore size. The pore size distribution of the catalyst matrix plays a key role in the
catalytic performance of the catalyst. An optimum pore size distribution usually helps
in a balanced distribution of smaller and larger pores, and depends on feedstock type
and cracking conditions. The pore size distribution of the matrix changes when another
component is added; e.g. by adding 35–40% kaolin to a silica–alumina gel, a pore
structure with a significant amount of micropores can be obtained. Figure 27.9
• Pore volume. Pore volume is an indication of the quantity of voids in the catalyst
particles and can be a clue in detecting the type of catalyst deactivation that takes
place in a commercial unit. Hydrothermal deactivation has very little effect on pore
volume, whereas thermal deactivation decreases pore volume.
• X-ray crystallinity. This characteristic is generally indicative of the zeolite content
of the catalyst. It is determined by measuring the area of one or several peaks in
the X-ray diffraction pattern of the catalyst and expressing it as a percentage of the
corresponding area of a reference material (usually a well–crystallized Na Y Zeolite).
X-ray crystallinity measurements are often used by refiners to monitor the quantity of
fresh and equilibrium catalysts.
• Loss on ignition (LOI, wt%). LOI is determined by measuring the loss of weight
(mostly water) upon ignition at 815◦ C for an hour. The measurement is required
because catalysts are paid for on a dry basis. LOI has no effect on catalyst performance.
This test is performed only on the fresh catalyst.
• Attrition index (AI, wt%). A fresh catalyst sample is subjected to high-velocity flu-
idization for a long time. In this process, wear on the particles occurs as they are
Thermally
decomposed
fragment
SA : Mainly
cracking
HZSM-5
mainly
reforming
Figure 27.9 Role of zeolite in pyrolysis

blown against each other and against the wall with a high velocity. The fines formed
are then weighed. The attrition index is defined as the weight % of fines generated
during the fluidization, with respect to the weight of fresh catalyst, excluding fines,
before fluidization. A high AI implies high resistance to attrition. AI levels up to 10
yield low catalyst losses in fines.
6 PYROLYSIS: OUTPUT CHARACTERISTICS
6.1 EFFECT OF TEMPERATURE ON PYROLYSIS PRODUCTS
Polymers are formed by a –C–C–bond skeleton. When a polymer is subjected to pyrol-

ysis, the heat supplied is utilized for breaking this skeleton and thus the process is
endothermic. At higher reaction temperature conversion of polymer to lower hydrocar-
bons increases with temperature and the presence of catalyst A higher ratio of thermal
to catalytic cracking suppresses hydrogen transfer in the C2 –C6 range and enhances the
olefinity, but decreases the degree of branching. Thus diene concentration of LPG and
gasoline increases markedly with temperature. The quality and quantity of output product
also depends upon the rate at which the temperature is raised.
If the contact time is very short it limits the secondary reaction, which contributes to
gas and coke. This results in a reduction of quantity and quality of gas and coke.
The cracking mechanism of polymers follows first-order kinetics.
6.2 BY-PRODUCTS OF PYROLYSIS
Pyrolysis is the process of thermal degradation of hydrocarbons in an oxygen-starved

environment in the presence or absence of catalyst at temperature about 500–700◦ C
for plastic. This process is utilized for the degradation of plastic to lower hydrocar-
bons. The physical state of products depends upon the size of hydrocarbon fraction.
Broadly, these products are classified as solid, liquid and gases. The total output product
by weight is equivalent to total input of feedstock; hence if the percentage of solids or
gases decreases; there is a corresponding increase in the percentage of the liquid fraction
and vice versa.
Gaseous products include LPG range gases; liquid products include liquid hydrocar-
bons; solids include coke/residue. The average composition and properties of the output
products depend upon the following factors.
• properties of catalyst (as discussed earlier);
• operating conditions;
• pressure.
Operating condition can have a great impact on the properties of liquid output, its
composition as well as the overall percentage output of solid, liquid and gaseous product.
When the temperature is increased, rate of reaction increases. Approximately for every
40◦ C rise in temperature, the decomposition rate doubles.
720 A. ZADGAONKAR
When the reactor pressure is high, then the residence time also increases which results
in more unsaturation in the product and hence lower octane number of the gasoline
is obtained. When the reaction is carried out at atmospheric pressure, shorter contact
time reduce the chances of secondary cracking and hydrogen transfer reactions, thereby
increasing the olefinity in the liquid product.
When pyrolysis is performed under vacuum, the spectrum and quality of products
obtained is distinct from other pyrolysis processes (atmospheric). The advantage of
reduced pressure is that the secondary decomposition reactions of gaseous hydrocarbons
are limited.
7 PYROLYSIS OF HETEROATOM POLYMERS

During the pyrolysis of mixed waste plastic, one of the main problems associated with
the feedstock recycling is the presence of plastic containing hetroatoms, e.g. PVC, ABS,
PVDC, etc. Efforts are made to remove the heteroatoms before pyrolysis. Chlorine can
be removed either by thermal degradation or by using a catalyst. The HCl generated in
the process can be used as industrial hydrochloric acid.
7.1 PYROLYSIS OF PVC
PVC degrades around 250–300◦ C, giving HCl. The mechanism of PVC degradation is
highly complex in nature; the free radical path seems to play a major role. The probable
mechanism is that a free radical R• , produced either by impurity or by reaching a desired
temperature, attaches to a methylene group and subtracts H with simultaneous transfer of
the free radical site onto the chain. The labile chlorine atom which is at a β-position with
respect to the free radical chlorine atom is now released as a free radical and stabilizes
the structure.
PVC is basically colorless and turns deep yellow-orange, brown or black, depending
upon concentration of conjugated double bonds, which in turn depends on the degree of
degradation. The role of HCl in this reaction is catalytic since the degradation is acceler-
ated as soon as HCl is evolved. Thus, chlorine is removed from PVC in inorganic form.
Sometimes if chlorine is not removed effectively, then during pyrolysis Chloro-organic
fuels will be obtained. Chloro-organic compounds containing waste-plastic-derived oil is
not useful, as it causes corrosion of equipment.
Azaruddin et al. [3] carried out dechlorination for removal of organic chlorine compos-
ite catalyst system without using hydrogen in the dechlorination reaction. The catalyst was
stable in the presence of HCl. The catalyst deactivated with time due to the adsorption
of HCl produced during the reaction on the catalyst surface.
In their study of decomposition of PVC, they reported that metal oxides with a large
enough metal ion radius such as iron oxide are able to dechlorinate the PVC by attracting
chlorine and weakening of C–Cl bonds in PVC and Chloro-organic compounds. Iron
oxide initially acts as catalyst and under the reaction conditions it is converted to iron
chloride by reacting with HCl. The iron chloride phase is also active for dechlorination
of chloroorganic compounds.
Alternatively, HCl formed in the process can be collected separately and utilized for
various industrial purposes.
Moriyama and Yoshioka [4] carried out dechlorination of plastic by extracting with a
50% NaOH solution at 250–300◦ C. The chlorine content was removed quantitatively and
reduced to 0.012%. A mixture of NaOH, water and a sample of waste plastic were heated
in an autoclave inserted in a Ni tube fitted with a stirrer to 250–300◦ C for 3 h under
N2 . The degree of dechlorination was calculated by chloride ion concentration in NaOH
solutions using an ion chromatograph. The chlorine content in the product dropped only
to 120 ppm at 300◦ C for 2 h, but increased gradually on lowering the temperature to
270 ppm at 275◦ C.
Yamada et al. [5] developed a PVC recycling system with an integrated dechlorination
pyrolysis process in which PVC waste plastics are crushed to optimum size in order to
remove the chain from PVC. The dechlorination is carried out in a rotary kiln furnace;
coarse coke is supplied to prevent an agglomeration of PVC particle and adhesion to the
inner wall of the kiln.
Shiraga and Uddin [6] carried out thermal and catalytic degradation of mixed plastic
containing PVC. The solid acid catalyst employed in this study is silica–alumina with
a chlorine sorbent such as goethite hydrated Iron Oxide FeO (OH). The dechlorination
ability effects of contact mode, liquid phase contact, (LP) or vapor phase contact (VP)
were studied. Dechlorination results show that the vapor phase contact was more effective
for chlorine removal.
Zadgaonkar in India developed a dechlorination method by heating PVC with coal
where the chlorine from PVC is removed quantitatively. The waste plastic and coal with
additive AZ5 is heated to a temperature of 200–225◦ C. The HCl gas evolved is absorbed
over distilled water. In this process coal acts as a hydrogen supplier and thus the unsatu-
ration of dechlorinated polymer backbone decreases. The Zadgaonkar process has proved
to be economically viable.
7.2 PYROLYSIS OF ABS

ABS containing brominated flame retardant is widely used for computer casings. ABS
with or without flame retardant also contains nitrogen as heteroatom. The majority of
nitrogen concentrates in the liquid product. If nitrogen remains as organic compounds
during the Pyrolysis it can produce toxic hydrogen cyanide (HCN). Thermal degradation
of ABS gives oil with high a content of benzene derivatives and also contains organic
nitrogen as aliphatic and aromatic nitriles or nitrogen-containing heterocyclic compounds.
This can be avoided by removing nitrogen before pyrolysis. Brominated flame retardants
in ABS give organic bromine compounds in oil. Liquid hydrocarbon products from ABS-
Br degradation are distributed in the range C5 –C23 with a majority of C6 , C9 and C16
hydrocarbons. The majority of bromine is present in wax products. Removal of bromine
before pyrolysis is a better option to avoid bromine contamination in output products.
8 REFINEMENT OF PYROLYSIS OUTPUT PRODUCTS
8.1 REMOVAL OF UNSATURATION AND OLEFINIC PRODUCTS
The major products in the pyrolysis of plastic are liquid hydrocarbons (50–80%), which
on fractional distillation separate into gasoline, kerosene, diesel and LCO. As discussed
722 A. ZADGAONKAR
earlier the operating conditions and type of catalyst largely affect the properties of the
liquid hydrocarbons. For a given type of zeolite catalyst, lowering the rare earth level
will result in a lower rate of hydrogen transfer relative to cracking; consequently the
gasoline fraction will contain more olefins. An increase in gasoline olefinicity initially
causes a boost in Research Octane Number (RON) and a less sharp increase in Motor
Octane Number (MON). At still higher olefinicity, the RON response levels off and the
MON gain vanishes. Further improvement requires a zeolite type with high carbonium
ion cracking to enhance isomerization and cyclization reactions.
There are two methods for upgrading the fuel obtained in pyrolysis of plastic
a) upgrading the catalyst;
b) upgrading the liquid hydrocarbon obtained in the process.
Besides feed properties and operational variables, the type of catalyst has a profound
effect on final olefins level in the gasoline product. Catalysis with better metal tolerance,
especially to nickel and vanadium, are most suitable for olefin reduction. Catalyst capacity
to saturate olefins and to form corresponding paraffins depend upon the hydrogen transfer
index (HTI).
Hydrogen transfer index = Isobutane(wt%)/total C4 wt%
A shape-selective catalyst such as ZSM-5 cracks midrange C7 –C10 gasoline olefins to

smaller olefins C2 –C6 in the light gasoline range. Thus, boosting the octane number is
due to formation of branched paraffins. This can be achieved by maintaining a high silica:
alumina ratio (Y-zeolite). Another method to reduce olefins is cracking in the presence
of hydrogen. This is also called destructive hydrogenation and leads to the formation of
saturated compounds of lower molecular weight.
Hydrocracking C3 H8 + C5 H12
C8 H18 + H2 −−−−−−−−→
(Propane + pentane)
Hydrocracking leads to high conversion to gasoline and also produces high-quality

diesel fuels.
8.2 VARIOUS EXAMPLES OF PYROLYSIS
Lingaiah et al. [7] carried out catalytic dehydrochlorination of PVC-containing waste plas-
tics-derived fuel oils over FeCl2 /SiO2 catalyst. This catalyst selectively dechlorinates
the chloroalkanes with high activity, except for an initial deactivation due to forma-
tion HCl. The FeCl2 /SiO2 catalyst was prepared by an impregnation method using the
required amount of aqueous iron (II) chloride solution. The dechlorination of the fuel
oil was carried out over 6 wt% FeCl2 /SiO2 catalyst at 350◦ C. It is noteworthy that
the carbon number distribution of the fuel oil does not change significantly during
dehydrochlorination.
Miskokzi et al. [8] studied the cracking characteristics of low-density PE in the presence
of different zeolite catalysts (Figure 27.10); H-ZSM-5, FCC catalysts and clinoptilolite
Nitrogen
Gases
Waste PE
E3
+Q
Liquid
E4
products
Residue
Figure 27.10 Pyrolysis of LDPE (Miskolczi)
containing rhyolite tuff (CRT) were used. The catalyst affected the yield of volatile
products most significantly, whereas the composition of the gas remains unaffected.
Further, each catalyst had a significant effect on the position of double bonds and
olefinic content. The catalyst also affects the other properties of liquid fraction such as
density. A decrease in density of the liquid indicates low average molecular weight. They
also observed that the pour points were lower with ZSM-5 and FCC catalyst than with
CRT. Maximum distillation temperatures of liquid products were lower after catalytic
cracking than for thermal cracking.
Uemichi et al. [9], carried out chemical recycling of polyethylene by catalytic degra-
dation into aromatic hydrocarbons using H-Ga silicate. This exhibits excellent catalytic
activity towards the formation of aromatic hydrocarbons, mainly benzene, toluene and
xylene. This catalyst is less acidic than H-ZSM-5, but the acid sites are significantly
stronger than those on silica–alumina which exhibit low cracking activity. H-Ga sili-
cate is highly effective as a catalyst for the production of aromatic hydrocarbons such
as benzene, toluene and xylenes; important raw material accounted for most of the aro-
matic products.
Huffman et al. [10], studied the effect of different catalyst on liquefaction of plastic and
coprocessing of coal with plastic. The various catalyst used were HZSM-5, ZrO2 –WO2 ,
TiCl3 –SiO2 , Al2 O3 , and TiO2 –SiO2 ; of these HZSM-5 gave the best oil yield and total liq-
uid yield. Although other catalysts tested have little effect on the quantity of oil produced
at temperatures greater than 430◦ C, they improve the oil quantity.
It is also reported that thermal pyrolysis gave a gasoline fraction of about 27% while
the HZSM-5 oil product exhibited a gasoline fraction of 42%; other catalysts gave inter-
mediate gasoline fractions ranging from 28 to 38%
Roy et al. [11] carried out vacuum pyrolysis of used tyres, with a bench-scale reactor
and with cross-ply tyres as feedstock. When the pyrolysis of rubber is carried out under
vacuum the spectrum of quality products obtained is distinct from the usual atmospheric
724 A. ZADGAONKAR
pressure pyrolysis process. The vacuum pyrolysis enables the recovery of commercially
useful products such as pyrolytic oil containing d,l-limonene. The naphtha fraction (IBP
<160◦ C) used as a high octane number component for gasoline middle distillate shows
lubricating properties like heavy oil used as feedstock for production of needle coke (aka
“acicular coke”) is a highly crystalline petroleum coke used in the production of electrodes
for the steel and aluminium industries.
8.3 COMPARISON OF PYROLYSIS OF PE AND PP
Different types of polymer degrade into liquid products at different temperature and form
hydrocarbons with structural differences according to the structure of the parent polymer.
The liquid hydrocarbons obtained by pyrolysis of PE are widely distributed from C3 to
C25 and are composed of linear olefins and paraffins. The liquid hydrocarbons obtained
from pyrolysis of PP are also distributed in the range C3 –C25 , but the gasoline fraction
obtained in PP pyrolysis has a higher octane number compared with gasoline obtained
from PE pyrolysis.
Both these polymers are linear polymers made up of a C–C backbone, with the only
difference that in PP one of the hydrogens in ethylene is replaced by a methyl group.
Hence the carbon atom which holds the methyl group becomes tertiary and scission occurs
mainly between secondary and tertiary carbon atoms, whereas in PE, all carbon atoms on
the polymer backbone are the same, and scission can occur randomly between any two
carbon atoms.
9 RECENTLY DEVELOPED INNOVATIVE TECHNOLOGIES
9.1 THERMOFUEL OF WASTE PLASTIC BY OZMOTECH
Ozmotech have developed a Thermofuel process whereby waste plastic is converted into
diesel by thermal degradation in the absence of oxygen. In this process the plastic waste is
first melted and then cracked in a stainless steel chamber at a temperature of 350–425◦ C
under inert gas (nitrogen). The catalytic reaction tower is designed in such a way that hot
pyrolytic gases take a spiral or zigzag path to maximize contact area and time with the
metal catalyst. The metal catalyst cracks hydrocarbon chains longer than C25 and reforms
chains shorter than C6 . This leads to the formation of saturated alkanes.
The catalyst is not consumed or poisoned, unlike zeolite catalysts. The catalyst metal
plate needs periodic cleaning and polishing.
Polymers containing heteroatoms other than carbon and hydrogen, such as chlorine,
oxygen, nitrogen, etc. (polyurethane, Nylon, PVC, ABS, PET) are not suitable for the
process as they may cause problems such as plant corrosion and poor fuel quality.
9.2 CONVERSION OF WASTE PLASTICS TO FUELS: ZADGAONKAR’S

PROCESS
The author has developed a process (see Figure 27.11) for depolymerization of waste
plastic which results in the formation of lighter hydrocarbons. The products obtained can
be classified into three categories: (a) solid–coke 5–7%; (b) liquid–fuels 75–80%; and
(c) gases (LPG range) 15–20%. Laboratory-scale and bench-scale processes operate in
batch mode and consist of the following steps:
1. Depolymerization,
2. Fractional distillation.
9.2.1 Process Description of Commercial Plant

The feed system consists of sizing equipment for sizing hard, thick flexible and thin
flexible materials, which normally constitute the municipal waste stream. The system
essentially consists of sorters and sizing equipment such as a crusher, a cutter and a
shredder. The various sizes and shapes of the material are sorted into categories suitable
for crushing, cutting and shredding. The sorted material is crushed, cut or shredded and
graded to uniform size for ease of handling and melting. The unwanted organic waste,
mud, metal, etc. are also separated in the process of sizing and grading. The graded
material is passed through cyclone filters to separate fine dust, clay and other impurities
from the graded waste plastic pieces. This process of sizing, grading and cleaning the
waste is semiautomatic. The cleaned feed is stored in a surge hopper before feeding to
the process by a conveyor feeder.
The graded and cleaned particles of waste plastic are then introduced into a melt-
ing/preheating system with an extruder feeder. The hard metal, clay and sand, glass,
etc. are separated here by sedimentation, and then the waste plastic is charged in the
dechlorination section. The solid metal, glass, etc. is removed from the melting/preheating
section periodically.
The dechlorination section of the plant consists of components which together effect
release of chlorine from plastics such as PVC in the presence of coal and additives. The
hot viscous waste plastic is fed from the upper end of the vessel and allowed to heat
up at 220–250◦ C. The coal acts as a source of hydrogen required for the reaction. The
released gaseous hydrochloride travels upwards through the vessel and is discharged to
gaseous product recovery.
This is a reaction involving polymer degradation by breaking the substituent groups,
but not the main chain. Although the mechanism of PVC degradation is highly complex
in nature, the free radical path seems to play a major role. The labile chlorine atom, which
is at a β-position with respect to the free radical carbon atom, is now released as a free
radical so as to stabilize the structure by substituting hydrogen. The chlorine-free radicals
attack free hydrogen released from coal.
The reactor section of the plant consists of the reactor, which together with other
equipment carries out a continuous conversion of waste plastic to fuels. The molten waste
plastic, free of chlorine, nitrogen and other organic impurities, is fed in to the reactor at
the top end and allowed to flow over a heated surface at 350◦ C in the presence of the
coal and patented additives. Upon contact with the hot surface and the mixture of coal
and additives, the viscous waste plastic converts to gaseous form.
The breaking of chemical bonds under the influence of heat is the result of overcoming
bond dissociation energies. Organic substances such as polymers are highly heat sensitive
due to the limited strength of the covalent bonds that make up their structures. Scission can
occur either randomly or by a chain-end process, often referred to as an unzipping reaction.
726
A. ZADGAONKAR
Figure 27.11 Schematic for Zadgaonkar’s process for conversion of waste plastics to fuels
The reaction breaks complex hydrocarbons into simpler molecules in order to increase
the quality and quantity of lighter, more desirable products and decrease the amount
of residuals. This process rearranges the molecular structure of hydrocarbon compounds
to convert heavy hydrocarbon feedstock into lighter fractions such as diesel, kerosene,
gasoline, LPG, heating oil, and petrochemical feedstock.
The reaction results in the formation of gases such as methane, ethane, ethylene,
propane, propylene, iso-butane, n-butane, hydrogen gaseous petrol, kerosene, diesel, heavy
oil (CLO). The gases are subsequently allowed to pass through a condenser.
The process includes a condenser for continuous separation of the mixture of gases and
the mixture of liquid fuels. The condensed heavier fractions are collected in the accumu-
lator and the uncondensed gases are collected and stored separately through the vent gas
stream consisting of noncondensable with gases up to C4 . The liquid hydrocarbons are
subjected to fractional distillation.
The analytical section houses the components and instrumentation necessary for anal-
ysis and sample collection of slipstreams of gas. The gases are analysed for residual
toxic gases such as furans and dioxins, as well as total organic carbon, total carbon and
suspended particles.
The analytical section also houses the instruments for analyzing the process products
for the quality of CNG and LPG range gases, hydrogen, gaseous hydrogen of chloride,
and distilled products such as petroleum ether, gasoline-I, gasoline-II, kerosene, diesel
and lubricating oil (CLO).
9.2.2 Unique Features of Zadgaonkars’ Process

A) The process is 100% eco friendly.
B) This process is not only a solution to the waste plastic problem, but can change the
global economic scenario by saving millions of dollars in imports of crude oil.
C) This is a unique process through which 100% of waste is converted into value-added
products.
D) Percentage composition of output can be altered by changing/adjusting reaction con-
ditions.
E) Liquid fuel obtained in the first stage i.e. Depolymerisation, can be directly utilized
as fuel for DG sets, thereby generating electricity through a nonconventional waste
plastic source, for applications such as agricultural pumps, as well as producing, boiler
fuels, marine fuel, fuel oil and input feed for petroleum refineries. Gaseous fuel can
be utilized as domestic or industrial fuel.
Solid fuel (coke) can be utilized in thermal power plants and metallurgical industries.
(Note: The utilization of solid, liquid and gaseous fuels is certified by the Indian Oil
Corporation, Government of India.)
F) Any type of waste plastic (i.e. Polypropylene, Polyethylene, PET, PVC, ABS, etc.) in
isolation or in combination can be converted into value-added fuel.
A full fledged commercial plant based on continuous mode is operating successfully
since February 2005, at K-13, Butibori Industrial Area, Nagpur, India, which is now under
expansion.
728 A. ZADGAONKAR
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Japan, 6 March, 90, 2000.
3. M. Azaruddin et al., Applied Catalysis, 207, 79–84 (2001).
4. M. Moriyama and T. Yoshioka, Department of Applied Chemistry, Graduate School
of Engineering Tohoku University II International Symposium on Feedstock Recy-
cling of Plastics and other Innovative Recycling Technologies, Belgium 2002, Japan.
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Industrial Technology Development Org. Eco-product International Fair, Malaysia,
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6. Y. Shiraga and M. A. Uddin, Energy and Fuels 13 428–432 (1999).
7. N. Lingaiah, M. A. Uddin and Y Sakata, Green Chemistry 3, 74–75 (2001).
8. N. Miskokzi, L. Bartha, G. Deak, B. Jover and D. Kallo Process Safety and Envi-
ronmental protection 82, 223–229 (2004) .
9. Y. Uemichi, K. Takuma and A. Ayame, Chem. Commun. 1 1998.
10. Huffman, J. Rockwed and N. Shati, CFFLs.
11. C. Roy, H. Darmstadt, B. Benallal, A. Chaala and A. E. Schwerdtfeger, Journal of
Analytical and Applied Pyrolysis 51 201–221 (1999).
28
Converting Waste Plastics into

Liquid Fuel by Pyrolysis:
Developments in China
YUAN XINGZHONG
Department of Environmental Science and Engineering, Hunan University, Changsha,
Hunan Province, 410082 P.R.China
1 PROGRESS IN CONVERTING WASTE PLASTICS INTO LIQUID FUEL

BY PYROLYSIS
Since the 1970s, shortage of energy and environmental pollution have become more and
more serious. As a way to ease this problem, the pyrolysis of waste plastics for recovery
of liquid fuel has been paid more and more attention, and various pyrolysis technologies
have been developed. The thermal cracking technology for waste plastics was investigated
in the early 1970s [1]. It was found that under high temperature, the carbon chains can be
broken up and various monomers, active molecular groups and some small molecules will
be formed. As a result, liquid products with relatively high H/C ratio can be obtained. The
process and mechanism of thermal cracking have been studied extensively [2–4], and a
series of thermal cracking processes such as the United Carbon process [5], the Hamburg
University process [6] and the BP process [7] were developed and industrialized.
The thermal cracking process is characterized by low costs and simple operation, but
the high energy consumption and the low conversion efficiency and yield have seriously
hampered its development. To improve the quality and yield of liquid fuel, great efforts
have been made by many researchers and a large number of experimental studies have
been carried out by introducing suitable catalysts [8–30], as listed in Table 28.1. The
use of catalysts can not only lower the activation energy, reduce the energy consumption
and increase the treatment efficiency, but can also improve the selectivity and quality of
products significantly. Some plastic pyrolysis processes have been developed and commer-
cialized, such as the Veba process [31], the USS process [32] and the Mazda process [33].
The Veba process has been shut down recently. Further improvement of the quality and
730 YUAN XINGZHONG
Table 28.1 Laboratory experiments on catalytic plastics cracking
Investigator Reactor Plastics species Catalysts

Uemichi et al. [8–11] Flow reactor PE, PP Silica–alumina, CaX
zeolite, activated carbon,
metal supported on
silica–alumina or
activated carbon
Ishihara et al. [12–16] Batch flow reactor PE, PP, PS Active charcoal,
silica–alumina, NaY
zeolite
Mordi et al. [17, 18] Sealed reactor LDPE, PP HZSM-5, H-mordenite,
H-theta-1 zeolite
Beltrame et al. [19, 20] Flow reactor PE, PS Silica gel, alumina,
silica–alumina, rare
earths, Y and H-Y
zeolites
Vasile et al. [21–23] Flow reactor LDPE, HDPE, PP Silica–alumina, ZSM-5
zeolite, dealkylation
catalyst
Ueno et al. [24, 25] Flow reactor PE, PS Silica–alumina, HZSM-5
zeolite, active carbon,
metal oxides
Sakata et al. [26–28] Flow reactor LDPE, HDPE, PP, Silica–alumina
PET, PVC
Gongzhao Liu et al. [29] Continuous PE, PP, PS Silica–alumina, aluminate
agitator reactor
Zhiyuan Yao et al. [30] Flow reactor PE, PP, PS, PVC, Reformed ZSM-5 zeolite
PET
yield of liquid fuel products can be achieved by cracking–catalytic reforming [34–36],

which is also called the ‘two-step’ process. This kind of process has been widely applied
in industry with good results. Currently, processes using this technology include the Fuji
recycling process [37, 38], the BASF process [39], the Likun process [40], the Hunan
University process [41, 42] and so on.
2 THEORY OF PLASTICS PYROLYSIS
2.1 MASS BALANCE FOR THE PYROLYSIS PROCESS
Waste plastic may be converted into gasoline-range hydrocarbons by pyrolysis [43]. The
thermal cracking of waste plastics proceeds by typical random decomposition, with prod-
ucts being mainly alkanes, alkenes as well as high-boiling-point hydrocarbon products
(carbon number > 24). The products of catalytic cracking are, however, composed of
more iso-alkanes and aromatics, which are highly desirable gasoline-range hydrocarbons.
Reforming catalysts have the highest selectivity to aromatics, and the products after cat-
alytic reforming are mainly aromatics.
All the plastics have their own activation energy when cracked. The corresponding
reaction temperatures required are different. At appropriate temperature, pressure and with
DEVELOPMENTS IN CHINA 731
a suitable catalyst applied, high yield of high-commercial-value products such as gasoline
and diesel can be achieved. PE and PP will be degraded under high temperature (>350◦ C)
and the yields of light fractions will keep growing with the increase of temperature: at low
temperature, the products will be mainly composed of high-boiling-point hydrocarbon and
polymers; At moderate temperature (400–500◦ C), gas will account for 20–40% of the
products, liquid 35–70% and residue 10–30% [45]. At high temperature (800◦ C), the
main products will be ethylene, propylene and methane [46]. When LDPE is pyrolyzed
for 2 h at 420◦ C, the products will be mainly composed of olefins (60%), terminal olefinic
bond hydrocarbons (35%) and non-terminal olefinic bond hydrocarbons (5%). High yield
of oil products (94.5%), mainly C10 –C30 , hydrocarbons will be achieved by pyrolysis of
HDPE at 400–450◦ C, and the gas fraction, which is mainly hydrogen gas and hydrocarbon
(C1 –C5 ), will account for only 5.5% of the products. At 400◦ C, a conversion rate of 95%
is achieved. The oil products mainly consist of C9 hydrocarbons (mainly composed of
2,4-dimethylheptene) and C6 , C11 and C14 hydrocarbons. When PP is pyrolyzed in a
fluid-bed reactor at 450–640◦ C, a conversion rate of 50–85% can be achieved. And if
catalyst is introduced, oil products with a research octane number (RON) of 83 can easily
be obtained by hydrogenation of PP in a high-pressure reactor. The liquid fuel obtained
is absolutely qualified for gasoline use. If water is added, the RON can even reach as
high as 86, and 40% of the oil products will be alkenes.
The components of products from thermal and catalytic cracking of HDPE, LDPE,
LP, PP, PS were analyzed [48], and the results are shown in Table 28.2 and Table 28.3.
The products from thermal cracking of HDPE, LDPE and LP (linear polyethylene) are
mainly wax-like substances at normal temperature. The fraction under 200◦ C recovered
from HDPE accounts for 16% of the total cracking products, while that from LP accounts
for 23%. Compared with the products of PE, PP produces less solid residue, but more
liquid components, and PS produces the highest proportion of liquid fraction, which is
99.17% by thermal cracking and 99.56% by catalytic cracking.
In another experiment conducted by Sakata [49], the degradation of PE produced liquid
products which consisted of C5 –C25 hydrocarbons with a yield of 70 wt%. In con-
trast, the degradation of PVC produced only 4.7 wt% liquid products which consisted
of C5 –C20 hydrocarbons while the degradation of PET surprisingly produced no liquid
products. The addition of either PVC or PET to PE decreased the overall liquid product
yield, however, it promoted the degradation of PE into low-molecular liquid hydrocarbon
products.
Table 28.2 Mass balance on thermal cracking of polyolefins
Feedstock HDPE LDPE LP PP PS

Liquid yield (%) 91.30 91.71 93.80 91.05 99.02
State of liquid Milk white Milk white Milk white Yellow Rufous
products at Wax Wax Wax Solid and liquid Liquid
normal mixture
temperature
Gas yield (wt%) 7.61 7.42 5.60 7.60
Coke yield (%) 0.14 0.15 0.14 0.14 0.15
Total (%) 99.05 99.28 99.54 98.79 99.17
Rufous = reddish-brown
732 YUAN XINGZHONG
Table 28.3 Mass balance on catalytic cracking of polyolefins
Feedstock HDPE LDPE LP PP PS

Liquid yield (%) 76.81 77.40 85.20 87.20 86.20
State of liquid Solid and Solid and Light yellow Light yellow Rufous
products at liquid mixture liquid mixture liquid liquid liquid
normal
temperature
Gas yield (wt%) 14.04 14.08 8.15 9.34 0.34
Coke yield (%) 8.30 8.04 6.52 3.35 13.02
Total (%) 99.15 99.79 99.87 99.89 99.56
2.2 ENERGY BALANCE FOR THE PYROLYSIS PROCESS
The temperature required in the process of catalytic cracking of waste plastics is much
lower than that of thermal cracking, and further heat supply is unnecessary when the
catalytic bed is preheated to some extent, because the energy carried by the gas products
from the reactor is enough to sustain the required reaction temperature. Therefore, only
the energy balance on the thermal cracking part is discussed here for simplification. Take
PE for example, after degradation and condensation, PE is converted into liquid fuel (a
mixture of gasoline and diesel oil) and gas fuel. To simplify the calculation, the average
molecular weight of PE is taken as 8.75 × 104 , and the average degree of polymerization
is considered to be 3125. The components of fuel gas, gasoline, diesel oil and residual
oil are represented by C3 H8 , C8 H18 , C16 H34 , C30 H62 respectively.
2.2.1 Energy Balance Calculation

The mass flow of thermal degradation of PE is shown in Figure 28.1. For the thermal
degradation of 1 kg PE feedstock, the overall energy needed [51] is calculated by:

Q= ni Hi − ni Hi (28.1)
out in
where Q is the overall energy required in the thermal cracking process (kJ), ni is the
molar number of component i (mol), Hi is the enthalpy of component i (kJ mol−1 ).
0.02kg petroleum gas(gas)

1kg PE (solid) 0.46kg gasoline (gas)
Pyrolysis Reactor
0.34kg diesel oil (gas)
0.18kg residual oil (liquid)
T1 (Temperature of feedstock) T2 (Temperature of pyrolysis production)
Figure 28.1 Mass Flow of PE pyrolysis

According to Equations (28.2–28.4), the enthalpy of formation of C3 H8 , C8 H18 and
C16 H34 (all gases) at temperature of T2 can be calculated respectively [52]:
Hf (C3 H8 , g, T2 ) = −59.94 kJ mol−1 , Hf (C8 H18 , g, T2 ) = −92.88 kJ mol−1

Hf (C16 H34 , g, T2 ) = −156.08 kJ mol−1
H
Cn H2n+2 (g, T1 )−−−→Cn H2n+2 (g, T2 ) (2)
Hf (Cn H2n+2 , g, T2 ) = Hf (Cn H2n+2 , g, T1 ) + H (3)
in which, T2
H = cp(Cn H2n+2 , g, T )dT (4)
T1
According to Equations (28.5–28.8), the enthalpy of formation of C30 H62 (liquid) at

T2 is obtained: Hf (C30 H62 , l, T2 ) = −384.69 kJ mol−1
H1 −HV H2
C30 H62 (g, T1 )−−−→C30 H62 (g, Tb )−−−→C30 H62 (l, Tb )−−−→C30 H62 (l, T2 ) (5)
Hf (C30 H62 , g, T2 ) = Hf (C30 H62 , g, T1 ) + H1 − HV + H2 (6)
Tb
H1 = cp (g, T )dT (7)
T1
T2
H2 = cp (l, T )dT (8)
Tb
in which Tb and Hv are the boiling point and the heat of evaporation under normal
pressure.
Based on the amount of mass flow of products and the enthalpy of formation calculated,
the overall output enthalpy is obtained, which is −808.6 kJ kg−1 . Under the conditions of
101–203 MPa, 200–300◦ C, the overall output enthalpy can be obtained as −2124.7 kJ
kg−1 according to Equation (28.9):
n(CH2 = CH2 )(g, T1 , 0.1MPa) −−−→ n(CH2 = CH2 )(g, Tr , 0.1MPa) −−−→
n(CH2 = CH2 )(g, Tr , 150MPa) −−−→ (-CH2 = CH2 -)n (s, Tr , 150MPa) −−−→ (9)
(-CH2 = CH2 -)n (s, T1 , 0.1MPa) −−−→ (-CH2 = CH2 -)n (s, Tr , 0.1MPa)
in which Tr is the reaction temperature.

According to Equation (28.1), the total energy needed for the thermal degradation of
PE can be obtained as 1316.1 kJ kg−1 .
2.2.2 Estimation of Energy Profit

Supposing PE is converted to gasoline, diesel oil, residual oil and fuel gas, the net energy
profit can be obtained by:
Qj = wi Qi − Q (10)
734 YUAN XINGZHONG
Table 28.4 The components and yield of thermal degradation products of PE
Gasoline Diesel oil Residual oil Petroleum gas

Percentage (%) 43–49 31–37 17–19 1–3
Yield/(mol kg−1 ) 3.77–4.30 1.37–1.64 0.40–0.45 0.23–0.68
Table 28.5 The heat values and net energy profit of various products (104 kJ kg−1 )
Gasoline Diesel oil Residual oil Petroleum gas Net energy profit
Theoretical heat value 4.320 4.290 4.180 4.620 4.170
Experimental heat value 4.462 5.263 6.571 4.900
in which wi and Qi are the weight percentage (shown in Table 28.4) and the heat value
(kJ kg−1 ) of component i, respectively.
The theoretical [53] and experimental heat values of various products and net energy
profit are shown in Table 28.5.
Taking the heat value of standard coal (29260 kJ kg−1 ) as the basis, the theoretical and
experimental values of net energy profit for the thermal degradation of 1 kg PE will be
approximated to the calorific value of 1.43 and 1.67 kg standard coal, respectively.
2.3 MECHANISM OF PLASTICS PYROLYSIS
Thermal degradation of plastics can be classified as depolymerization, random decom-

position and mid chain degradation [54, 55]. In the process of depolymerization, the
conjunction bonds between monomers are broken up, which leads to the forming of
monomers. Depolymerization type plastics mainly include α-polymethyl styrene, poly-
methyl methacrylate and polytetrachloroethylene. In the random decomposition process,
scission of carbon chains occurs randomly, and low-molecular hydrocarbons are pro-
duced. Random-decomposition-type plastics include PP, PVC and so on. In most cases,
both decompositions take place. To be more specific, the degradation of polyolefins can
be classified as the following three types:
(a) polymers are degraded to monomers;
(b) the chains break up randomly and low-molecular polymers are generated (random
chain scission happens in the pyrolysis of most polyolefins);
(c) the substituent groups or functional groups are removed and low molecular polymers
are produced, accompanied by the formation of unsaturated hydrocarbons and cross-
linking, even coking.
A comprehensive treatment of the mechanism of plastics pyrolysis has been presented
by Cullis and Hirschler [56]. Four types of mechanisms of plastics pyrolysis have been
proposed:
(a) End-chain scission or depolymerization: the polymer is broken up from the end
groups, successively yielding the corresponding monomers; this is also considered
the main manner of polymer pyrolysis by Prakash et al. [57] and Songip et al. [58].
(b) Random-chain scission: the polymer chain is broken up randomly into fragments of
uneven length.
(c) Chain-stripping: elimination of reactive substitutes or side groups on the polymer
chain, leading to the evolution of a cracking product on one hand, and a charring
polymer chain on the other.
(d) Cross-linking: formation of a chain network, which often occurs for thermosetting
polymers when heated.
These different mechanisms and product distributions, to some extent, are related to
the bond dissociation energies, the chain defects of the polymers, and the degree of
aromaticity, as well as the presence of halogen and other heteroatoms in the polymer
chains. Large amount of styrene monomers can be obtained by pyrolysis of PS, while a
wide range of hydrocarbons are produced by random degradation of PE and PP [3, 59,
60].
Thermal degradations are carried out by a free radical mechanism, while catalytic
degradation are realized by carbonium ions, which consist of hydrocarbon ions carrying
a single positive charge.
A mechanisms of catalytic pyrolysis of waste plastics was proposed by Buekens [61],
using PE as an example, in which FCC catalyst is adopted and the main content include:
1. Initiation may occur on some defect sites of the polymer chains. For instance, an
olefinic linkage could be converted into an on-chain carbonium ion by proton addition.
Then the polymer chain may be broken up through β-scission. Initiation may also take
place through random hydride ion abstraction by low-molecular-weight carbonium ions
(R+ ), The newly formed on-chain carbonium ion then undergoes β-scission.
2. Depropagation: the molecular weight of the main polymer chains may be reduced
through successive attacks by acidic sites or other carbonium ions and chain cleav-
age, yielding an oligomer fraction (approximately C30 –C80 ). Further cleavage of the
oligomer fraction probably by direct β-scission of chain-end carbonium ions leads to
gas formation on the one hand, and a liquid fraction (approximately C10 –C25 ) on the
other.
3. Isomerization: the carbonium ion intermediates can undergo rearrangement by hydro-
gen or carbon atom shifts, leading to, e.g. a double-bond isomerization of an olefin.
Other important isomerization reactions are methyl group shift and isomerization of
saturated hydrocarbons.
4. Aromatization: some carbonium ion intermediates can undergo cyclization reactions.
An example is when hydride ion abstraction first takes place on an olefin at a position
several carbons removed from the double bond, the result being the formation of an
olefinic carbonium ion. This carbonium ion could undergo intramolecular attack on
the double bond, which provides a route to cyclization and formation of aromatics.
2.4 METHODS FOR PLASTICS PYROLYSIS
There are mainly three methods for pyrolysis of plastics, namely: thermal cracking, cat-
alytic cracking, and cracking–catalytic reforming [62]. Each has its own suitable process,
as shown in Figure 28.2. Other methods for plastics pyrolysis include hydrogenation
736 YUAN XINGZHONG
Normal fixed-bed
Fixed-bed
thermal pyrolysis Melting fixed-bed
Thermal cracking Sand fixed-bed
Flow-bed
thermal pyrolysis
Flow-bed
thermal pyrolysis
Mixing of catalyst
Pyrolysis of and waste plastics
Catalytic cracking
waste plastics
Fixed-bed
thermal pyrolysis
Melted Waste Plastics Flow
through catalyst layer
Thermal cracking – Catalytic reforming

Cracking-
Catalytic reforming
Catalytic cracking – Catalytic reforming
Figure 28.2 Main methods for waste plastics pyrolysis and their relative processes
[63, 64], gasification [65, 66], pyrolysis in supercritical water [67, 68], coliquefaction
with coal [69–71], and so on.
2.4.1 Thermal Cracking

Thermal cracking is the simplest form of waste plastics pyrolysis. In the process of thermal
cracking, plastics are degraded simply by heat, which overcomes the required activation
energy [72]. The process is simple, but quite rough at the same time, and hydrocarbons
with a wide range of boiling points are produced; furthermore, the yields of oil products
(mainly gasoline and diesel oil) are low. The gasoline obtained contains large amounts of
olefins and has a very low RON value. The diesel oil produced is high in freezing point
and low in cetane value. Most products of PE by pyrolysis are straight-chain alkanes and
α-alkenes [48].
2.4.2 Catalytic Cracking

In the process of catalytic cracking, characteristic reactions such as chain scission, hydro-
gen transfer and condensation take place under certain temperature and pressure conditions
and when an appropriate catalyst is utilized, products with certain range of molecular
weights and structures are obtained. Catalysts with surface acid sites and with the ability
of hydrogen ion donation such as silica–alumina and molecular sieve catalyst have been
already widely utilized. These catalysts can also enhance the isomerization of products
and increase the yield of isomeric hydrocarbons. However, large amounts of coke will
deposit on the surface of catalysts and consequently lead to their deactivation. Therefore,
the recycling of catalysts is difficult to achieve.
With thermal cracking and catalytic cracking taking place at the same time, the process
can achieve very high reaction rates. Large amounts of isomers and aromatics can be
produced in a short period of time. The catalyst is usually mixed, however, with sand
contained in the plastics and the coke produced, which will result in difficult recycling.
To solve this problem, various processes have been developed such as precleaning the
waste plastics and making the melted plastics flow through a bed of catalyst [73–75].
2.4.3 Cracking–Catalytic Reforming

In cracking–catalytic reforming (also called the two-step process, as distinct from the one-
step process described above), plastics are first cracked under high temperature and then
undergo catalytic reforming; oil products with relatively high quality are finally obtained
the end. The liquid fuel products of thermal cracking consist mainly of hydrocarbons with
a wide range of boiling points, among which the yields of light fraction such as gasoline
and diesel oil are low, and the quality is poor. In order to improve the RON, the content
of isomers, cycloparaffins and aromatics must be improved, which can be achieved by
catalytic reforming. To further raise the reaction rate, catalysts can also be added during
thermal cracking. High yields of liquid fuel with good quality can be obtained by the
cracking–catalytic reforming process; moreover, the operation is flexible. This method
is also suitable for the treatment of mixed waste plastics, and most important of all, the
catalysts can be recycled. All these have greatly contributed to the fast development of
this technology and made it the most widely applied process in industry.
2.4.4 Other Methods

Hydrogenation [63, 64] or hydrocracking involves the pyrolysis of plastics under a hydro-
gen atmosphere at a pressure of approximately 10 MPa, in three steps: depolymerization;
hydrogenation of the liquid phase; and hydrogenation of the products. Owing to the pres-
ence of hydrogen, saturated hydrocarbons are produced in the reaction process. Moreover,
plastics containing heteroatoms (e.g. Cl, N, O, S) can be easily treated by hydrogenation.
Gasification [65, 66] is the partial oxidation and pyrolysis of plastics under high tem-
perature, with steam and oxygen as gasification agents. This process produces products
which consist mainly of H2 , CO, CO2 and CH4 . No pretreatment is needed here, and
mixtures of various plastics, even mixtures of plastics and municipal solid waste, can be
easily degraded. And most of all, this technology can effectively prevent coking.
Pyrolysis in supercritical water [67, 68]: owing to the many special characteristics of
supercritical water, waste plastics can be degraded efficiently in supercritical water, which
has recently received great attention has been studied comprehensively. This technology
can not only realize the recovery of valuable products from waste plastics, but also provide
a solution to the ever-growing energy crisis and environmental pollution. No catalysts or
reaction agents are needed here, so the cost is very low.
Coliquefaction with coal [69–71]: in the process of coal and waste plastics coliquefac-
tion, the hydrogen atoms contained in plastics transfer from plastics to coal, leading to
partial or even total liquefaction of coal. On the one hand, as hydrogen donors, plastics
can reduce the hydrogen consumption for coal coliquefaction dramatically. On the other
738 YUAN XINGZHONG
hand, the existence of coal as catalyst can also greatly promote the pyrolysis of plastics.
This technology has not only provided a solution for the ‘white pollution’ problem, but
also reduced the cost of coal coliquefaction.
3 PROCESS OF PLASTICS PYROLYSIS
A series of industry-scale processes for recovery of liquid fuel from waste plastics have
been developed and applied in countries such as the United States, Japan, Germany and
England. Some of the processes, such as the Veba process, the BP process, the Fuji process
and the Hunan University process have been applied widely and successfully in industry.
Some typical pyrolysis processes are listed in Table 28.6.
3.1 VEBA PROCESS
In the Veba process [31], a mixture of vacuum residue, lignite and waste plastics is
pyrolyzed under conditions similar to the case of crude oil hydrogenation. The main
products include gaseous hydrocarbons, alkanes, cyclanes and aromatics.
The main difference between Veba process and other processes lies in that hydrogena-
tion technology is used in this process, which improves the quality of products. At the
same time, waste plastics are stirred and fully mixed by hydrogen. This whole appara-
tus is capable of disposing of 40 000 tons of waste plastics per year, but is relatively
complicated and expensive.
3.2 BP PROCESS
The BP process [7] is based on a sand fluidized-bed pyrolysis reactor. The cracking
temperature is kept at 400–600◦ C. Low-molecular hydrocarbons can be obtained. The
process mainly involves converting waste plastics into normal linear hydrocarbons, the
average molecular weight of which is 300–500. Most plastics can be treated by this
process. Polyolefins are decomposed into small molecules with the same linear structure.
PS is converted into styrene monomers and PET into mixture of hydrocarbons, carbon
monoxide and carbon dioxide. A maximum of 2% PVC is allowed in this process, and the
content of chlorine in the products is lower than 5 ppm. The distribution of alkene products
in this process is like that in petroleum pyrolysis. The BP process was industrialized in
1997.
The biggest difference between this process and the others lies in the reactor, which
was originally a fixed-bed reactor. A sand fluidized-bed reactor has been adopted for the
BP process, which can guarantee a uniform temperature in the reactor due to the uniform
particle size and fluidized nature of sand. In traditional processes, because of the poor heat
transfer properties of plastics, a uniform temperature is difficult to achieve in the plastics
feedstocks so a long reaction time was always required. On the other hand, after waste
plastics are heated and melted, they usually adhere to the surface of reactors owing to
their poor flow characteristics. The BP process has successfully solved all these problems,
and a continuous production of liquid oil is achieved.
Table 28.6 Typical pyrolysis process of waste plastics
Developer Scale Feedstock Reactor Temperature Catalyst Main Yield of

(◦ C) products products
(%)
United Carbon 35–70 kg/d PE, PP, PS, PVC, Extruder 420–600 Wax
Company PA, PET
Japanese PE, PP, PS Extruder 500–600 Monomers
Carbon
Company
DEVELOPMENTS IN CHINA
Fuji Recycle 5000 t/a PE, PP, PS (industrial Melting furnace 390 ZSM-5 Gasoline 80–90
Company waste)
Fuji Recycle 4000 t/a PE, PP, PS, PET Melting furnace 310 ZSM-5 Light oil, 80–90
Company (PC<15%) kerosene
USS 250 kg/h PE, PP, PS, PET, Batch agitator 400 Al,Ni,Cu C9 fuel oil 80–90
FRP reactor
Mitsubishi 170 kg/h PP Melting furnace 550 Light oil 95
Heavy
Industry
Sanyo Engine 128 kg/h PE, PP, PS Melting furnace 510–560 68
Company
Mitsu Ship 24∼30 t/d PE, polymers with Agitator tank 420∼455 Fuel oil 85
Company low molecular
weight
Veba Company 40000 t/a polyolefins Hydrogenation Lignite Fuel oil
reactor
BP Company 20 kg/h PS, PET Sand flow-bed 400–600 Petrochemicals
reactor
Japan Physics 300 t/d Thermoplastic Melting furnace First phase: Al,Ni,Cu,etc. Gasoline,
and polymers 200–250 kerosene
Chemistry Second
Research phase:
Institution 360–450
739
740
Developer Scale Feedstock Reactor Temperature Catalyst Main Yield of

(◦ C) products products
(%)
BASF PVC < 5% Melting furnace 400–500 Fuel oil, fuel 90

Company gas, α-olefins
Mazda 2 kg/batch PE, PP, PS, PU, ABS Electric furnace 400–500 AlCl3 , ZrCl4 , Gasoline, 60
Company etc. kerosene
Hamburg 80–240 kg/d PE, PS, PVC Flow-bed 640–840 Aromatics
University reactor
Hamburg PE, PS, PVC Molten salt 600–800 Aromatics
University reactor
Hunan 1 t/h Waste plastics, heavy Flow-bed 430–450 YNN, silica– Gasoline, 75–80
University oil reactor alumina/ kerosene
PPA zeolite
Amoco PE, PP, PS Melting furnace Hydrocarbons
Company
China Likun PE, PP, PS Gasoline,
Company kerosene
YUAN XINGZHONG
3.3 FUJI PROCESS
The Fuji process [37, 38] is a typical two-step process, as shown in Figure 28.3. Waste
plastics are converted into gasoline, kerosene and diesel oil by pyrolysis and reforming
over ZSM-5 catalyst. After being crushed, the waste plastics enter the molten bath through
an extruder and are mixed with the part of uncracked plastics which was returned from
the thermal cracking reactor. Then the mixture is heated to 280–300◦ C in the molten
bath and then enter the thermal cracking reactor and are pyrolyzed at a temperature of
350–400◦ C. The products of thermal cracking enter the catalytic reforming reactor and
are converted into gasoline, kerosene and diesel oil, with a yield of 80–90%. This process
has the following characteristics: first, a centrifugal blender is used, which can greatly
accelerate the heat transfer process and stir the melted material by cycling them from the
thermal cracking reactor to the molten bath. Furthermore, it can avoid the accumulation
of residue in the molten bath. Second, recycling instead of mechanical stirring of plastics
is adopted in this process, which is a big difference between this process and others.
Finally, the process makes full use of the low decomposition temperature of PVC, with
HCl being removed before the pyrolysis of mixed plastics takes place.
3.4 BASF PROCESS
The BASF process [39] has some resemblance to the Fuji process; it is also a two-step
process, and a PVC content lower than 5% is required in the feedstocks. The waste plastics
are melted at 250–380◦ C and volume reduction and better uniformity are achieved. In
this process, relatively cheap alkaline solid substances such as calcium oxide, sodium
carbonate or other alkalis in solution are used to remove HCl by absorption. Depending
on the different plastics processed, oil product yields ranging from 20 to 70% can be
achieved. This process is suitable for the treatment of mixed plastics containing heteroatom
contaminants.
3.5 HAMBURG UNIVERSITY PROCESS
Hamburg University [6] developed a fluid-bed reactor cracking process. In the process,
plastics are fed into the reactor by a screw and cracked. The cracked gases are preheated
Heat exchanger Oil
Waste Plastics Reforming reactor Gas-liquid seperator
Gas
Extruder Molten bath Cracking reactor
Centrifugal blender Heater
Figure 28.3 Flow chart of the Fuji process

742 YUAN XINGZHONG
to 400◦ C, passed through a heat exchanger and then separated from the solid residue and
dust in a cyclone separator. A high yield of alkenes can be achieved. One advantage of
this process is that the type of fluid gas is changeable, so various products can be obtained.
For instance, if steam instead of hot hydrocarbon gases is adopted as the fluidizing agent,
more ethylene can be recovered from PE by this process. An experimental factory which
applies this technology has been built in Ebenhousen, German. The production capacity
of the factory is 5000 t/a.
3.6 HUNAN UNIVERSITY PROCESS
A new fluid-bed reactor cracking process was developed by Hunan University [41, 42]
and the Hunan Waste Resources Recycling Company to treat waste plastics. The process
is shown in Figure 28.4. After cleaning and granulating, the waste plastics are fed to the
fluidized-bed reactor by a double screw feeder, at the same time, catalysts are added while
a stirrer keeps running at a velocity of 2 rpm. Waste plastics get fully cracked and the solid
residue, mainly coke, sand and catalyst, is transferred to the reactivation reactor. After
reactivation, the catalyst enters a cyclone separator with gas flow, be collected and finally
returned to the fluid-bed reactor again. The cracked gas enters the cyclone separator,
where the heavy fractions drop to the bottom and go to the reforming reactor while the
light fractions escape from the top. The reformed fractions then enter a fractionating
rectifying tower and are cooled. In the end, oil products such as gasoline, diesel oil and
heavy oil are obtained and the residual gases are compressed and burned. Currently, a
demonstration project using this process has already been put into operation in Changsha,
China. It can treat 30 000 t waste plastics per year.
Waste Plastics
1 7
4
2
5
3 6
Gasoline
8
Diesel Oil
Heavy Oil
Catalyst Solid Residue
4
Gas product 8
Solid Residue
Figure 28.4 Flow chart of the Hunan University process. 1 twin screw feeder; 2 flu-
idized-bed reactor; 3 catalyst feeder; 4 cyclone separator; 5 catalytic reforming column;
6 rectifying tower; 7 condenser; 8 compressor; 9 reactivation reactor
3.7 UNITED CARBON PROCESS
The United Carbon plastics cracking system [5] includes four main parts: electrically-heated
extruder, thermal cracking reactor, heat exchanger, and product-collecting facilities. The
extruder is mainly used for compressing, melting plastics polymers and transferring them
to the cracking reactor. The cracking reactor is a pipe structure which makes it easier for
plastics to achieve a uniform temperature quickly. The products are cooled down in the
heat exchanger before finally entering the collecting facilities. This process is suitable for
all types of plastics. The reaction temperature is 420–600◦ C. No catalyst is added in the
process, and the main product is wax. The flow chart of the United Carbon process is shown
in Figure 28.5.
3.8 LIKUN PROCESS
The Likun process [40] is another two-step cracking process operated under normal pres-
sure. The process is shown in Figure 28.6. Waste PE, PP and PS are used as raw materials
for oil recovery. In the first phase, the plastics are pyrolyzed at 350–400◦ C. In the second
phase, the cracked gases undergo catalytic reforming over zeolite at 300–380◦ C. The
Bin Cracking reacor
Extruder
Heat exchanger
Figure 28.5 Flow chart of the United Carbon Process

Catalytic reforming
Gas product
Fractionating
Gasoline
reactor
Cracked gases
tower
Waste plastics Diesel oil

Heavy oil
Pyrolysis
Heating the pyrolysis retort

retort
Figure 28.6 Flow chart of the Likun process

744 YUAN XINGZHONG
main products are gasoline and diesel oil. A conversion rate of 75% can be achieved.
This process has the following advantages: (1) the process is simple, conducted under
normal pressure and can achieve continuous production, and (2) high energy efficiency is
achieved, so investment and operation cost are relatively low. In this process 700–750 kg
gasoline and diesel oil products can be recovered from 1 tonne of waste plastics.
3.9 OTHER PROCESSES
The USS process [32] adopts a single reactor cracking system with stirrer. The upper
part of the reactor acts as a catalytic reaction tower and the bottom part as the thermal
cracking reactor. Although its structure is complicated, this process can reduce the total
process flow path and thereby reduce the equipment and capital needed. The process can
be applied in treating PE, PP and PS, but is not suitable for PVC pyrolysis.
The Kurata process [76] is a two-step process which uses thermoplastic resins as raw
material and adds catalysts that consist of five metallic elements such as Ni, Cu, Al and
so on. The temperatures of the two phases are 200–250◦ C and 360–450◦ C, respectively.
During the cracking reaction, the polymer molecules are rearranged. Equipment for HCl
neutralizing is positioned at the end of the process, so there is no clear limitation on the
content of PVC in feedstocks. HCl can be easily removed at a rate of 99.91%, even when
the content of PVC is as high as 20%, and the concentration of chlorine in the products
is lower than 100 ppm. An important difference between this process and the others is
that its products are mainly composed of kerosene.
A high-capacity oil recovery equipment was developed by Libond Industry [77] and
the Macromolecule Cracking Research Institution of Japan, which is capable of treating
100 kg waste plastics per hour. The yield of coke can be controlled at less than 1%, and
a high conversion rate (97%) and oil quality can be achieved. There is a screw pump
and a screw roller in the center of the reactor. Plastics are fed into the reactor after being
granulated, cracked under high temperature and then collected. Part of the uncracked
plastics are pumped back to the reactor by the screw pump and cracked again. The solid
residue is discharged from the bottom of the reactor by the screw auger. The temperature
is kept at around 450◦ C. The plastics are rolled along the wall of the reactor throughout
the whole process, so the heat loss is very small and the cracking efficiency is greatly
improved. By this process, the yield of coke can be controlled at less than 1%, and a high
conversion rate (97%) and good oil quality can be achieved.
4 MAIN FACTORS IN PLASTICS PYROLYSIS
4.1 TEMPERATURE
Temperature is one of the most important factors that affect the process of plastics pyrol-
ysis. The required temperature varies with different types of plastics and the desired
composition of products. At a temperature above 600◦ C, the products are mainly com-
posed of mixed fuel gases such as H2 , CH4 and light hydrocarbons; At 400–600◦ C, wax
and liquid fuel are produced. The liquid fuel products consist mainly of naphtha, heavy
oil, gasoline, diesel oil and kerosene. PE and PP are converted mainly to fuel oil and
gas by pyrolysis, while PS produces more styrene monomers and light hydrocarbons. If
appropriate catalysts are added, the cracking temperature can drop to 200–300◦ C while
the yield of liquid products is increased.
4.1.1 Effects of Temperature on Thermal Cracking

With increase of temperature, the yield of gas products and light hydrocarbons(C3 –C4 )in-
crease, while that of high carbon number products (C21 –C30 ) decreases [78]. In the thermal
cracking process, the proportions of the gasoline and diesel fractions in the liquid products
increase with temperature, while that of heavy oil fraction decreases. The maximum
carbon number of the heavy oil fraction at the end boiling point also increases with the
reaction temperature. Furthermore, owing to the acceleration of dehydrogenation under
high temperature, the yield of coke increases, too.
Prakash et al. [79] reported that the reaction time required to achieve the highest con-
version rate from plastics to oil decreased with increase of temperature, and the conversion
rate of plastics increased, but the selectivity of liquid fuel products decreased dramati-
cally.
Karaduman [80] investigated the effects of temperature on the yields in flash pyrolysis
of PE. The gas yield continued to increase with temperature. The yield of liquid products
and the total conversion rate also kept increasing up to a certain temperature, but after
this point, began to fall slowly due to partial decomposition of the expected products.
The yield of solid residue decreased with the increase of temperature.
4.1.2 Effects of Temperature on Catalytic Cracking

The introduction of catalysts can lower the activation energy for plastics cracking, which
can greatly lower the reaction temperature needed. But temperature is still a very important
factor that can greatly affect the pyrolysis process.
High temperature can accelerate the scission of carbon chains, and as a result, gasoline
yield and the conversion rate from plastics into heavy oil are improved significantly. The
effects of temperature on catalytic cracking of various plastics have been investigated by
Huang et al. [81]. With the increase of temperature, the conversion rate increases initially,
but then gradually slows down and ultimately levels off. But the gasoline yield began to
drop after certain temperature point, and large amounts of gas and coke are produced. It
was found that the optimum temperature varies with different types of plastics. Generally,
the larger substituent in the side chain, the easier the plastic can be degraded. Therefore,
the order of required temperature for pyrolysis of PS, PP and PVC is: PS<PP<PVC. The
main conditions and products of PE, PP, and PVC are listed in Table 28.7.
The effects of temperature on catalytic cracking of various plastics over FZ-W cata-
lyst have been investigated [84] and are shown in Table 28.8. In the temperature range
300–350◦ C, the highest yield of oil products was achieved. When the temperature is
below 300◦ C, yields of residue and noncondensed gases are low, large amount of feed-
stocks were left uncracked; Above 350◦ C, the yields of residue and noncondensed gas
increased, and the amount of oil products obtained decreased relatively.
746 YUAN XINGZHONG
Table 28.7 Main pyrolysis conditions and products of PE, PP and PVC [82, 83]
Species Temperature Catalyst Product

range(◦ C)
PE 120–140 O2 Olefin oxide
350–500 H2 , ZnCl2 Gasoline with high RON
350–450 Al2 O3 · SiO2 Fuel oil
400–650 Silica–alumina Isobutene
PP 320–380 Y-molecular sieve Gasoline and diesel oil
200 Cu Ethylene chloride
PVC 350 Phosphoric acid, sodium silicate Aromatics
400–500 AlCl3 , ZrCl4 , etc. Gasoline and diesel oil
PS 400–450 Solid acid, solid base, transition Styrene monomers
metal oxide
Table 28.8 Effects of temperature on yield of oil products [84]
Reaction temperature (◦ C) 200 250 280 300 330 350 400 450 500
Oil products yield (wt%) 60.5 61.2 63.8 70.8 75.5 71.6 68.7 64.3 60.2
4.2 CATALYST
Two sorts of catalyst have been widely applied in plastics pyrolysis [85], namely: molecu-
lar sieve catalyst or reformed molecular sieve catalyst, such as Y-zeolite and REY zeolite;
metal oxide catalyst, such as silica–alumina, Al2 O3 , CuO, ZnO, Fe2 O3 , cerium oxide and
Co–Mo oxide.
4.2.1 Molecular Sieve Catalyst

Molecular sieve catalyst is composed of silica oxide and alumina, with a special structure.
Since its first introduction in pyrolysis of heavy oil by America Mobil Co. in the 1960s,
molecular sieve catalysts have been widely used in the petrochemical industry. The quality
and yield of gasoline as well as the oil production scale have been greatly improved.
Similarly, a large number of investigations on the function of molecular sieve catalysts
in plastic pyrolysis have been carried out, and it has been proven that molecular sieve
catalyst can also greatly promote the pyrolysis of plastics and improve the quality and
yield of oil products.
Catalysts tend to be deactivated in the process of plastics pyrolysis because of coke
deposition on their surface. The deactivation of HZSM-5, HY, H-zeolite and silica–
alumina was compared by Uemichi et al. [86]. In the case of PE pyrolysis and HZSM-5
added as catalyst, no deactivation occurred due to the low coke deposit, and high yields
of light hydrocarbons (mainly branched hydrocarbons and aromatics) were achieved. In
the case of PS, however, coke production increased dramatically, so HZSM-5 was deacti-
vated very quickly. Silica–alumina catalyst was deactivated gradually and slowly with the
increase of cracking gas, while HY- and H-zeolite molecule sieve catalysts were deac-
tivated very quickly. Walendziewski et al. [87] studied the catalytic cracking of waste
plastics over platinum catalyst, and more than 90% yield of gas and liquid fractions was
attained at a temperature of 390◦ C.
4.2.2 Metal Oxide Catalyst

Metal oxide catalysts have also been widely used in the pyrolysis of waste plastics. It is
reported that PET can be successively decomposed over FeO(OH) [88], a transition metal
oxide catalyst with high activity. The yield of sublimate substances such as terephthalic
acid or benzoic acid were greatly decreased, which effectively avoid the blockage of pipes.
FeO(OH) is transformed to porous Fe2 O3 after steam treatment above 600◦ C so the num-
ber of active sites on the surface increased greatly. Other metal oxide catalysts, such as
ZnO and TiO2 have also been applied [89]. Compared with the noncatalyst condition, the
yields of coke and gas products decreased while the yield of liquid oil increased. ZnO can
promote the forming of 2,4-dimethyl-1-heptene, but has almost no effects on other frac-
tions. TiO2 can restrain the formation of volatile fractions and has little influence on others.
5 PYROLYSIS OF PVC
In the decomposition process of heteroatom-containing plastics such as PVC, EVA and
ABS, heteroatom contaminants are produced which may cause corrosion of equipment
and deteriorate the quality of the fuel products. Therefore, these types of plastics should
be treated by special process. Taking PVC as a example, it is one of the most thermally
unstable polymers, 58.5 wt% of which is chlorine. HCl is generated when PVC is heated
to about 300◦ C. Because HCl may corrode equipment, deactivate catalysts and deteriorate
the quality of products it needs to be removed. Generally, HCl can be removed in three
ways: before degradation, during degradation and after degradation [90].
After preliminary removal of HCl, PVC products can be further degraded at higher
temperature, and linear and cyclic light hydrocarbons are produced. However, HCl can
be only partially removed by the above methods, and the conversion rate of PVC to oil
products is relatively low. Therefore, PVC is generally not degraded separately, but mixed
with other plastics such as PE, PP, PS and PET in a certain ratio before degradation.
There are all kinds of processes and reactors for pyrolysis of PVC-containing mixed
plastics which can be basically divided into three classes: thermal cracking, catalytic
cracking and hydrogenation. The main products are gasoline, diesel oil, fuel gas and HCl.
In the thermal cracking process, reactors such as a molten bath reactor or a fluidized
bed reactor are usually adopted. A special thermal cracking process for the degradation of
mixed plastics containing PVC was developed by Mitsubishi Heavy Industry [91]. After
being granulated to certain dimensions, the mixed plastics were transferred to the screw
extruder through a nonreturn valve. Before entering the cracking reactor, the mixed plastics
are heated and melted in the extruder. The molten plastics are pyrolyzed at a temperature
of 400–450◦ C in the reactor. A condensor is installed on the top of cracking reactor,
and the temperature is kept at 200–300◦ C. High-boiling-point substances (i.e. ‘heavies’)
in the cracked gas are condensed and returned to the reactor for further cracking. The
noncondensed gases are cooled to normal temperature by a cooler, and the liquid products
enter the oil collector. The HCl generated in the process and other noncondensed gases
pass into the absorption tower. Hydrochloric acid is obtained by mixing with water and
748 YUAN XINGZHONG
then separated by a decanter. The other gases enter the neutralizing tank, where the
residual hydrochloric acid is removed, before collection in the gas holder. A conversion
rate of 55.7% was achieved in this process.
Good results were also achieved by catalytic cracking in the Fuji and BASF [92]
processes, in which mixed plastics containing PVC were pyrolyzed over ZHSM-5 [93].
After granulation and removal of metal and glass, plastics can be mixed with oil and
then cracked and removed of HCl in a hydrogenation reactor at 500◦ C and 40 MPa
pressure in hydrogen atmosphere [91, 95]. A high yield of gas and oil products can be
achieved by hydrogenation.
Among other methods, the recovering of fuel oil from mixtures of residual oil, lignite
and plastic waste under high pressure and in hydrogen atmosphere was successfully real-
ized by Veba [94]. Lignite acts as both feedstock and catalyst here. Na2 CO3 and CaO are
added to neutralize the HCl generated in the reaction process. Gaseous C1 –C4 , hydrocar-
bons alkanes, cycloalkanes and aromatics were obtained. However, the high pressure and
the hydrogen atmosphere greatly increased the cost.
Another cracking technology was developed by the Toshiba company [95]. After being
crushed into pieces, mixed plastics containing PVC entered the cracking reactor and were
heated; highly concentrated alkali liquor is added to neutralize the HCl. After chlorine
is removed, the other fractions continued to be heated and cracked in the reactor. High-
quality gasoline and diesel oil products were achieved by this process.
The pyrolysis of mixed plastics containing PVC in supercritical water has also been
demonstrated [96]. The temperature in the reactor increases from 200◦ C at the top to
1200◦ C at the bottom. HCl is generated in the first reaction zone. In the second zone,
HCl continues to react with alkali metal and is removed, and residue and fuel gas which
mainly consists of H2 and CH4 are produced by reaction of plastic waste and supercritical
water. In the third reaction zone, part of the residue produced was oxidized and CO and
fuel gases were generated.
A gasification process for mixed plastics containing PVC without special dechlorination
equipment was developed by Borgianni [97]. Experimental results showed that addition
of Na2 CO3 can effectively remove the chlorine generated, the concentration of pollutants
in gas products is pretty low and the fuel gas obtained can be used directly for power
generation or for heating.
6 CATALYTIC REFORMING OF CRACKED GAS

The RON of gasoline obtained by thermal cracking or catalytic cracking is generally just
about 80, and the flash point of diesel oil product is also very low. By isomerization and
aromatization, catalytic reforming of cracked gas can greatly improve the quality of liquid
fuel products.
The results of catalytic reforming of cracked gas over three isomerization catalysts
(JD-01, JD-02, BJ-01, which have been developed by the oil refining industry in China)
are listed in Table 28.9 [98].
It is shown that after catalytic reformation, the quality of liquid fuel produced is
improved greatly. RON of gasoline reached more than 90 and the flash point of diesel oil
also increased.
It has been reported [34] that normal catalysts such as silica–alumina (SA) and HZSM-5
zeolite have little effects on the reforming of waste-plastics-derived heavy oil, but good
Table 28.9 Experimental results of catalytic reforming
Catalyst Overall yield of oil Yield of Yield of diesel RON

products (%) gasoline (%) oil (%)
JD-01 82.0 53.0 29.0 93.66
JD-02 80.3 52.6 27.7 91.00
BJ-01 82.4 53.9 28.9 90.28
No isomerization 83.03
results can be achieved by the application of HY and REY zeolite because they have
larger hole dimensions. Under the REY condition, the gasoline yield reached 48% with a
RON of 67. By comparison, under of SA and HZSM-5, the gasoline yield and RON are
only 18% and 23 respectively.
The results of ZrO2 in cracked gas reforming was compared with FCC catalyst [36].
When ZrO2 is applied, the yield of both gasoline and diesel oil reached a very high level,
and high-quality gasoline is obtained. In the case of FCC catalysts, however, both the
yield and quality of liquid products are just a little better than the nonreforming case.
Therefore, it is obvious that ZrO2 is a better catalyst for cracked gas reforming.
In the Fuji process, molecular sieve catalyst is used for catalytic reforming, and the
results are shown in Table 28.10.
When no reforming process is carried out in the pyrolysis of PP, 90.50% of the gaso-
line fraction in the products is olefin, and the yield fractions of isomerized paraffins,
cycloalkanes and aromatics are very low. The gasoline has a RON of no more than 80
and is very unstable [99]. However, after reforming and fractionation [100], the results
improved significantly, as shown in Table 28.11. Two kinds of molecular sieve catalysts
were adopted for the process.
Table 28.10 Components and yield of products by the Fuji process [37]
Plastics Components (%) Yield (%) Density g/cc
Paraffin Olefin Aromatics Fuel oil Cracked gas Residue

PE+PP 48.2 13.0 38.8 80 15 5 0.8036
PS 4.8 3.7 91.5 90 5 5 0.8880
Table 28.11 The composition and properties of gasoline fraction
Thermal Thermal pyrolysis–Catalytic Catalytic pyrolysis

pyrolysis reforming (440◦ C)
Temperature (◦ C) and catalyst 440 A(380) B(340) A(440) B(440)
applied
Paraffin 9.07 5.45 3.34 2.55 2.31
Isomerized paraffin 5.09 23.69 18.69 30.92 28.53
Olefin 81.43 53.80 61.13 48.66 52.73
Cycloalkane 3.38 6.05` 6.37 11.87 9.69
Aromatics 1.03 11.01 10.20 6.00 7.11
RON 80.0 87.3 90.8 86.6 88.6
Stability Bad Good Good Good Good
A, B are two kinds of molecular sieve catalysts

750 YUAN XINGZHONG
Table 28.12 Properties of diesel oil fraction
Thermal Thermal Catalytic pyrolysis

pyrolysis pyrolysis–catalytic (440◦ C)
reformation
Temperature (◦ C) and 440 A(380) B(340) 440
catalyst applied
ρ20 (g/cm3 ) 0.8568 0.8617 0.8567 0.8687 0.8674
T50 /◦ C 280 280 270 298 300
Cetane number 45.35 42.72 42.42 44.06 45.30
Stability Bad Good Good Good Good
The characteristics of the diesel fraction by pyrolysis of PP at 440◦ C are shown in

Table 28.12.
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Index
Note: page references with suffix ‘f’ represent a Figure, and ‘t’ represents a Table
ABS degradation of plastics 231t, 617

catalytic cracking of 78 effect of catalysts 197, 231
heteroatoms from 77 gasification reactions 182, 183t
pyrolysis of 330–1, 721 hydrocracking of PE 62f, 63, 64f, 65f, 66
acetophenone, from catalytic cracking of PET additives 4–5
166, 167 effect on recycling 5, 14
acicular coke, production of 724 environmental impact 376
acid catalysts 46, 80–1, 118, 172, 195–6, advantages
211 catalytic cracking 76–7, 194, 210, 226
coprocessing of MWP/HVO blends fluidized-bed reactors 135, 210, 436, 444,
218–21 547, 627
limitations 211 free-fall reactors 615, 616, 617
plastics-derived heavy oil cracked by microwave heating 571, 582, 586
172–5 pyrolysis 384–5, 431, 494, 532–3
polyolefin cracking by 46–54, 82, 83f, rotary kiln reactors 547, 551, 711
84f, 93f, 118, 195, 386
agricultural plastics
temperature effects 716
conversion to diesel 412–13
acid-catalyzed hydrolysis, of PET 647–8
pyrolysis of 598
acidity of catalysts 173t, 183t, 239
factors affecting 196, 239 air pollution 133, 135, 193, 376, 532
measurement of 173, 196 AIST glycolysis process 644, 645f
for various catalysts 240t Akzo fluidized-bed pyrolysis process 438t,
acrylonitrile–butadiene–styrene copolymers 468–9
see ABS commercial status 469
activated carbon Al-MCM-41 catalyst 395
production of 552, 574, 657 alkyl aromatics
regeneration of 573 from catalytic cracking
activated carbon catalysts 48, 211 of PE 49, 50, 50f, 51, 52f, 53–4, 76f,
hydrocracking by 216 152f
activated carbon/transition metal catalysts of PS 54–9, 116
84, 103f, 149, 211 see also toluene
see also Co-AC catalyst alumina
activation energy catalytic cracking by 147, 148–9, 148t
calculations 227 see also silica–alumina catalysts
758 INDEX
aluminium/plastic laminates, pyrolysis of fixed-bed 441t
385, 573 fluidized-bed 440t, 466, 469, 470
aluminium–zinc composite, catalytic cracking fuels produced 278t, 279t, 331
by 96 rotary kiln 442t, 443t, 557
Amat Ltd 586 see also shredder light fractions
American Plastic Council (APC), waste
plastics sample 214 base-catalyzed hydrolysis, of PET 648–9
Amoco process 438t, 740t
BASF process 17, 27–8, 122, 368, 369f,
amorphous silica–alumina (ASA) 80–1, 147
439t, 740t, 741, 748
HDPE catalytic cracking by 148t
batch reactors
physicochemical properties 147, 240t
catalytic cracking in 86, 195
see also silica–alumina catalyst
pyrolysis in 289t, 290t, 393–4, 710–11
AMRA fluidized-bed pyrolysis process 438t
Battelle fluidized-bed pyrolysis process 438t,
antioxidants, in fuel oils 400, 402
Arabian crude oils, vacuum residues, 468
properties 365t BC-Pyrocom rotary kiln 555t, 558–9
aromatics Beijing Roy Environment Technology
in commercial gasoline 179t, 185f Company see Royco process
from catalytic cracking Belgium, packaging waste data 33t
of mixed waste plastics 236, 236t benzene
of PE 49, 50, 50f, 51, 52f, 53–4, 140, from catalytic cracking
143f, 145f, 148t, 151–2, 151f of PE 76f
of PS 54–9, 151f of PS 54, 55f, 56, 59, 116
of pyrolytic waxes 213t from pyrolysis
from heavy-oil conversion 178f, 179f, of PET 266
184, 185f of PS 618, 619f
from pyrolysis of PVC 264
of PET 266 benzoic acid, from PET cracking 166, 167,
of PS 262, 307–8 329
of PVC 264, 308–9 Bergius Pier hydrogenation technology 30,
see also PONA distributions 118
aromatization reactions 238, 735 Berlin Consult see BC-Pyrocom rotary kiln
Arrhenius equation 227, 228 beta zeolite catalyst
Arrhenius plots, catalytic cracking of cracking of olefins 149, 495
plastics-derived heavy oil 182f physicochemical properties 80t, 240t
Asia, recycling of PET bottles 642t β−scission
asphaltenes 365 in catalytic cracking 51, 57–8, 75, 115,
amount in vacuum residues 365t 211, 237, 243
removal from distillation residues 366 in pyrolysis 75, 320, 715f
Association of Plastics Manufacturers in bifunctional catalysts 132–3, 214, 241–3
Europe (APME) 36, 38 reaction mechanisms 132–3, 214
Ateklab free-fall reactor biomass
experimental procedure 611–12 co-gasification with plastics 120
LDPE pyrolysis using 613–17 gasification of 438t, 468
PS pyrolysis using 617–20 pyrolysis of 274, 608
set-up 610–11 bis-2-hydroxyethylene terephthalate
Atkinson–McCaffrey kinetic model 228 formation of 643, 644
attrition index, catalysts 718–19 polycondensation into PET 644
auger kiln reactors 515, 522, 550 bituminous coal, devolatilization of 606, 607
see also Conrad process BKMI rotary kiln process 554t
autoclave reactors 16t, 117, 144, 195 blast furnaces, plastics waste used in 8, 20,
automobile shredder residue (ASR) 33–4 23, 30, 37, 368–9, 669t, 704
collection of 26 Blowdec depolymerization process 429–30
composition 557 boiling point distributions, liquid products
feedstock recovery from 34 203–4, 352f, 376
pyrolysis 329–31 bond energies
INDEX 759
carbon–carbon bond 596, 635 calcium ion-exchanged X-type zeolite catalyst
carbon–fluorine bond 635 see CaX catalyst
carbon–hydrogen bond 635 calorific (heating) value
BP fluidized-bed pyrolysis process 28–30, coal 734
122, 438t, 467–8, 738, 739t fuel oils 155t, 305–6, 305t, 533t
economic considerations 30, 468 plastics 710
operating experience 467–8 pyrolysis oils 155t, 304t, 429t, 674t
preliminary experiments in Hamburg 476, carbenium/carbonium ion formation, in
486 catalytic cracking 51–3, 76, 114, 132,
products 29, 122, 468 211, 228, 230, 735
typical input specification 392t carbon, as microwave absorbent 572
British Gas/Lurgi slagging gasifier 277 carbon black
brominated fire/flame retardant materials as microwave absorbent 574, 584
high-impact polystyrene see HIPS-Br recovery from tyres 466, 490
thermal degradation of 339–40, 558, 721 carbon–carbon bond energy 596, 635
Brönsted acid sites on catalysts 51, 76, 81, carbon composite HCl sorbents
147, 196, 219 adsorption capacity 511t
bubbling fluidized beds 436 experimental procedure 498
comparison with other reactor types factors affecting 511–13
446–9t HCl reaction profiles 510f
gasification in 276, 438t laboratory evaluation of 509–14
pyrolysis in 394, 438t, 440t, 467 experimental procedure 496–7
effect of process variables on products preparation of 496
458–61t see also calcium carbonate carbon
of mixed plastics 458t, 459t, 464–6 composite; iron oxide carbon
zones 452–3, 453f composite; potassium carbonate
butadiene rubber, pyrolysis products 333 carbon composite
by-products carbon–fluorine bond energy 635
plastics pyrolysis 14–15 carbon–hydrogen bond energy 635
coke formation 15 carbon nanotubes 464, 465f
effects of additives 14 carbon number distribution
effects of hetero-atoms 14 catalytically cracked plastics 384f, 505f,
secondary reactions 15 507f
plastics-derived heavy oils 172f, 687f
C-NP gram, pyrolysis oils 687f pyrolysis products 384f, 504f, 505f, 507,
calcium carbonate carbon composite (Ca-C) 509f, 521f, 523f, 524f, 687f
sorbent after catalytic cracking 186f, 188
adsorption capacity 511t carbon residues, in fuels 155–6, 155t, 305t,
effect of inlet HCl concentration 399
512–13 carbon-supported metal catalysts 84, 103,
effect of particle size 513, 513f, 514t 149
effect of temperature 511–12, 512f carbonization 251
dechlorination of PVC/PP/PE/PS mixed predictive model 271–2
plastics by 514–18, 556 process parameters 253t, 287t
dehalogenation of PVC/PP/PE/PS/HIPS-Br product distribution and yield affected by
mixed plastics by 518–21 operating conditions 254t
effect of temperature 511–12, 512f slow process 251, 253t
HCl reaction profile 510f time factors 252
physical properties 496 see also gasification; pyrolysis; thermal
preparation of 496 degradation
calcium carbonate/hydroxide/oxide, catalysts 79–85, 146–9, 239–44, 715–19,
dehalogenation by 29, 119, 123, 212, 746–7
390–1, 397, 467, 482, 540, 541t, 556, acidity 173t, 183t, 239
673, 682, 741 factors affecting 196, 239
calcium hydroxide, effect on pyrolysis of PET listed for various catalysts 240t
390, 655, 656f, 693 measurement of 173, 196
760 INDEX
catalysts (continued ) mass balance 731, 732t
activity 404–5, 716 multistage processes 97–9
loss in fluid catalytic cracking 228 PE 45–6, 46–54, 75–6, 79–85, 93, 94,
bifunctional 132–3, 241–3 139–41, 140–9, 746t
Brönsted acid sites 76, 81, 147, 196, 219 PET 78, 233t, 416–17, 655–7
chemical properties 146–7, 173t, 183t, plastics derived heavy oil 172–88
716–17 plastics suitable for 77–8, 113, 416
alumina content 717 PP 148–9, 404, 746t
hydrogen factor 716–17 products obtained 48–59, 78–9, 130,
rare earth content 717 139t, 143f, 148t, 212
sodium content 717 PS 46, 54–9, 77, 116, 232t, 233t, 406–7,
deactivation by coke deposits 95, 123, 746t
144, 174, 218t, 404, 746 PVC 233t, 746t, 748
disposable/throwaway 122 reaction mechanisms 51–3, 76, 114–15,
effect on product properties 116, 141–4, 211, 228, 230–8, 422
241t solvents used 103
effect on pyrolysis temperature 231, 710, temperature effects 93–4, 139–41, 231,
716 404, 745, 746t
external 406 in Thermofuel process 408, 410f, 411
heterogeneous 79–85 as upgrading step for pyrolysis products
homogeneous 79 86–7, 96, 99–101, 172–88, 406
Lewis acid sites 76, 81, 147, 196, 219 vapor-phase reactions 146
micro activity test for 716 catalytic dehalogenation 96, 407, 420, 496,
monofunctional 239–41 505–8, 563
physicochemical properties 80t, 147, catalytic isomerization dewaxing 398, 417
173t, 183t, 240t, 717–19 catalytic pyrolysis
apparent bulk density 717 early research 194–5
attrition index 718–19 in fluidized-bed reactors 445t
loss on ignition 718 further research required 205
particle size distribution 717–18 HDPE 140–53, 232t, 233t, 495
pore size 80t, 173t, 240t, 718 effect of catalysts 141–4
pore volume 240t, 718 effect of PS addition 149–53
surface area 240t, 717 LDPE/EVA mixture 394–5
X-ray crystallinity 718 NanoFuel/Polymer-Engineering process
poisoning of 77, 211, 219, 717 418–22
purpose of 10, 115, 386, 715–16 suitability of various reactor types 448t
selectivity 404–5 various studies listed 232–3t
Smuda process 416 catalytic reforming 748–50
see also acid catalysts; zeolite catalysts see also cracking–catalytic reforming
catalytic cracking 10, 43–247, 736–7 CaX catalyst, gasification using 182
advantages 76–7, 194, 210, 226 centrifuges, in pyrolysis plant 397
compared with thermal cracking 74–7, ceramics industry, microwave heating
116, 118, 133, 194, 209–10, 383–6 in 572
direct process 97–9 cetane number (for diesel)
effect of operational variables 92–6, 117, calculation 317
118 catalytically cracked products 236t, 418,
catalyst concentration 94–5, 196–8, 750t
199f, 233–4 pyrolysis products 304t, 324, 326, 327,
plastics waste composition 95–6 429t, 674t, 685t, 698t, 750t
temperature 93–4, 117 chain-end scission 114, 130, 131f, 132, 456,
time 95 457, 630, 714–15, 715f, 734
industrial processes 418–22, 438t, 440t, chain-stripping reactions 131, 132, 735
441t, 741–4 char
laboratory experiments listed 730t from hydropyrolysis of coal 609
limitations 74, 77, 97, 129, 144, 226, 386 from pyrolysis of various wastes 278t
liquid-phase reactions 146 energy contents 279t
INDEX 761
charcoal production 251, 287 microwave pyrolysis of 574, 582
chemical analysis methods 296, 316 coal-tar pitches, co-coking with plastics 120
chemical feedstock potential, oils/waxes for coal-to-oil hydrogenation plant 30, 369
pyrolysis 306–9 cobalt resinate catalysts 416
chemical recycling 225, 367, 612–13 co-gasification, biomass with plastics 120
in Japan 669t coke deposits
see also feedstock recycling catalysts affected by 95, 123, 144, 174,
chemical structure of plastics 294f, 364–5 218t, 404, 406, 746
classification 364 characteristics 403
China
formation of 15, 54, 95, 123, 201
Hunan University process 740t, 742
Likun process 431, 740t, 743–4 effect of catalyst types 148t, 201, 202
Royco process 422–3 from coprocessing of MWP/HVGO
survey article 729–55 blend 218t
Chiyoda process 429 test for coking tendency 156
chlorinated hydrocarbons leachability potential (in landfill) 403
from pyrolysis of PVC mixed plastics prevention of build up during pyrolysis
517, 522–3 392–3
GC-AED chromatograms 517f uses 112
chlorine cold filter plugging point (CFPP), diesel
fixation of 29, 96, 119, 123, 212, 349, 399–400, 401
390–1, 397, 467, 482 collection systems (for waste) 24–5, 667
problems caused by 15, 77, 217, 367, costs 26t, 33, 703–4
390, 495, 747 combined power plant, pyrolysis fractions as
chlorodifluoromethane, pyrolysis of 574 feed 553
2-chloro-2-phenylpropane 517 commingled plastic waste
circulating fluidized beds 436 catalytic liquefaction of 210–21, 234–7,
advantages 436
347–50
comparison with other reactor types
446–9t pyrolysis of 267–71
disadvantages 437 see also mixed plastics waste
gasification in 276, 438t Compact Power pyrolysis/gasification process
pyrolysis in 394, 438t, 443t, 468–9 439t
circulating-spheres reactor 168, 394, 552 computer circuit boards
see also stirred heat-medium-articles pyrolysis of 561f
reactor see also electrical/electronic equipment
clay-based catalysts 81–2, 195, 405–6 waste
liquid yields 202 condensation polymers, see also ABS; PC;
Climax Plus method 586 PET; polyamide; polyester; polyurethane
cloud point 399, 401 conduction heating 570
diesel 401 Conrad process 430, 537–41, 550, 555t
effect of linear hydrocarbons 317, 387, dehalogenation methods 540, 541t
400 flow diagram 538f
lubricating base oils 357t product analysis 540t, 541t
plastics-derived fuels 399, 400 product yield at various temperatures
Co-AC catalyst
539t
hydrocracking by 218, 219, 220, 221
product distribution 218t PVC mixed plastics 515, 522, 556
coal Conradson carbon test 156
calorific/heat value 734 Consortium for Fossil Fuel Science 346
coprocessing with plastics 101–2, 216, consumption data (for plastics) 73, 205, 285,
370, 723, 737–8 286t
dechlorination of PVC using 721, 725 Containers and Packaging Law (Japan) 37,
desulphurization of 609 666–7
flash pyrolysis of 606–8, 609 waste plastics specified 678
hydro-gasification of 34, 607, 609 ConTherm process 553, 555t
762 INDEX
continuous pyrolysis plants 394 thermal methods 5, 39, 99, 117, 210, 211,
see also extruder reactors 217, 278, 294, 327, 328f, 377f, 495,
continuous stirred tank reactors 395 584, 696, 701–2, 741, 747
agitators/impellers in 396 degradation of plastics
conventional pyrolysis see slow pyrolysis kinetics 226–38
conversion rates, comparison of pyrolysis types 225
reactor types 447t dehalogenation
coprocessing various approaches 24, 29, 39, 96, 99,
coal with plastics 101–2, 216, 370, 723, 117, 563
737–8 see also chlorine fixation; dechlorination
distillation residues with plastics 369–74 dehydrocyclization 132
Fischer–Tropsch wax with LDPE 356, dehydrogenation, of naphthenes 132–3
357t, 358 Denmark, recycling of packaging waste
HDPE with PET 356, 356t plastics 33
limitations 217 density
naphtha with polyolefins 13–14 fuel oils 155t, 305t
oil wastes with plastics 102–3, 119 plastics pyrolysis oils 155t, 304t
petroleum fractions with plastics 102–3, Department of Energy (DOE, USA) sponsored
113, 119, 195, 205, 217, 369–74, study 346
418, 422 depolymerization 11, 74, 90
solvents with plastics 103 destructive distillation see pyrolysis
corrosion problems 15, 77, 217, 367, 390, destructive hydrogenation see hydrocracking
393, 747 desulphurization of coal/lignite 608, 609
cost considerations DGEBA-type epoxy resin 339
collection and recycling of waste plastics DHC-8 catalyst
26t, 33, 703–5, 706–7 hydrocracking by 217, 218, 219, 220, 221
landfill 206 product distribution 218t
various industrial plants 28, 30, 31, 350, see also amorphous silica–alumina
359, 376–8 DHC-32 catalyst 371t
various pyrolysis reactor types 449t dielectric loss tangent 571
cracking–catalytic reforming 431, 730, 737 diesel
see also two-stage processes additives 401
cross-linked polymers 364–5 cold flow improvers 401
see also thermosets commercial
cross-linking reactions 131, 735 GC spectra 410f
crude oil prices 20t
limited resources 531 properties 155t
prices 20t nitrogen oxides emissions 413
as reference point for economic plastics-derived 97–8, 99, 150, 151f,
considerations 124, 273, 350, 155, 235, 236t, 384, 603–4
359 commercial processes 407–14
Cycleplast project 12, 13 composition 236t
instability 400
kinetic data 21t
low-temperature properties 399–400
cyclization reactions 238, 318, 319f
properties 236t, 749t
stabilization of 400–1
DAL rotary kiln process 555t storage stability 401–3
DBA process 439t unsaturated hydrocarbons in 399, 402
decalin, in catalytic cracking process 103 sulfur content 155t, 413
dechlorination Thermofuel process 411f, 413
by Ca-C sorbent 514–21, 556, 563 diesel sludge 400
catalytic 96, 407, 420, 496, 505–8, 563, differential scanning calorimetry (DSC) 7
720–1, 722 differential thermal analysis (DTA) 7, 201
chemical methods 29, 119, 123, 212, 349, microwave method 575
390, 397, 467, 482, 556, 673, 682, dimethyl terephthalate
721, 741, 748 recovery from waste PET 644–5
INDEX 763
transesterification with ethylene glycol fluidized-bed 438t, 440t, 466, 469,
643 470
2,4-dimethylhept-1-ene 387, 388f rotary kiln 552–3, 555t, 557–62
diphenylmethane diisocyanate (MDI), from see also waste from electrical and
pyrolysis of polyurethanes 335, 336, electronic equipment (WEEE)
337 electrical pulse heating, coal pyrolysis using
Dispons continuous pyrolysis process 606
598–604 electromagnetic spectrum 570f
continuous feeding of waste plastics elimination reactions 318
598–9 end-chain scission 114, 130, 131f, 132, 456,
heating methods 599–603
457, 630, 714–15, 715f, 734
schematic of plant 601–2f
end-of-life-vehicles (ELV) waste 33
disposable/throwaway catalysts 122
disproportionation, chain termination by 130, see also automobile shredder residue
131f, 238 end-use of plastics, analysis by sector 286f
distillation, fractional 153–4 energy balances
distillation columns, in pyrolysis plants 397, fluidized-bed pyrolysis of PMMA 634
429, 673, 682 Japanese liquefaction plants 675–6, 677f,
distillation range 688–9, 691t, 700f
fuel oils 157–8, 157f, 305t pyrolysis process 732–3
pyrolysis oils and distillates 157–8, 157f, energy profit calculations 733–4
304t, 675f, 686f, 699f energy recovery 10, 252
distillation residues 365 industrial processes 439t, 440t, 441t,
upgrading of 366, 369 469, 494, 553, 555t
double rotary kiln pyrolysis 550 see also waste-to-energy (WTO)
downdraft gasifiers 276, 277 engine oils, viscosity index 351
drink carton material, microwave pyrolysis of entrained bed gasifier, in Texaco gasification
573, 580–1 process 277, 367
DSD packaging waste collection system entrained-flow reactors 274–5, 278, 441t
(Germany) 27, 346–7 environmental considerations 38, 376, 678,
mixed plastics waste 27, 214, 347 692–3
composition 210t, 485t Environmental Waste International 586
fluidized-bed pyrolysis of 459t, 482 epoxy resin
pyrolysis products 347–50, 485t
chemical structure 294f
dual-functional catalysts 214
pyrolysis of, oil/wax products, FT-IR
see also bifunctional catalysts
dump fees 20 spectra 299f, 300
see also gate fees; tipping fees pyrolysis products 339–40
ethical considerations 37
ethylbenzene see alkyl aromatics
Ebara Company (Japan) ethylene glycol
fluidized-bed plants 8, 26, 34, 440t glycolysis of PET with 644
see also Ube-Ebara reaction with dimethyl terephthalate
Ebara TwinRec process 440t, 469–71
643–4
commercial status 470–1
reaction with terephthalic acid 643
economic considerations 470
performance 470 recovery from PET 644–5
economic considerations 22, 30, 36, 124, Europe
205–6, 279–80, 350, 359, 376–8 plastics consumption/waste data 73, 209,
monomer recovery 627 285, 286t, 363, 612
Eddith process 439t recycling of PET bottles 642t
electrical/electronic equipment waste tyre waste 573
collection and recycling of 25, 26, 34, European Union
391 End of Life Vehicles Directive 33
EU recycling quotas 558t Packaging and Packaging Waste Directive
pyrolysis 35, 337–41 24, 33, 73
764 INDEX
recycling quotas/targets 558t supply logistics 25–6
WEEE Directive 33, 558 waste collection systems 24–5
EVA copolymer, thermal and catalytic fire/flame retardants 24, 391, 466, 558
cracking of 85 see also polybrominated flame-retardant
exchangeable/removable heating coil 121 materials
external catalysts 406 first-order kinetics 226–7
extruder reactors 15–16, 16t, 91, 120–1, Fischer–Tropsch waxes 351
440t copyrolysis with LDPE 356
comparison with other reactor types lube oil produced 356, 357t, 359
446–9t pyrolysis products 357t, 358, 359f
extruders (to feed plastics) 394, 414, 422, hydroisomerization of 357t, 359
440t fixed-bed reactors
extrusion–rotary kiln reactors 531–67 catalytic cracking in 86, 88, 95, 135,
compared with fluidized-bed reactors 165–6, 169, 173, 183
546–7 comparison with other reactor types
industrial-scale processes 533–47 446–9t, 580t, 654t
see also rotary kiln reactors gasification in 276, 277, 439t
EZ-Oil Generator process 422 hydrolysis of PET 659
pyrolysis in 16, 16t, 135, 375, 615
gas products 293t
far-infrared heating system, in Royco process PET pyrolysis 653–4
423 product distribution 289t, 290t
fast pyrolysis see flash pyrolysis; ultra-fast flame retardants see fire/flame retardants
pyrolysis flammability testing 7
FAU type zeolites see zeolite Y flash point
Faulkner rotary kiln system 550–1 liquid fuels 305, 305t, 317
FCC catalysts 147, 195, 196 pyrolysis oils and distillates 325, 429t,
coking tendency 202 674t, 685t, 698t
coprocessing of distillation residues with see also ignition point
waste plastics 370, 371t, 374t flash pyrolysis
in fluidized-bed pyrolysis 459t coal 606–8, 609
liquid products produced over, boiling compared with slow pyrolysis 253t, 287t,
point distribution 204f 617
physicochemical properties 240t of mixed plastics waste 268t, 271
pyrolysis of PS affected by 406–7, 459t PE 254t, 255, 258f, 613–17
pyrolytic waxes cracked using 212–13 product distribution 255t
spent 81, 130 temperature effects 255t, 258f, 745
HDPE/PS mixtures cracked using of PET 266
150–3f of PP 258–9, 261f
polyolefin cracking by 81, 86, 87f, 90, process parameters 253t, 287t, 605,
97, 116, 140–1f, 141–2, 142f, 144 606–9
feedstock recycling of PS 262, 264f, 617–20
advantages 286 of PVC 264
halogen content limit 562–3 pyrolysis technologies 273, 274–5
hetero-atom considerations 23–4, 562–3 see also fluidized-bed pyrolysis; free-fall
industrial plants 27–32, 367–9 reactors
meaning of term 6, 367, 494 fluid catalytic cracking 120, 394
mixed plastics waste catalytic activity loss 228
gas composition 295 effect of catalyst surface area 717
with low PVC content 367–9 in Reentech process 425
product yield 291–2 see also FCC catalysts
reasoning behind 22–3 fluid-bed coking 394
single plastics fluidized-bed pyrolysis 16t, 17, 18, 19,
gas composition 292–5 89–90, 115, 116–17, 210, 274, 290–1,
oil/wax composition 295–309 394, 435–91
product yield 288–91 Blowdec process 429–30
INDEX 765
BP process 28–30, 122, 438t, 467–8 high-temperature pyrolysis in 439t, 440t,
carbon path within bed 450f 445t
compared with microwave pyrolysis 576, hydrodynamic aspects 18, 435–7, 457
580t hydrolysis of PET 659
defluidization times for various plastics lean-phase systems 436
455f low-temperature pyrolysis in 438t, 439t,
degradation mechanisms 456–7 441t, 442t, 443t, 445t
effect of process variables on products particle size effect on fluidization 717
456–66 predictive defluidization models 454–5
first used for plastics 437, 475 residence time effects 90, 447t, 457, 627
gas products 293t segregation of aggregates in 451f, 454
gas-phase operations 19, 450f, 453f sintering of particles in 451f, 454
Hamburg process 9, 27, 89–90, 123, 195, see also bubbling...; circulating fluidized
437, 475–91 beds
high-temperature 439t, 440t, 445t fluoropolymers 635
industrial/demonstration plants listed see also PTFE
122–3, 438–43t, 467–71 Flynn–Wall equation 227t
key features 212 Fost Plus (Belgium) packaging waste
low-temperature 438t, 439t, 441t, 442t, collection and recycling scheme 33, 34t
443t, 445t Foster Wheeler rubber pyrolysis process 16,
oils/waxes 300–4 16t
operability range for 453–6 Fourier transform infrared (FT-IR)
PE 458t, 459t, 460t, 461t, 462 spectrometry
PET 455f, 464, 654–5 PET pyrolysis products 164f, 297f, 298,
PMMA 90, 629–34 652, 653f
pyrolytic oils/waxes 296–300
polymer degradation processes 452–3
fractional distillation 153–4
polyolefins 27, 90, 123, 458–61t, 462–4,
gas products stream 154
482–3, 484t, 486–7
heavy oil products stream 154
effect of steam on product distribution
light oil products stream 154
483, 486t, 742 free-fall reactors
PP 459t, 461t, 462–4 advantages 615, 616, 617
primary cracking step 450f, 451f Ateklab system
coated particle vs molted drop experimental procedure 611–12
approaches 452, 452f LDPE pyrolysis results 613–17
product distribution 289t, 290t PS pyrolysis results 617–20
PS 90, 123, 459t, 464, 618, 635 set-up 610–11
PTFE 636–8 coal pyrolysis using 606–8, 609
sequence of steps in reactor 444, 450, design aspects 609–10
450–1f earliest publication 606
see also BP process; flash pyrolysis; free-radical mechanisms
Hamburg process in catalytic hydrocracking 219
fluidized-bed reactors 88–90, 120, 135, 711, in thermal cracking 22, 114, 219, 318,
712f 320–1, 331–2, 630–1, 713–14, 715,
advantages 135, 210, 436, 444, 547, 627 720
bed defluidization in 451f, 453–4, 655f Friedmann equation 227t
catalytic cracking in 90, 93, 94, 195 FSM-16 catalyst 81
catalytic pyrolysis in 445t fuel oils
compared with other reactor types additives 401, 402
446–9t ash content 155t, 156, 305t
microwave pyrolysis 576, 580t calorific/heating values 155t, 305–6,
rotary kilns 446–9t, 534, 546–7, 553 305t, 533t
dense-phase systems 436 carbon residues in 155–6, 155t, 305t,
disadvantages 135, 437, 444, 617 399
economically viable limit 123 cloud point 399, 401
gasification in 276, 438t, 440t density 155t, 305t
766 INDEX
fuel oils (continued ) PS catalytic cracking 54, 55f, 57f
distillation range 155t, 157–8, 305t pyrolysis products 316
flash point 305, 305t of ABS 331f
ignition point 155t, 156 of brominated epoxy resin 340f
pour point 155t, 305, 401 of HDPE 323f
properties 155t, 156, 305t of LDPE 615f
sulfur content 155t, 156, 305t microwave pyrolysis 580
suspended sediments in 155, 155t of natural rubber 332f
viscosity 155, 155t, 305t of Nylon-6, 6 334f
water content 155, 155t, 305t of PET 330f, 656f
fuel prices 20t of phenol–formaldehyde resin 341f
fuel properties 307–8, 317 of polycarbonates 338f
pyrolysis oils/waxes 304–6 of polyurethanes 336f, 337f
relation to chemical composition of of PP 325f
pyrolysis liquids 317–18 of PVC 328f, 500
standards covering 304–5 repetitive injection studies 47
fuel quality, factors affecting 79, 399–403 see also repetitive injection GC/MS
fuel valorization 278–80 gas oil
by gasification 279–80 calorific/heating value 305t, 533t
by pyrolysis 278–9 commercial prices 20t
fuels optimum temperature in catalytic cracking
boiling point distributions 203–4 177
catalytic cracking processes for production properties 305t
of 96, 97–8 as pyrolysis product 17
economic considerations 205 see also vacuum gas oil (VGO)
petroleum-derived, properties 155t, 305t gas phase pyrolysis 19, 146
plastics-derived 188–90, 346–50, 358–9 gas products
low-temperature properties 399–400 characterization of 203
properties 304t, 391t as distillation fraction 154
see also diesel; gasoline; kerosene; syngas economic value 194
Fuji process 123, 211, 431, 440t, 739t, 741, from catalytic cracking
748 of MWP 235
melt circulation system 396, 741 of plastics-derived heavy oil 174t,
product distribution 749t 174f, 176t, 177f
FZ-W catalyst 745 of polyolefins 50f, 52f, 53f, 78, 139t,
143f, 144, 145f, 201, 203
from coprocessing of MWP/HVGO blend
gallosilicates, PE catalytic cracking by 218t
84–5, 233t, 723 from coprocessing of petroleum residues
Garrett coal gasification process 607 with waste plastics 375
gas chromatography from pyrolysis
diesel, Thermofuel process 411f of HDPE 293t
HDPE pyrolytic waxes 306f, 307f of LDPE 293t
LDPE cracking products 75f, 76f of LLDPE 293t
PS pyrolytic oil 308f of mixed plastics 293t, 295, 403
gas chromatography with atomic emission of PE 139t, 255t, 257t, 293t
detector (GC-AED), halogen analysis of PET 266t, 267t, 293t
498, 517, 519 of polyesters 293t
gas chromatography with mass selective of polyurethanes 293t
detector (GC-MSD) 498 of PP 259t, 260t, 293t
gas chromatography with mass spectrometry of PS 293t
(GC/MS) of PVC 293t
compared with 1 H NMR 203 heating value 235, 276, 279
PE catalytic cracking 47–8, 48–50f, gas residence time
52–3f, 61f, 63f, 65f in fluidized-bed reactors 457
polyolefin catalytic cracking 203 in free-fall reactors 609
INDEX 767
gas–solid fluidization 435 industrial pilot plants
see also fluidized-bed reactors Ebenhausen 27, 123, 440t, 476,
gas–solid reactors, comparison between main 488–9, 742
types 446–9t Grimma 476, 489–90
gas turbine generators 604 PMMA pyrolysis 90, 629–34
gasification 10, 23, 251, 737 polyolefin pyrolysis 27, 90, 123, 482–3,
activation energy for 182, 183t 484t, 486–7
compared with pyrolysis 251, 275–6, 287 process parameters variation 476t
fluidized-bed gasifiers 438t PS pyrolysis 90, 123, 635
fuel valorization by 279–80 PTFE pyrolysis 635–8
industrial plants 23, 32, 277–8, 367, 368f pyrolysis of tires 480–2, 488, 489–90
of PE 258, 258f HDPE
of PP 261, 262f catalytic cracking of 93, 94, 140–9, 404
of PS 263 effect of polymer-to-catalyst ratio 197
reactor types 276–7 effect of PS 149–53
technologies 275–8 initial degradation mechanism
see also co-gasification 199–201
gasoline product distribution 137f, 148t, 495,
as catalytic cracking product
732t
from plastics-derived heavy oil 174f,
various studies listed 232t, 233t
175–88, 213, 214
coprocessing with petroleum distillation
from waste plastics 97–8, 99, 150,
151f, 154, 235, 349f, 748–9 residues 370, 371t, 373t
RON values 184, 185f, 213, 749t fluidized-bed pyrolysis of 458t, 459t,
commercial 460t, 461t, 487t
prices 20t microwave pyrolysis of 578f, 579f
properties 155t, 204f pyrolysis of
RON values 179t, 185f gas products 257t, 292, 293t, 294
composition 179t, 184, 185f, 213t kinetic data 21t
quality index (RON) 175 oil/wax products
gate fees, for various industrial plants 28, chemical feedstock potential 307
30, 31 FT-IR spectra 296–7, 296f
glycolysis, of PET 644 molecular weight range 301f, 302t
products 148t, 256t, 257t, 289t, 323f,
352f, 356t, 731t
H-gallosilicates, PE catalytic cracking by
various studies listed 231t
84–5, 233t, 723
1 uses 345
H NMR
compared with GC/MS 203 HDPE/PET mixture, pyrolysis of 356
olefinic/paraffinic hydrogen ratios 203 heat balances
Haloclean rotary kiln process 552–3, 555t, pyrolysis reactors 20–1
559–62 see also energy balances
condition of kiln after continuous operation heat exchange characteristics, comparison of
562, 563f pyrolysis reactor types 446t
pyrolysis residues 561f, 562f heat transfer limitations, pyrolysis of plastics
halogenated plastics 577–8
problems encountered during pyrolysis heating methods 570
15, 23–4, 77, 217, 391 heating value see calorific (heating) value
see also dehalogenation heavy fuel oil
Hamburg fluidized-bed pyrolysis process 9, commercial prices 20t
27, 89–90, 123, 195, 437, 440t, 475–91, properties 305t
628–9, 740t, 741–2 heavy metals, problems encountered 118
catalytic cracking modification 90, 195 heavy oil
description 89–90, 476–80, 628–9 calorific/heating value 155t, 305t, 533t
fire tubes for heating 478f, 479f coprocessing with plastics 217
flow scheme 89f, 477f, 628f as distillation fraction 154
768 INDEX
heavy oil, plastics-derived physicochemical properties 173t, 183t,
carbon number distribution 172f, 687f 240t
cracking over acidic catalysts 172–5 plastics-derived heavy oil cracked by
cracking over Ni-REY catalyst 183–8, 174f, 174t, 184, 185f
233t polyolefins cracked by 45, 46, 48, 49, 51,
cracking over REY catalysts 52, 53–4, 404
kinetics 180–3 see also Pt-HY
product distribution and yield 175–9, hydrochloric acid
213 analytical results 688t
reaction pathway 181, 182f recovery from dechlorination processes
hydrocracking of 214, 347, 349 30, 39, 210, 278, 674, 682, 685–6,
production of 137, 162–72, 673, 682, 696 720, 747–8
properties 155t, 674t, 685t, 698t hydrocracking 60–7, 113, 214, 722, 737
heavy oil, see also diesel; kerosene catalysts used 60, 214, 217, 218, 219,
helical impellor 188, 189f 220, 221
heteroatomic polymers co-processing of distillation residues with
pyrolysis of 720–1 waste plastics 113, 370, 371t, 374t
see also ABS; PET; PVC distillation residues upgraded by 366
hetero-atoms gasoline from 214, 722
catalysts affected by 77, 211, 217, 219 of PE 60–7
fuel quality affected by 10, 390 pyrolysis-derived heavy oils 214
process difficulties due to 4, 7, 14, 23–4, reaction mechanisms 215f
77, 367, 393 hydrodesulphurization catalysts 216, 221
removal by hydrotreating 398 hydrogen adsorption properties, PET pyrolytic
heterogeneous catalysts 79–85 carbon 657
high-density polyethylene see HDPE hydrogen chloride, removal see dechlorination
HIPS-Br with PVC mixed plastics, pyrolysis hydrogen sulfide, free-radical mechanisms
of 518–21 affected by 219–20
Hitachi Zosen pyrolysis process 427–9 hydrogen transfer index 722
features 427 hydrogen-transfer reactions
fuel properties 429t in catalytic cracking 238
mass balance 428f in thermal cracking 22, 75, 130, 131f,
pyrolysis vessel 428f 320, 388f, 650f
HMCM-41 catalyst hydrogenation 737
polyolefin cracking by 82, 83f, 84f, 93f, economic considerations 30
118 end-product affected by 10
PS cracking by 406 industrial plants 23, 30–2, 369
HNZ zeolite catalyst, physicochemical reaction mechanisms 215f
properties 240t see also hydrocracking
Hokkaido University (Japan) hydroisomerization 351
stirred heat-medium-particles reactor of Fischer–Tropsch wax pyrolysed
bench-scale reactor 168–72 products 357t, 358
pilot plant 188–90 of LDPE + FT wax pyrolysed products
homogeneous catalysts 79 356, 357t, 358
see also Lewis acid catalysts hydrolysis, of polyesters 164, 166, 329,
Horowitz–Metger equation 227t 647–9, 658–9
household waste, costs of hydropyrolysis 374
collection/sorting/recycling 26t, 704t hydrotreating, pyrolysis-derived fuels 397–8
household waste plastics see municipal waste HZSM-5 zeolite catalysts
plastics deactivation by coke deposits 95, 174,
HSD Stabilizer (for diesel) 402–3 404, 746
Hunan University process 740t, 742 hydrocracking by 214, 217, 218, 219,
HY zeolite catalysts 220, 221, 347, 349, 494–5
deactivation by coke deposits 174, 404, product distribution 218t
746 physicochemical properties 82, 173t, 175,
gasoline fraction reformed by 749 240t
INDEX 769
plastics-derived heavy oil cracked using Japan
174f, 174t, 213 factory waste 161, 668t
polyolefin cracking by 46, 48, 49–51, history of plastics liquefaction 665–6
53–4, 76f, 82, 83f, 93, 94, 95, 116, household waste 161, 209, 668t
140, 226, 394, 404, 723 legislation on recycling 37, 666
PS cracking by 406 liquefaction plants 8, 26, 34, 37, 670–702
see also Pt-HZSM-5; ZSM-5 cost comparison with other techniques
705t
Mikasa plant 695–702
ignition point Niigata plant 670–8
fuel oils 155t, 156 Sapporo plant 678–95
pyrolysis oils 325 PET bottle recycling 642t, 667
see also flash point plastics recycling/recovery initiatives
incineration 10, 252, 494 36–7, 666t
air pollution due to 193, 532 plastics waste data 209, 667, 668t
costs compared with recycling 704t scope for liquefaction 706–8
disadvantages 494, 532 cost-reduction considerations 706–7
incoming feedstock specification 391–2 local recycling systems 707–8
indanes, from PS catalytic cracking 55f, 56, new outlets for pyrolysis oils 707
57f Thermofuel process plants 411–12
India, pyrolysis plants 724–7 tyre waste 573
induction heating 570 Japan Container and Package Recycling
inert purge gas, in pyrolysis plant 396 Association (JCPRA) 667
infrared heating system waste plastics bid system 705
in Dispons process 599 baling system requirements 667, 705
in Royco process 423 Japan Energy Co, Ltd, pyrolytic light oil used
internally circulating fluidized beds, pyrolysis in refinery 691, 694, 707
in 440t, 469, 613, 614 Japan Fluid Cracking process 475
investment costs, relative, plant capacity Japan Physics and Chemistry Research
affecting 14, 14t, 378 Institution, pyrolysis process 739t
iron oxide, hydrated form [FeOOH] Japanese Carbon Company plant 739t
catalytic hydrolysis by 166–7, 171, JFE Steel (Japan)
188–9, 747 blast furnaces, plastics waste used in 37,
dechlorination of PVC-containing mixture 669t, 704
by 505, 506t gasification plants 669t
structure and morphology 168, 507
iron oxide carbon composite (Fe-C) sorbent
HCl reaction profile 510f kerosene
laboratory evaluation of 509–11 addition to diesel 401
physical properties 496 calorific/heating value 155t, 305t, 533t
preparation of 496 as catalytic cracking product 99, 150,
iron oxide catalysts 151f, 155, 349f
dechlorination using 407, 496, 505–8 commercial, properties 155t, 305t
pyrolysis products from PVC/VGO mixture as pyrolysis product 17
374t kettle reactors 393
isomerization dewaxing 398, 417 KIER process 137, 138f
isomerization reactions 132, 237–8, 242, gas product 137, 139t
388f, 735 heavy oil, properties 155t, 157, 158
isoparaffins light oil, properties 155t, 157–8
in commercial gasoline 179t, 185f liquid product 137, 155–8
from heavy-oil conversion 178f, 179f, kinetics
184, 185f catalytic cracking 180–3
from PE catalytic cracking 148t degradation of plastics 226–38
from pyrolytic wax catalytic cracking pyrolysis of plastics 12–13, 21, 719
213t Kissinger equation 227t
770 INDEX
KOB-627 catalyst 213, 217 lifetimes of plastics 6
Kobe rotary (pyrolytic) kilns 554t light cycle oil (LCO), coprocessed with
Kobe Steel (Japan), blast furnaces, plastics plastics 90–1, 102, 119, 217, 422
waste used in 669t light fuel oil (LFO), properties 305t
Koheöl-Anlage Bottom (KAB) liquefaction light oil
plant 30, 346 components 376
Korea as distillation fraction 154
mixed plastics waste 153 pyrolytic, properties 155t, 673, 674t,
Reentech process 423–7 685t, 698t
see also KIER process taxation in Japan 706, 707
Kubota Co., Ltd, thermal cracking process see also gasoline
669t, 695 light paraffin oil fraction, as catalytic cracking
Kurata process 744 product 235, 236t
KWU process 554t lignite
as catalyst in Veba process 739t, 748
desulphurization of 608
laboratory-scale pyrolysers 316 devolatilization of 606, 607
batch reactor 348f Likun process 431, 740t, 743–4
continuous reactor 353f linear low-density polyethylene see LLDPE
landfill liquefaction
cost considerations 206 catalytic, mixed plastics waste 210–21,
disposal of plastics in 26, 73, 193, 252 234–7, 347–50
Japan 668t plastics waste 346–7
layered clay catalysts 405–6 cost comparison with other techniques
LDPE 705t, 706–7
catalytic cracking of 76f, 91, 95, 149, in Japan 20, 665–708
232t, 233t, 405, 722–3 liquid products
product distributions 137f, 406, 495, boiling point distributions 203–4, 352f,
545t, 732t 376
coprocessing with petroleum distillation characterization of 203
residues 370, 371–3t from catalytic cracking
copyrolysis with Fischer–Tropsch waxes, of LLDPE 199f
products 356, 357t, 359 of various plastics 137f, 201,
pyrolysis of 203–4
in fluidized bed 613 from coprocessing of MWP/HVGO blend
in free-fall reactors 613–17 218t
gas products 257t, 292, 293t, 294, 614 from coprocessing of petroleum residues
liquid products 615–16, 617f with waste plastics 375–6
oil/wax products from KIER process
chemical feedstock potential 307 PONA distributions 145f
FT-IR spectra 296–7, 296f properties 155–8
molecular weight range 301f, 302t yields with various catalysts 148t
product distribution 75f, 256t, 257t, from pyrolysis
289t, 617, 731t chemical composition 317–21
in screw kiln reactor 542, 543t of polyolefins 603–4
uses 345 of PS 263t
LDPE/EVA mixture, catalytic pyrolysis of of PVC mixed plastics 504f, 505f,
394–5 506t, 507f
lead bath reactor 16t, 17 see also gasoline; heavy oil; light oil; oils
legislation, effect on recycling rates 33, 37 liquid selectivity 202
Lewis acid catalysts, polyolefin cracking by liquid yield, effect of various catalysts 148t,
46, 79 202, 218t
Lewis acid sites on catalysts 76, 81, 147, liquid-phase pyrolysis 19
196, 219 LLDPE
Libond Industry/Macromolecule Cracking catalytic cracking of 198, 199f, 232t
Research Institution process 744 pyrolysis of 289t, 292, 293t, 294, 487t
INDEX 771
local processing plants, economic aspects cost comparison with other techniques
124, 707–8 705t
logistics problems, in waste collection 25–6, and feedstock recycling 39–40, 667, 705
32, 704–5 PET bottles 641, 642t, 643, 667, 682
low-density polyethylene see LDPE problems encountered 595
low-temperature carburization 551 mechanisms see reaction mechanisms
LPG-type gases 604 melting vessel
lubricating oils comparison with other reactor types
base oils 351 446–9t
production of in industrial plants 408f, 409f
from Fischer–Tropsch wax and waste mesoporous catalysts 81
plastics 351, 356, 357t, 358 see also amorphous silica–alumina;
from mixed waste plastics 351, 356, FSM-16; MCM-41; SBA-15
356t, 359–60
metal oxide catalysts 166–8, 747
from polyolefins 100, 120, 353, 360
metal-supported activated carbon (M-AC)
pyrolysis pilot plant 354–8
waste catalysts 46, 211
amount dumped in USA 351 methanolysis, of PET 644–7
coprocessed with plastics 102–3, 119, methyl methacrylate, recovery from PMMA
123 11, 12t, 74, 90, 627, 629, 631t, 633t
Lurgi fixed-bed grate gasifiers 277 MFI type zeolite catalyst
Lurgi multi-purpose gasifier 277 HDPE cracked using 149
plastics-derived heavy oil cracked using
mass balance 184, 185f, 186f
catalytic cracking of plastics 731, 732t properties 183t
catalytic cracking of plastics-derived heavy see also ZSM-5
oil 181 micro activity test (for catalysts) 716
Japanese liquefaction plants 675, 677f, microporous catalysts see zeolite catalysts
687–8, 690f, 690t, 698, 699f microwave absorbents 572, 574
pyrolysis of plastics 19–20, 136–7, patents 584, 585
730–1, 731t, 732f microwave differential thermal analysis 575
in Hitachi Zosen process 428f microwave effect 581–2
PE 255t, 256t microwave heating
PET 266t advantages 571, 582, 586
PP 259t ceramics industry 572
PS 262t, 263t industrial applications 572
PVC 264t, 265t mechanisms 571
mass spectrometry plastics 572
analysis of PET pyrolysis products 650–2 principles 570–2
collision-induced dissociation tandem mass microwave pyrolysis
spectrometry (CID-MS/MS) 651–2
advantages 573
negative chemical ionization mass
bench-scale semi-batch experiments
spectrometry (NCI-MS) 650–1
see also gas chromatography with mass equipment 576–7
spectrometry (GC/MS) results 578–81
Maxwell–Wagner polarization 571 commercial processes 587–8
Mazda process 441t, 740t compared with fluidized-bed pyrolysis
MCM-41 catalyst 81, 82f, 147, 195 576
physicochemical properties 240t meaning of term 572, 584
polyolefin cracking by 46, 48, 49, 51, patents covering 582–5
53–4, 53f, 91, 116, 144, 149 plastic wastes 573, 580–1, 584–6
PS cracking by 46 rubber waste 35
see also Al-MCM-41; HMCM-41; scientific studies 575–82
Pt-HMCM-41 thermogravimetric experiments
mechanical recycling 6, 193, 209, 493–4, equipment 575–6
667 results 577–8
772 INDEX
Mikasa waste plastics liquefaction plant from PTFE 636, 637, 638t
(Japan) 695–702 see also ethylene glycol; methyl
carbon residues 700, 701t methacrylate; styrene; terephthalic
dehydrochlorination treatment 696, acid; tetrafluoroethylene
701–2 mordenite catalyst
environmental considerations 702 HDPE cracked using 148, 149, 404
flow diagram 697f physicochemical properties 80t, 240t
liquefaction/pyrolysis stage 696, 697f pore size 80t, 239
oils as products 696, 698 moving-bed catalytic cracking process 423
properties 698t, 699f moving-bed furnaces 273–4
pretreatment stage 695–6, 697f multiple hearth furnaces, gasification in 276
Mitsubishi thermal cracking process 17, municipal solid waste (MSW)
739t, 747 amount of plastics in 209, 288, 668t
Mitsui process 17, 441t, 739t incineration of 10, 668t
mixed plastics waste polymer types in 113, 129, 210t, 218t,
catalytic liquefaction of 210–21, 234–7, 235, 287, 288f, 345, 346f, 524, 673t,
347–50 682, 684f
composition 210t, 485t, 537t, 673t pyrolysis of
flash pyrolysis of 268t, 271 in fluidized-bed reactors 440t, 471
fluidized-bed pyrolysis of 458t, 459t, fuels produced 278t, 279t
464–6 microwave pyrolysis 585, 586
by Hamburg Process 440t, 485t, 487t, in rotary kilns 439t, 441t, 442t, 443t,
489t, 490t 554t, 555t
liquefaction of 346–7 in tubular reactors 439t
pyrolysis of 267–71, 385 see also household waste
fuels produced 278t, 279t municipal waste plastics (MWP)
gas products 293t, 295 baling costs 704t, 705
oil/wax products catalytic liquefaction of 210–21, 234–7
FT-IR spectra 298, 299f liquid-phase contact 210–11
molecular weight range 301–2 co-processing with other materials
slow pyrolysis of 268–70 216–21
tertiary recycling of 366–9 collection costs 26t, 33, 703–5
economic evaluation 376–8 composition, Japanese data 523, 524,
molecular sieve catalysts 80, 746–7 673t, 682, 684f
see also zeolite catalysts European data 73, 209, 363
Molecular Waste Technologies Inc. 586 Japanese data 209, 668t
molecular weight range PVC in 210t, 218t, 288f, 346f, 524, 673t,
effect of catalysts 393 682, 684f
polydispersity 300 pyrolysis of 13, 442t, 521–3
for various pyrolytic oils and waxes catalytic upgrading of product 211–16
302t Japanese plants 670–702
for various pyrolytic oils and waxes pilot plant studies 523–5
300–4
US data 345, 363
molten-metal bath reactors 16t, 17, 627
see also mixed plastics waste
monofunctional catalysts 239–41
MVU Rotopyr rotary kiln process 555t
see also amorphous silica–alumina; HY;
MWW type zeolite catalyst, HDPE cracked
HZSM-5; MCM-41; mordenite;
using 149
zeolites
monomers 4
recovery nanocrystalline zeolites 82
from PET 12t, 164, 389, 644–9, 655, see also HZSM-5
658 NanoFuel Diesel process 418–22
from PMMA 11, 12t, 74, 90, 627, see also Polymer Engineering process
629, 631t, 633t naphtha
from PS 90, 123, 262, 301, 302, 389, as catalytic cracking product 235, 236t
464, 618, 619f, 635, 636t commercial prices 20t
INDEX 773
copyrolysis coke ovens, plastics waste used in 36, 37,
kinetics and mechanism studied 21–2 669t
with polyolefins 13–14 two-stage thermal cracking/catalytic
from hydrocracking of MWP/HVGO blend cracking plant 99, 100f
220–1 nitrogen oxides emissions, Thermofuel diesel
as pyrolysis product 17 413
size of typical cracking plant 25 NKT process 442t
specifications and test methods 18t Noell rotary (pyrolytic) kilns 274t, 441t,
naphthenes 399 554t
from PE catalytic cracking 143f, 145f, Noell-KRC gasification process 278, 441t
148t, 151f nomenclature 4–6
from PS catalytic cracking 56, 57f, 151f North America
from pyrolytic wax catalytic cracking recycling of PET bottles 642t
213t tyre waste 573
see also PONA distributions see also Canada; USA
natural rubber, pyrolysis products 332 number average molecular weight
needle coke, production of 724 meaning of term 300
negative chemical ionization mass for various pyrolytic oils and waxes 302t
spectrometry (NCI-MS), pyrolysis nylons
products of PET 650–1 pyrolysis of
Ni-REY catalyst effect of steam 165
nickel content 184, 185f fuel properties of oils produced 304t,
plastics-derived heavy oil upgraded over 391t
88, 183–8, 189, 214 pyrolysis products
properties 183t of nylon-6 333–4
nickel catalysts 408, 424, 717 of nylon-6, 6 334–5
nickel hydroxide, catalytic cracking of PET by
octane number
166
factors affecting 241
nickel oxide, catalytic cracking of PET by
see also research octane number (RON)
166 Octel FOA-6 (fuel additive) 400
nickel-based zeolite catalysts 86, 88, 118, ohmic heating 570
183 oil wastes, coprocessing with plastics
Niigata (Japan), municipal waste plastics, 102–3, 119, 123
composition 210t, 673t oils
Niigata waste plastics liquefaction plant 20, chemical analysis of 296–300, 316
666t, 670–8 coprocessed with plastics 102–3, 119
composition of waste plastics 673 pyrolysis-derived, properties 155t,
dechlorination stage 671–2 157–8, 304t
energy balance 675–6, 677f oils/waxes
environmental considerations 678 pyrolytic
flow diagram 672f chemical feedstock potential 306–9
mass balance 675, 677f FT-IR spectrometry 296–300
oils as products 673–4 fuel properties 304–6
properties 674t, 675f molecular weight range 300–4
pretreatment of waste 670, 671 olefins 399
pyrolysis residue 675, 676 from polyolefin catalytic cracking 50f,
analytical composition 676t, 678 52f, 53f, 78, 143f, 144, 145f, 236t
applications 678 from pyrolytic wax catalytic cracking
pyrolysis stage 672–3 213t
view of plant 671f see also PONA distributions
Nikon process 441t operability maps, fluidized-bed pyrolysis
NiMo catalysts, coprocessing of distillation 455–6
residues with waste plastics 370, oxidation 10
371–4t oxidation stability test, diesel fuels 402
Nippon Steel Corp. (Japan) oxidative pyrolysis, of PET 657–8
774 INDEX
oxygen-containing plastics see nylons; PBT; by Hamburg Process 123, 483t, 487t,
PC; PET; polyamides; polyesters 489t, 490t
Ozarawa equation 227t mass balance 255t, 483t, 487t, 613
Ozmotech Thermofuel process 407–14, 724 gasification of 258, 258f
hydrocracking of 60–7, 139t, 494–5, 556
Packaging and Packaging Waste (EU) by PtHMCM-41 catalyst 63–6
Directive 24, 33, 73 by PtHY catalyst 63, 63f, 64f
packaging waste by PtHZSM-5 catalyst 60–3
collection systems for 24, 25t, 33, 33t pyrolysis of 255–8, 322–4, 387
logistics of recycling 25–6 compared with PP pyrolysis 724
packaging waste plastics effect of PVC 501
composition 617 effect of steam 165f, 258f
pyrolysis of 267–71, 321–9 energy balance calculations 732–3
paper recycling refuse, fuels produced by energy profit calculation 733–4
pyrolysis 278t, 279t fuel properties 304t, 387, 391t
paraffins 399 gas products 292, 293t, 294
n-paraffins kinetic data 21t
in commercial gasoline 179t, 185f oil/wax products
in diesel 387 FT-IR spectra 296–7, 296f
from heavy-oil conversion 178f, 179f, molecular weight range 301f, 302t,
184, 185f 613
from PE catalytic cracking 46–7, 50–1, products 11, 12, 12t, 115, 139t, 148t,
50f, 52f, 53f, 148t, 150–1, 151f 255t, 257t, 289t, 322–4, 462,
from pyrolytic wax catalytic cracking 463f, 731t, 732f
213t effect of operating conditions 254t,
particle size 580t
catalysts 717–18 reaction mechanism 713–14, 714f
comparison of pyrolysis reactor types temperature effects 137, 255, 255t,
446t 256f, 257t, 258, 258f
particulate (smoke) emissions, diesel 413 slow pyrolysis of 254t, 256–8
PBT, thermal degradation of, effect of steam see also HDPE; LDPE; LLDPE
164, 165 PE/PET mixtures, pyrolysis of 508–9
PC PE/PET/PP mixtures, fluidized-bed pyrolysis
pyrolysis of of 455f
effect of steam 164, 165 PE/PP mixtures, fluidized-bed pyrolysis of
product distribution 290t 484t
PE PE/PS mixtures, pyrolysis of 268–9f
calorific value 533t PE/PVC mixtures
catalytic cracking of 45–6, 46–54, 75–6, pyrolysis of 502–4
79–85, 93, 94, 139–41, 140–9 liquid products 504f
chain reactions 51–2 product distribution 503t
in fluidized-bed reactor 90 PET
product distribution 148t, 732t bottles 641
in screw kiln reactor 91, 116 recycling of 641, 642t, 643, 667, 682
in stirred semi-batch reactor 86, 87f world demand data 642t, 643t
temperature effects 139–41, 746t catalytic cracking of 78, 233t, 655–7,
chemical structure 294f 747
flash pyrolysis of 255, 255t, 258f, 613 in Smuda process 416–17
in free-fall reactor 613–17 in steam atmosphere 165–8, 655
product distribution 255t chemical structure 294f
temperature effects 255t, 258f, 745 effect on pyrolysis of PVC mixed plastics
fluidized-bed pyrolysis of 521, 522t, 523, 523f, 524f
defluidization times 455f flash pyrolysis of 266
effect of process variables on products fluidized-bed pyrolysis of 455f, 464,
458t, 459t, 460t, 461t, 462, 556, 654–5
580t glycolysis of 644
INDEX 775
hydrolysis of 166, 647–9, 658–9 pyrolysis of, oil/wax products, FT-IR
acid-catalyzed hydrolysis 647–8 spectra 299f, 300
base-catalyzed hydrolysis 648–9 phthalates (in PVC) 329, 376
manufacture of 162, 164, 643–4 phthalic anhydride, recovery of 97, 309
methanolysis of 644–7 physical recycling see mechanical recycling
batch process 646f pillared clay catalysts 81–2, 195, 404
continuous process 646f liquid products produced over
in municipal waste plastics 210t, 218t, boiling point distribution 204f
288f, 346f, 524, 673t, 682, 684f
olefinic/paraffinic hydrogen ratio 203
oxidative pyrolysis of 657–8
yields 202
pyrolysis of 162–4, 266–7, 329, 389–90,
653–5 PKA process/rotary kilns 273, 274t, 442t
activated carbon produced 657 PKA-Keiner process 554t
effect of calcium hydroxide 390, 655, plasma reactor, gasification in 121
656f, 693 Plastic Containers and Packaging Recycling
effect of steam 163, 164, 165f, 658–9 Law (Japan, 2000) 37, 666
in fixed-bed reactor 653–4 effect on recycling activities 703f
in fluidized-bed reactor 455f, 464, plastic film, in municipal solid waste 288
654–5 Plastic Waste Management Institute (PWMI,
gas products 293t, 294–5 Japan), support by 36, 666t, 669t, 670
kinetic data 21t plasticizers, PVC 329
molecular weight range of products plastics
301f, 302t classification criteria 5
oil/wax products 297f, 298, 301f, 302t consumption data 73, 205, 285, 286t
products 12, 12t, 164, 266, 266t, 267t, meaning of term 4
290t, 291, 329, 389–90 Plastics Europe see Association of Plastics
reaction mechanisms 389f, 650, 650f,
Manufacturers in Europe
651, 653f
plastics waste
recovery of monomers from 12t, 164,
389, 644–9, 655, 658–9 European data 73, 209, 363, 612
slow pyrolysis of 266–7 household data 33, 209
solvolysis of 643–9 incoming feedstock specification 391–2
thermal degradation of increase in amount 193
FT-IR spectra 164f, 297f, 298, 652, Japanese data 209, 667, 668t
653f US data 345, 363, 532
mass spectrometry analysis 650–2 platinum-catalyzed hydrogenation 66–7
thermogravimetry curves 163f, 165f see also hydrocracking; PtHMCM-41;
uses 641, 642t PtHY; PtHZSM-5 catalyst
world consumption data 641, 642t platinum-impregnated catalysts 242
PET/HDPE mixtures, pyrolysis of 356 Pleq rotary kiln process 554t
PET/PP mixtures, pyrolysis of 655, 657f PMMA
PET/PS mixtures, pyrolysis of 270f cross-linked 634
PET/PVC mixtures, pyrolysis of 502 filled, pyrolysis of 631–4
petroleum fractions, coprocessing with waste fillers 628
plastics 102–3, 217, 372–3, 374t
pyrolysis of 460t, 556–7, 629–34
petroleum residues 365
energy balance 634
coprocessing with waste plastics 369–74
upgrading of 365–6, 369 monomer recovered 11, 12t, 74, 90,
petroleum-derived fuels 627, 629, 631t, 633t
molecular weight distribution 303f products 11, 12t, 74, 90, 630t, 631t,
see also diesel; gasoline; kerosene 633t
phenol–formaldehyde resin, pyrolysis reaction mechanism 630–1, 714–15,
products 340–1 715f
phenolic resin Poland, thermal cracking plant 123
chemical structure 294f political considerations 11, 37, 39
776 INDEX
poly(acrylonitrile-co-styrene-co-butadiene) see fluidized-bed pyrolysis of 458t
ABS effect of steam as fluidizing gas 90,
polyalkene plastics see polyolefins 486t
polyamides general scheme for processing 112–13
hydrolytic decomposition of, effect of PVC pyrolysis of 255–61, 322–6, 595–604
502 Dispons continuous process 598–604
pyrolysis of 333–5 heating by gas products 596
kinetic data 21t mechanism(s) 22, 75, 113–14
products 11, 12, 12t, 290t, 333–5 oil/wax products
reaction mechanisms 319f chemical feedstock potential 307
see also nylons FT-IR spectra 296–7, 296f
polybrominated flame-retardant materials, molecular weight range 301, 301f,
thermal degradation of 520 302t
polybutadiene product distribution 11, 12t, 111, 289t
thermal stability 333 wax products 597
see also butadiene rubber see also HDPE; LDPE; PE; PP
polycarbonate see PC polypropylene see PP
polycyclic aromatic hydrocarbons (PAHs) polystyrene see PS
413, 495 polytetrafluoroethylene see PTFE
polyester resin, pyrolysis of, oil/wax products, polyurethanes (PU)
FT-IR spectra 298, 299f pyrolysis of
polyester/styrene copolymer gas products 293t, 295
pyrolysis of product distribution 290t
fuel properties of oils produced 304t products
oil/wax products, chemical feedstock of polyester-segmented PU 335–6
potential 307 of polyether-segmented PU 336–7
polyesters reaction mechanisms 319f, 335
chemical structure 294f poly(vinyl chloride) see PVC
hydrolysis of 164, 165 poly(vinylidene chloride) (PVDC) 682
pyrolysis of 164, 165 PONA (paraffins/olefins/naphthenes/aromatics)
gas products 293t, 295 distributions 399
products 290t, 329 HDPE degradation products 87f, 143f,
reaction mechanisms 319f 145f
see also PBT; PC; PET HDPE/PS catalytic degradation products
polyethylene see HDPE; LDPE; PE 151f
poly(ethylene terephthalate) see PET LDPE catalytic degradation products 87f
polyisoprene potassium carbonate carbon composite HCl
pyrolysis of 332 sorbent, laboratory evaluation of
see also natural rubber 509–11
Polymer Cracking Process pilot plant 367–8, pour point
467–8 liquid fuels 155t, 156, 305, 399, 401
see also BP fluidized-bed pyrolysis process lubricating base oils 351
Polymer Engineering process 418–22 pyrolysis oils 304t, 674t, 685t, 698t
advantages 422 pour point depressants 401
catalyst 418, 420–1 PP
compared with Thermofuel process 422 calorific value 533t
flow diagram 421f catalytic cracking of 148–9, 404
output rate 421, 422 product distribution 137f, 495, 732t
polymer-to-catalyst ratio 94–5, 196–8, 199f temperature effects 746t
polyolefins various studies listed 232t, 233t
acid-catalyzed cracking of 45–72, 77, chemical structure 294f
78f, 83–4f, 93–6 coprocessing with petroleum distillation
reaction mechanisms 76, 114–15, residues 371t
199–201 copyrolysis with brominated flame
composition 7, 113, 596 retardants 563, 564f
copyrolysis with naphtha 13–14 flash pyrolysis of 258–9, 261f
INDEX 777
fluidized-bed pyrolysis of gasification of 263
defluidization times 455f pyrolysis of 262–4, 327, 388–9
effect of process variables on products effect of steam 165
459t, 461t, 462–4 in free-fall reactors 617–20
by Hamburg Process 484t, 487t, 489t, fuel properties 304t, 388, 391t
490t gas products 293t, 294
mass balance 259t, 484t, 487t kinetic data 21t
operability map 456f monomer from 90, 123, 262, 301, 302,
gasification of 261, 262f 389, 464, 618, 619f, 635, 636t
pyrolysis of 258–61, 324–6, 387 oil/wax products
compared with PE pyrolysis 724 chemical feedstock potential 307–8
effect of steam 165f, 262f FT-IR spectra 297–8, 297f
fuel products 304t, 391t, 749t, 750t molecular weight range 301f, 302t
gas products 292, 293t, 294 product distribution 11, 12, 12t, 90,
kinetic data 21t 262t, 263t, 290t, 291, 389, 618,
oil/wax products 635t, 636t, 731t
FT-IR spectra 296–7, 296f various studies listed 231t
molecular weight range 301f, 302t slow pyrolysis of 262–3, 264f
products 11, 12, 12t, 115, 259t, 260t, PS/PE mixtures, pyrolysis of 268–9f
261f, 289t, 324–6, 387, 388f, 731t PS/PET mixtures, pyrolysis of 270f
reaction mechanism 387, 388f, 714 PS/PVC mixtures
various studies listed 231t pyrolysis of 270f, 502–4
slow pyrolysis of 259–61 liquid products 504f
PP/PS mixtures, pyrolysis of 269f product distribution 503t
PP/PVC mixtures Pt-HMCM-41 catalyst, hydrocracking of PE
pyrolysis of 502–4 by 63–6
effect of catalyst 504, 505f, 506t, 507f Pt-HY catalyst, hydrocracking of PE by 63,
liquid products 504f, 505f, 506t, 507f 63f, 64f
product distribution 503t, 506t Pt-HZSM-5 catalyst, hydrocracking of PE by
predictive carbonization model 271–2 60–3
primary recycling 111, 205, 285, 363 PTFE
printed circuit boards filled, pyrolysis of 637–8
pyrolysis of 24, 559–62 pyrolysis of 635–8
see also electrical/electronic equipment monomer recovered 636, 637, 638t
waste thermal decomposition products 12t,
process flexibility, comparison of pyrolysis 636–7
reactor types 447t publications on recycling 38
PS PVC
calorific value 533t catalytic cracking of 233t, 746t, 748
catalytic cracking of 46, 54–9, 77, 116, chemical structure 294f
232t, 233t, 406–7, 746t combustion of 500
product distribution 55f, 137f, 732t construction products 194
reaction mechanism 54, 56–8, 59, coprocessing with petroleum distillation
243–4 residues 372–3, 374t
various studies listed 232t, 233t dechlorination of
chemical structure 294f by Ca-C sorbent 514–21, 556, 563
coprocessing with petroleum distillation catalytic 96, 407, 420, 496, 505–8,
residues 370, 371t, 373t 563, 720–1
effect on catalytic degradation of HDPE chemical methods 29, 119, 123, 212,
149–53 349, 390, 397, 467, 482, 556, 673,
flash pyrolysis of 262, 264f, 613 682, 721, 741, 748
in free-fall reactor 617–20 other plastics affecting 270, 501, 502
fluidized-bed pyrolysis of 459t, 464, 618, thermal methods 5, 39, 99, 117, 210,
635, 636t 211, 217, 278, 294, 327, 328f,
effect of process parameters 635t 377f, 495, 584, 696, 701–2, 741,
products 636t 747
778 INDEX
PVC (continued ) dechlorination stage 397
flash pyrolysis of 264, 468 dewaxing 398
fluidized-bed pyrolysis of 438t, 468–9 distillation columns 397
in municipal waste plastics (MWP) 210t, hydrotreating 397–8
218t, 288f, 346f, 524, 673t, 682, 684f inert purge gas 396
plasticizers in 329 pyrolysis chamber construction 396
pyrolysis of 264–5, 327–9, 390–1, pyrolysis chamber design 395, 710–11
720–1, 747–8 scrubbers 397
fundamental studies 498, 500–2 factors affecting product distribution
gas products 293t, 294 8–10, 9t
hydrogen chloride generated during fluid-mechanical aspects 18
17, 19, 28, 29, 30, 77, 119, fuel valorization by 278–9
327–8, 390, 500 gas products 139t, 255t, 257t, 259t, 260t,
kinetic data 21t 266t, 267t, 293t, 375, 719
oil/wax products heat balances 20–1
chemical feedstock potential 308–9 industrial plants 27–32, 89–90, 123,
FT-IR spectra 297, 297f 367–9, 407–18, 422–3, 427–9, 430,
molecular weight range 301f, 302t 738–44
products 11, 12, 12t, 264t, 265t, 290t, in laboratory-scale reactors 316, 348f,
291, 327–9, 376, 500–1 353f
limitations 209–10, 385
reaction mechanisms 500, 501, 501f,
liquid products 317–21, 375, 603–4,
714, 715f, 720
719, 721–2
recycling initiatives 26
liquid vs gas phase operations 19
slow pyrolysis of 264–5
mass balance 19–20, 136–7, 730–1,
see also PE/PVC...; PET/PVC...;
731t, 732f
PP/PVC...; PS/PVC mixtures meaning of term 6, 374, 383, 533–4,
PVC mixed plastics 549, 709–10
catalytic cracking of 233t, 721 of mixed plastics waste 267–71, 385
dechlorination of, by Ca-C sorbent operating conditions 253t, 287t
514–21, 556 operating margins 19–20
with HIPS-Br, dehalogenation by Ca-C operational considerations 392–5
sorbent 518–21 batch plants 393–4
pyrolysis of 495–6, 514–18, 693–4, 721, catalytic cracking 394–5
747 coking prevention 392–3
analysis of products 497–8, 499f continuous systems 394
experimental procedure for study corrosion prevention 393
496–7 fluid catalytic cracking 394
pilot plant studies 523–5 fluid-bed coking 394
PVDC 682 fluidized-bed processes 394
Pyrocom rotary kiln 555t, 558–9 reflux effects 393
pyrolysis 6–22, 251 tank/kettle reactors 393
of ABS 330–1, 721 of PE 255–8, 322–4, 387
advantages 384–5, 431, 494, 532–3 of PET 266–7, 329, 389–90
by-products 14–15 plastics suitable for 113, 385, 710
characteristics 253t, 287t, 605 of PP 258–61, 324–6, 387
compared with gasification 251, 275–6, process flow diagram 133–6
287 process parameters 253t, 287t, 605
compared with waste-to-energy combustion product distribution 11, 12–14, 12t, 251,
252 286, 348f, 349f, 719–20
decomposition modes 11, 12t of PS 261–4, 327, 388–9
economic viability 22, 36, 129 of PVC 264–5, 327–9, 390–1, 500–1,
effect of catalysts 231, 710, 715–16 720–1
engineering design aspects 395–8 reaction mechanisms 22, 75, 113–14,
burner characteristics 396 130–2, 228, 318–21, 456–7,
centrifuges 397 713–15, 734–5
INDEX 779
PE 713–14, 714f depropagation steps 130, 131f, 132, 211,
PET 389f, 650, 650f, 651, 653f 735
PMMA 630–1, 714–15, 715f hydrocracking 215f, 216
PP 387, 388f, 714 hydrogen chain transfer steps 130, 131f,
PVC 500, 501, 501f, 714, 715f, 720 238
in reactive gases 9t, 10, 30–2 hydrogenation 215f
reactor types 15–17, 375, 448t, 711–12 initiation steps 130, 131f, 228
effect on product distribution 9, 9t pyrolysis 22, 75, 113–14, 130–2, 228,
see also extruder...; fixed-bed...; 318–21, 456–7, 713–15, 734–5
fluidized-bed...; rotary kiln...; PE 713–14, 714f
screw...reactors PET 389f, 650, 650f, 651, 653f
residence time factors 9, 9t, 134, 253t, PMMA 630–1, 714–15, 715f
287t, 385, 605 PP 387, 388f, 714
in steam atmosphere 162–4 PVC 500, 501, 501f, 714, 715f, 720
suitability of various reactor types 448t termination steps 130, 131f, 238
survey of previous work 7–8 Reactive Energy company 586
temperature effects 8–9, 9t, 13t, 117t, reactor types 15–17, 86–92, 381–623
135, 231, 233, 385–6, 719, 745 for pyrolysis 15–17, 375, 549
thermodynamics 21 product distribution affected by 9, 9t
various studies listed 231t reactors, factors affecting design 85
see also catalytic pyrolysis; flash pyrolysis; rearrangement reactions 318, 319f, 339f
slow pyrolysis; thermal cracking reciprocating grate process 443t
pyrolysis oils recombination, chain termination by 130,
applications 533f 131f, 238
chemical feedstock potential 309 recycling
distilled oils, properties 155t, 304t, 674t, cost comparison for various techniques
675f, 685t 705t
pyrolysis products 12–14 packaging waste plastics 33
catalytic upgrading of 99–101, 140, 722 data for various countries 642t
factors affecting 8–10 logistics 25–6
value 11, 20 targets
Pyropleq (rotary kiln) process 274t, 442t California (USA) 345
European Union 558t
Japan 669t
quaternary recycling 111, 363 types 6, 111
see also incineration see also feedstock recycling; mechanical
recycling; primary recycling;
secondary recycling; thermal
radio-frequency heating 570 recycling
random-chain scission 114, 130, 131f, 132, red mud catalyst 95–6
292, 307, 387, 457, 464, 713–14, 714f, dechlorination using 407
735 Reentech process 423–7
Raney nickel catalyst 408 capacity of plant 425
rapid pyrolysis see flash pyrolysis catalysts regeneration system 425, 427f
rare earth metal exchanged Y-type zeolite fluid catalytic cracking in 425
catalysts see REY catalysts gasoline fraction, properties 425
reaction mechanisms process flowchart 426f
catalytic cracking 51–3, 76, 114–15, product yield 424
211, 228, 230–8, 422 reflux effects, in pyrolysis 393, 417, 577
aromatization steps 238, 735 Rekisei Kouyu Co., Ltd, liquefaction plant
formation of secondary unstable 669t, 670
compounds 237–8 repetitive injection GC/MS studies 47
initiation steps 51, 114, 211, 228, 230, PE catalytic cracking 47–8, 48–50f,
735 52–3f, 61f, 63f, 65f
isomerization steps 237–8, 735 PS catalytic cracking 54, 55f, 57f
plastics-derived heavy oil 181, 182f research octane number see RON values
780 INDEX
residence time features 423
carbonization 252, 253t, 287t heating system 423
catalytic cracking 87f, 153, 176 liquid fuel yield 422
fluidized-bed reactors 90, 447t, 457, 627 rubber, meaning of term 5
effect on pyrolysis products 464 rubber plastics 331–3
heavy-oil conversion 176f, 179, 179f thermal decomposition of 331–3
pyrolysis 9, 9t, 134, 253t, 287t, 385, 605 reaction mechanism 331–2
comparison of pyrolysis types 253t, see also butadiene rubber; natural rubber;
287t, 605 styrene–butadiene rubber
comparison of reactor types 447t rubber waste
rotary kilns 447t, 542, 553, 559 pyrolysis of 35
semi-batch reactors 87f see also tyres
REY catalysts 86, 98
catalytic cracking of gasoline fraction 749
plastics-derived heavy oil cracked using salt bath reactors 16t, 17
174f, 174t, 175–9, 185f, 186f, 213, Sanyo process 17, 739t
406 Sapporo (Japan), municipal waste plastics
kinetics 180–3 523, 524, 682, 684f
reaction mechanism 181, 182f Sapporo waste plastics liquefaction plant
properties 173t, 175t, 183t 678–95
Rice–Herzfeld (free radical) mechanism 22 applications of outputs 691, 691t
Rice–Kossiakoff cracking mechanism 387, calcium hydroxide added to input plastics
388f 682, 693
riser simulator reactor 90 composition of waste plastics 682, 684f
RON (research octane number) values consumption data 688, 690t
calculation 175–6, 317 dechlorination stage 682
commercial gasoline 179t, 185f energy/heat balance 688–9, 691t
gasoline fraction environmental aspects
after catalytic reforming 748, 749t waste gas 692–3, 693t
from plastics-derived heavy oil 179t, wastewater 692
184, 185f, 213, 214, 722 flow diagram 681f
from pyrolysis of plastics 324, 325, heat recovery ratio 694
326, 425, 748 mass balance 687–8, 690t, 690f
naphtha fraction, from thermal cracking of off-gas from pyrolysis 682, 692–3
MWP 236t oils as products 682, 694
rotary kiln reactors 531–67, 711–12, 712f applications 694
advantages 547, 551, 711 properties 684, 685t, 686f
compared with other reactor types process description 680–2
446–9t pyrolysis of PET-/PVC-containing plastics
with fluidized-bed reactors 446–9t, 693–4
534, 546–7, 553 pyrolysis reactor 682, 683f
disadvantages 547 pyrolysis residue 682, 686
double kiln system 550 analytical composition 689t
effect of temperature on pyrolysis products applications 686, 694
544–6 recycling ratio 694
gasification in 277 running costs 694–5
industrial processes listed 274t, 439t, system flow diagram 680f
442t, 443t, 554–5t, 682 view of plant 679f
principles 553 Saudi Arabia
pyrolysis in 16, 273, 274t, 439t, 442t, economic evaluation of (possible) waste
443t, 531–67 plastics processing plant 377–8
state-of-the-art technology 551–3, waste plastics data 377
554–5t SBA-15 catalyst 81
see also auger kiln reactor; screw kiln SBR
reactor fluidized-bed pyrolysis of 460t
Royco process 422–3 pyrolysis products 333
INDEX 781
scale-up dynamic method 254
pyrolysis processes 272 characteristic parameters 257t, 260t,
comparison of various reactor types 263t, 267t
449t isotheral–static method 254
Schwarze Pumpe gasification plant 276, 277 of mixed plastics waste 268–70
scraped surface heat exchangers 392 of PE 254t, 256–8
scraped-wall reactors 121, 414 of PET 266–7
screw extruder reactors 15–16, 16t, 91, pilot-plant scale-up 272
120–1 of PP 259–61
screw kiln reactors 91, 92f, 102, 195, 375, predictive carbonization model 271–2
542–4, 552 process parameters 253t, 287t, 605
effect of temperature on LDPE degradation of PS 262–3, 264f
542, 543t of PVC 264–5
thermal compared with catalytic pyrolysis technologies 272–3, 273–4
degradation of LDPE 144, 146f, Smuda process
544, 545t advantages 416, 417
screw pyrolysers 273–4, 712, 713f agitator speed 396, 416, 417
scrubbers, pyrolysis plant 397 catalysts 416
secondary recycling 111, 252, 286, 363 coke removal in 393, 417
semi-batch reactors, catalytic cracking in 86, compared with Thermofuel process 418
87f, 93, 94, 123, 195 distillation column 416
semi-continuous pyrolysis reactors 375 fuels produced by 414, 418
sewage sludge hydrotreating stage 398
microwave pyrolysis of 574, 583 plastics suitable for 416
pyrolysis of 439t, 440t, 441t, 443t, 471 reflux return in 417
shaft reactors shortcomings 416, 417–18
gasification in 276 stirred-tank reactor 415f
pyrolysis in 16, 16t sodium carbonate, dechlorination by 349,
Shell gasification process 23, 32, 122 397, 741, 748
shift factor (catalytic cracking) 228 solid acid catalysts 46, 80–1, 118, 172,
shredder light fractions 195–6, 211
pyrolysis of 552, 554t, 557 PP/PVC mixture degraded by 505, 506t,
see also automobile shredder residue 507f
(ASR) see also silica–alumina catalyst
side-group elimination, in pyrolysis 501f, solid alkalis, as catalysts 243–4
714, 715f solvents, coprocessing with plastics 103
Siemens–KWU rotary kiln process 551–2, solvolysis, of PET 643–9
554t, 557 sorting of plastics waste 26, 252
silica–alumina catalysts 80–1 spouted-bed reactors 90–1, 394
deactivation by coke deposits 95, 404 steam
dechlorination by 721 as carrier gas 88, 162
plastics-derived heavy oils 174f, 174t effect on catalytic cracking of
polyolefins 45, 139, 148–9, 404, 406, plastics-derived heavy oil 183–8
459t, 495 effect on fluidized-bed pyrolysis of
PP/PVC mixtures 504, 505f polyolefins 483, 486t, 742
properties 173t effect on polyester pyrolysis 163–72,
PS 46, 54, 55f, 406 183
silica–alumina/transition metal catalysts steam gasification
241–2 of PE 258
simulated distillation, boiling point curves of PP 261
from 349f, 352f, 376 syngas produced using 276, 279
Slovakia, Blowdec depolymerization process stirred heat-medium-particles reactors 394
429–30 bench-scale reactor 168–72
slow pyrolysis pilot plant 188–90
compared with flash pyrolysis 253t, 287t, stirred-tank reactors 16, 16t, 393, 395, 408f,
617 415f, 427, 672
782 INDEX
styrene PE 255, 255t, 256f, 257t, 258, 258f
as diesel pour point depressant 401 in rotary kiln reactors 544–6
from catalytic cracking of PS 55f, 56, temperature profile, comparison of pyrolysis
116, 151–2, 243 reactor types 446t
from pyrolysis of PS 90, 123, 262, 301, temperature range, comparison of pyrolysis
302, 389, 464, 618, 619f, 635, 636t reactor types 446t
from pyrolysis of SBR 333, 460t temperature-programmed desorption (TPD)
styrene–butadiene rubber see SBR method, acidity of catalysts measured by
styrene copolymers 173, 196
pyrolysis of terephthalic acid
fuel properties of oils produced 304t catalytic cracking of 165, 166–7
oil/wax products, chemical feedstock as PET monomer feedstock 164, 643
potential 307 reaction with ethylene glycol 643
product distribution 329–31 recovery from PET 164, 389, 464, 540,
sublimate compounds 161, 165, 390, 693 647–9, 658–9
sulfur content sublimation of 161, 165, 390, 693
fuel oils 155t, 156, 305t tertiary recycling 111, 363
pyrolysis oils and distillates 304t, 429t, economic considerations 124
674t, 685t, 698t see also catalytic cracking; feedstock
sulfur oxides emissions, Thermofuel diesel recycling; pyrolysis
413 tetrafluoroethylene, from PTFE pyrolysis
Sumitomo Metal Industries gasification system 636, 637, 638t
34
Tetrapak material, pyrolysis of 573, 580–1
superacid catalysts, cracking by 84, 147
Texaco gasification process 23, 32, 277–8,
supercritical water
367, 368f
pyrolysis in 737, 748
thermal analysis 7
rubber waste treated by 35
thermal conductivity, plastics 21
superheated steam, polyolefin pyrolysis using
599, 600, 603 thermal cracking 225, 385–6, 736
supply logistics, plastics waste collection and compared with catalytic cracking 74–7,
recycling 25–6 116, 118, 133, 194, 383–6, 736–7
syncrude, production of 31, 369, 377, 537 disadvantages 209–10, 385
syngas (synthesis gas) features 736
heating values 276, 279 reaction mechanisms 22, 75, 113–14,
production of 8, 34, 74, 120, 276, 278, 130–2, 228, 456–7, 734–5
367 temperature effects 745
syringes, fluidized-bed pyrolysis of 483t various studies listed 231t, 458–61t
see also pyrolysis
take-back schemes 6, 33, 34t thermal dehalogenation 24, 39, 99, 117, 210,
Takuma SBV process 443t 211, 217
tank reactors 16, 16t, 393 thermal recycling 6
tar formation, in gasification 276 thermocatalytic degradation 225
Teijin Fiber Ltd, PET recycling by 37, 647 see also catalytic pyrolysis
television circuit boards Thermofuel process 407–14, 724
pyrolysis of 562f agitator speed 396
see also electrical/electronic equipment basic steps 407–8
waste catalytic converter/reaction tower 408,
temperature effects 410f, 411, 724
catalytic cracking 93–4, 139–41, 231, coke removal in 393, 414
404, 745, 746t compared with other processes 418, 422
Conrad process 539t diesel fuel produced by 411f, 413
dechlorination capacity of Ca-C sorbent flow diagram 409f
511–12, 512f plants in Japan 411–12
heavy-oil conversion 176–9 pyrolysis chamber 407, 408f, 413
pyrolysis 8–9, 9t, 13t, 117t, 135, 231, emissions from 414
233, 719, 745 thermogravimetric analysis (TGA) 7
INDEX 783
catalytic cracking studied by 85–6, 197f, tubular reactors 16, 116, 121, 175, 234
199, 226 TwinRec process 440t, 469–71
curves two-stage pyrolysis/catalytic processes 86–7,
PET in nitrogen and steam atmospheres 96, 99–101, 172–88, 406, 407–14, 431,
163f 730, 737
various plastics in nitrogen and steam see also Hunan University process; Likun
atmospheres 164, 165f process; Thermofuel process
limitations 199 two-stage pyrolytic gasification processes
microwave pyrolysis apparatus 575–6 258, 261, 263
thermolysis see pyrolysis tyre rubber 5, 35
thermomechanical testing 7 tyres
thermoplastics composition of 35, 574
chemical structure 294f pyrolysis of 35, 273, 274, 274t, 333,
meaning of term 5, 187, 364 550–1
see also HDPE; LDPE; nylons; PE; PET; in fluidized-bed reactors 460t, 466,
PP; PS; PVC 480–2, 489–90
thermosets by microwave pyrolysis 35, 573–4,
chemical structure 294f 583, 585, 586
meaning of term 5, 287 products 278t, 279t, 483t
pyrolysis of 290t, 291 in rotary kilns 550–1, 552, 554t, 555t
oil/wax products recycling of 35, 573–4
chemical feedstock potential 309 vacuum pyrolysis of 35, 723–4
FT-IR spectra 298, 299f, 300 waste data for various countries 573
see also epoxy resin; phenolic resin
time factors
catalytic cracking 153, 176 Ube Industries (Japan), gasification plant 23
heavy-oil conversion 176f, 179, 179f Ube-Ebara gasification plants 8, 37, 669t
pyrolysis 9, 9t, 134 ultra-fast pyrolysis
see also residence time
of polyalkenes/polyolefins
tipping fees
gas products 293t
in economic appraisal 350, 359
product distribution 289t, 291
see also gate fees
process parameters 287t
tire see tyre...
toluene United Carbon process 739t, 743
from pyrolysis United Resource Recovery Corporation
of PET 266 PET hydrolysis process 648
of PS 619f PET recycling process 643
of PVC 264 UnPET process 648
toothpaste tube laminate, microwave pyrolysis unzipping reactions 11, 12t, 457, 725
of 573, 578f, 580–1, 581f updraft gasifiers 276, 277
Toshiba pyrolysis processes 443t, 678, 748 URRC process 643
TPD see temperature-programmed desorption US-Y zeolite
T.R. Environtech Co. Ltd 586 catalytic cracking by 95, 196, 213, 226,
transition metal based catalysts 416 404, 495, 717
see also iron...; nickel... boiling point distribution of liquid
transition metal catalysts, on activated carbon product 204f
support 84, 103f, 149 initial degradation mechanism
transition metal oxide catalysts, cracking of 199–201
PET by 166–8, 747 liquid product produced 203, 204
transportation costs, waste plastics 705 olefinic/paraffinic hydrogen ratio 203
transportation fuels USA
conversion of waste plastics 346–50, lubricating oil waste 351
358–9 recycling of PET bottles 642t
feasibility study 350 waste plastics data 345, 363, 532
see also diesel; gasoline; kerosene waste-to-energy (WTO) facilities 124
treatment costs 26t, 36 USS process 739t, 744
784 INDEX
vacuum gas oil (VGO) logistics problems 25–6, 32, 704–5
coprocessed with plastics 90, 102, 113, ethical and political considerations 37–8
119, 217, 232t, 373, 374t in Europe 33, 35–6
hydrocracking of 216 in Japan 36–7, 666–7
vacuum pyrolysis 396 plastics pyrolysis as option 35–9
of polyolefins 289t, 290t environmental aspects 38
process parameters 287t safety aspects 38
of tyres 35, 723–4 plastics waste 33–5
vacuum residues 365 principles 32
properties 365t rubber waste 35
upgrading to fuel oils 369, 377–8 waste oils
see also petroleum residues amount dumped in USA 351
value of products coprocessed with plastics 102–3, 119,
comparison of pyrolysis reactor types 125
448t waste plastics
gas products 194 European data 73, 209, 363
Veba Combi Cracking (VCC) technology 30, Japanese data 209, 667, 668t
369, 377 Saudi Arabian data 377
Veba Oel pyrolysis process 23, 30–1, 443t, US data 345, 363, 532
534–7, 729, 738, 739t, 748 see also plastics waste
coal-to-oil conversion using 30, 369 waste prevention/reduction strategies 23
for coprocessing of vacuum residues with waste-to-energy (WTO) plants 439t, 440t,
waste plastics 118, 377–8 441t, 469, 494, 553, 555t
distillation residues processed using 369 compared with pyrolysis plants 252
flow diagram 535f in USA 124
mixed plastics waste processed using waxes
30–1, 377, 535–7 catalytic cracking of 171, 212–13
vinyl polymers from coprocessing of MWP/HVGO blend
pyrolysis of 326–9 218t
see also PS; PVC; PVDC pyrolysis-derived 212, 295–309, 597
viscosity chemical feedstock potential 306
fuel oils 155t, 305t FT-IR analysis 296–300
pyrolysis products 155t, 304t, 305, 429t, molecular weight range 300–4
674t, 685t, 698t properties 213t, 302t
viscosity index, lubricating base oils 351 thermal cracking of 603
Von Roll RCP process 443t uses 295, 304, 597
vortex ablative pyrolytic reactor 275 WEEE see waste from electrical and
VTA rotary kiln process 274t, 551, 555t electronic equipment
advantages 551 weight average molecular weight
vulcanized rubber 5, 365 meaning of term 300
see also rubber; tyres for various pyrolytic oils and waxes 302t
Williams–Landel–Ferry equation 228
waste from electrical and electronic equipment wood carbonization 251, 287
(WEEE)
collection and recycling of 25, 26, 34, Z3A Process and Technology 586
391 Zadgaonkar dechlorination process 721
EU directive on 33, 558 Zadgaonkar depolymerization process 724–7
plastics in 337 advantages 727
pyrolysis 35, 337–41 analytical section 727
fluidized-bed 438t, 440t, 466, 469, commercial plant 727
470 condenser section 727
rotary kiln 552–3, 555t, 559–62 dechlorination section 725
see also printed circuit boards features 727
waste management feed system 725
collection systems 24–5, 667 flow diagram 726f
INDEX 785
gas products 727 zeolite Y (type FAU) catalyst
liquid products 727 physicochemical properties 80t, 196,
reactor 725 240t, 717
zeolite catalysts 717 polyolefin cracking by 148, 149, 722
advantages 147, 239 see also HY
dewaxing by 398 zirconia, sulfated, catalytic cracking by 54,
limitations with PVC-containing wastes 55f, 57f, 84, 147, 749
405 ZSM-5 zeolite catalyst
molecular structure 80, 195–6, 239 coprocessing of distillation residues with
physicochemical properties 80t, 240t waste plastics 370, 371–2t, 374t
polyolefin cracking by 45, 46–54, 76f, PE cracking by 148, 149, 404
118, 140, 148–9, 195, 404 physicochemical properties 80t, 196,
pyrolysis gases cracked by 140 240
silicon/aluminium ratio 80t, 240t upgrading of plastics-derived gasoline
see also HY; HZSM-5; MFI type; REY; 722
US-Y; ZSM-5 see also HZSM-5
With thanks to Paul Nash for the compilation of this index.

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Feedstock Recycling

and Pyrolysis of Waste

Converting Waste Plastics into Diesel

Dendrimers and Other Dendritic Polymers

Modern Styrenic Polymers

Light Emitting Polymers

Environmentally Degradable Polymers

WILEY SERIES IN POLYMER SCIENCE

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Library of Congress Cataloging-in-Publication Data:

Feedstock recycling and pyrolysis of waste plastics / editors, John

British Library Cataloguing in Publication Data

Typeset in 10/12pt Times by Laserwords Private Limited, Chennai, India

1 Introduction to Feedstock Recycling of Plastics . . . . . . . . . . . . . 3

2 Acid-Catalyzed Cracking of Polyolefins: Primary Reaction

3 Catalytic Upgrading of Plastic Wastes . . . . . . . . . . . . . . . . . . . 73

5 Thermal and Catalytic Degradation of Waste HDPE . . . . . . . . . 129

6 Development of a Process for the Continuous Conversion of

4 Continuous Production of Fuels from Waste Plastics . . . . . . . 188

7 Catalytic Degradation of Plastic Waste to Fuel over Microporous

8 Liquefaction of Municipal Waste Plastics over Acidic and

9 Kinetic Model of the Chemical and Catalytic Recycling of Waste

10 Production of Gaseous and Liquid Fuels by Pyrolysis and

11 Yield and Composition of Gases and Oils/Waxes from the

12 Composition of Liquid Fuels Derived from the Pyrolysis of

4.2 Vinyl Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . 326

13 Production of Premium Oil Products from Waste Plastic by

14 The Conversion of Waste Plastics/Petroleum Residue Mixtures to

IV REACTOR TYPES 381

15 Overview of Commercial Pyrolysis Processes for Waste

5 Quality of the Output Fuels . . . . . . . . . . . . . . . . . . . . . . . 399

16 Fluidized Bed Pyrolysis of Plastic Wastes . . . . . . . . . . . . . . . . . 435

17 The Hamburg Fluidized-bed Pyrolysis Process to Recycle

18 Liquefaction of PVC Mixed Plastics . . . . . . . . . . . . . . . . . . . . 493

19 Liquid Fuel from Plastic Wastes Using Extrusion–Rotary Kiln

20 Rotary Kiln Pyrolysis of Polymers Containing Heteroatoms . . . . 549

21 Microwave Pyrolysis of Plastic Wastes . . . . . . . . . . . . . . . . . . . 569

22 Continuous Thermal Process for Cracking Polyolefin Wastes to

23 Waste Plastic Pyrolysis in Free-Fall Reactors . . . . . . . . . . . . . . 605

V MONOMER RECOVERY 625

24 Monomer Recovery of Plastic Waste in a Fluidized Bed Process . 627

25 Feedstock Recycling of PET . . . . . . . . . . . . . . . . . . . . . . . . . . 641

VI ASIAN DEVELOPMENTS 663

26 The Liquefaction of Plastic Containers and Packaging

27 Process and Equipment for Conversions of Waste Plastics into

9.1 Thermofuel of Waste Plastic by Ozmotech . . . . . . . . . 724

28 Converting Waste Plastics into Liquid Fuel by Pyrolysis:

José Aguado, Thallada Bhaskar,

Jean Dispons, G.P. Huffman,

André Fontana, Walter Kaminsky,

Guido Grause, Ali Karaduman,

Andreas Hornung, Kyong-Hwan Lee,

Keiji Wakai, Toshiaki Yoshioka,

Introduction to Feedstock Recycling

Plastics are a generic group of synthetic or natural materials, composed of high-molecular

3 PYROLYSIS OF PLASTICS AND RUBBER

3.1 SURVEY OF PREVIOUS WORK

3.2 PRODUCTS FROM POLYMERS