Optimal Design and Operation of Isomerization Process

Ministry of Higher Education and Scientific Research
University of Tikrit
College of Engineering
Optimal Design and Operation of

Isomerization Process
A THESIS SUBMITTED TO THE

COLLEGE OF ENGINEERING UNIVERSITY OF TIKRIT
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
MASTER OF SCIENCE
IN CHEMICAL ENGINEERING
BY
Ahmed Mohammed Ahmed

B.SC. IN CHEMICAL ENGINEERING
SUPERVISED BY
Asst. Prof. Dr. AYSAR T. JARULLAH Prof. Dr. FAYAD M.
ABED
1438 A.H. 2017 A.D
‫بسم اهلل الزمحه الزحيم‬
‫ً َ َ ً َْ َ ُ‬ ‫َ‬ ‫ٌ َ َ َّ ْ‬ ‫َ َّ ْ ُ َ َ‬
‫اجدا وق ِائما َيذر‬
‫﴿أمه هو ق ِاوت آواء اللي ِل س ِ‬
‫َ‬ ‫َّ‬ ‫ُ ْ َ َْ ْ َ‬ ‫َ َ َ َ ْ ُ َ ْ َ َ َ ِّ‬ ‫ْ‬

‫ذيه‬
‫خزة ويزجو رمحت رب ِه قل هل يست ِوي ال ِ‬ ‫اْل ِ‬
‫َّ َ َ َ َ َّ ُ ُ ُ‬ ‫َ َ َ ْ َُ َ‬ ‫َ ْ َ ُ َ َ َّ‬
‫ذيه َل يعلمون ۗ ِ إَّنا يتذكز أولو‬
‫يعلمون وال ِ‬
‫ْ َ َْ‬
‫اب﴾‬
‫اْللب ِ‬
‫سىرة السمر‬
‫اآليت (‪)٩‬‬
Supervisor Certification
We certify that this thesis entitled "Optimal Design and Operation of

Isomerization Process Reactor" presented by Ahmed Mohammed
Ahmed, that has been carried out completely under our
supervision at the Department of Chemical Engineering-
University of Tikrit in partial fulfillment of the requirements for
the degree of Master of Science in Chemical Engineering.
Signature: Signature:
Asst. Prof. Dr. Aysar T. Jarulla Prof. Dr. Fayad M. Abed
(Supervisor) (Supervisor)
In view of the available recommendation, I forward this thesis

for debate by the Examining Committee.
Signature:
Asst. Prof. Dr. Ahmed D. Wiheeb
Name: Head of the Chemical Engineering Department.
Date: / /
We, the members of the Examining committee, certify that after
reading this thesis and examining the student in its contents, we think that
is adequate for the award of degree of (Master of Science in Chemical
Engineering)
Asst. Prof. Dr. Ahmed D. Wiheeb Dr. Saad A. Jaafar
(Member) (Member)
Asst. Prof. Dr. Aysar T. Jarullah Prof. Dr. Fayadh M. Abed
(Supervisor) (Supervisor)
Signature:
Prof. Dr. Ammar S. Abbas
(Chairman)
Approved by the Council of the College of Engineering/ University of

Tikrit
Signature:
Prof. Dr. Fayadh M. Abed
Dean of College of Engineering

Abstract
ABSTRECT
Owing to the strict environmental regulations that request lower

content of olefins and aromatics in gasoline in addition to the strength
limits on using of tetraethyl lead (TEL), high octane number product
(isomerizate) obtaining via isomerization process is added to the pool of
gasoline. Thus, naphtha isomerization process is an important issue in
petroleum industries technology to produce clean and high octane number
gasoline components.
The optimal isomerization process of naphtha is studied here by a

complete mathematical model using continuum type to predict the
performance of an industrial isomerization fixed bed reactor at Baiji north
refinery and improving of such reactor. The operating variables of the
reactor; with zeolite catalyst and gases feed stocks, are as same as those of
isomerization reactor in Biji north refinery with the following ranges:
temperature (523-527 K), pressure (2.3-2.5 MPa), liquid hourly space
velocity (1.489-1.622 hr-1) and hydrogen to hydrocarbons mole ratio (3.2-
3.4 mol H2/mol HC).
The optimal values of the kinetic parameters of the relevant process is

also estimated in this study via optimization technique utilizing non-linear
approach based on the experimental results obtained from the actual unit of
Baiji north refinery. The kinetic parameters has been estimated depending
on minimizing the sum of squared errors between the predicted and
experimental results with absolute error less than 0.1% among all results.
Based on the analysis of the operating variables, the results indicated

that the isomerization reactor can be improved by using the optimal
variables of temperature, pressure, H2/HC mole ratio and LHSV for such
feed stock compositions and the type of the catalyst used.
V
Abstract
Increasing the research octane number (RON) has also been

investigated here via employing the isomerization technologies based on
maximizing of RON and isomerizate yield in addition to minimizing the
economic cost of such process. Several technologies (7 technologies in
addition to the technology that proposed in this study) reported in the
literature has optimized and a novel configuration of the isomerization
process is proposed in this study to get the maximum yield and RON
minimum cost of the relevant process. It has been observed that the new
technical proposed here having the highest RON (90.93) and yield (99.33),
and lowest overall annual cost (14770103$/yr) in comparison with those
reported in public domain.
The heat integration of the advanced configuration process of the

isomerization process suggested from this work has also been studied here.
A pinch technology is utilized for such issue in order to find the optimal
design of the heat exchanger network as a result of reducing the energy
consumption and maximizing the heat recovery.
VI
Acknowledgments
ACKNOWLEDGMENTS
Firstly, I thank ‗Allah‘ to all blessings that I gave. I would like to begin by
thanking my advisor, Asst. prof Dr. Aysar and prof. Dr. Fayadh for their
guidance and support. They always guides me to do the best. For this, I am
very thankful for them.
I'd like to thank all my lecturers and professors in Chemical Engineering
Department, College of Engineering at Tikrit University for their patience
and continuous support.
On a personal side, my appreciation to my parents. They are always
believing and supporting me. I cannot put into words how I grateful to their
presence in my life.
My thanks also go to my brothers, sisters and friends for their love and
patience.
Ahmed
VII
Dedicate
I dedicate this thesis to my parents
VIII
Contents
CONTENTS
ABSTRACT I
ACKNOLODGMENT III
CONTENTS V
LIST OF TABLES X
LIST OF FIGURES XIII
NOMENCLATURES XVI
GREEK LETTERS XXII
ABBRIVIATIONS XXV
CHAPTER 1 – Introduction
1.1 Introduction 1
1.2 Isomerization Process 2
1.3 Types of Isomerization Process 3
1.4 The Problem Statement 4
1.5 The Objectives 4
1.6 Scope 5
1.6 Thesis Organization 5
CHAPTER2 – Literature Review
2.1 Introduction 7
2.2 Light Naphtha Isomerization Process 7
2.3 Fundamental Reactions 8
2.4 Thermodynamic of Isomerization 10
2.5 Primary Reactions Mechanism 11
2.6 Reactors in Isomerization Process 12
2.7 Catalyst Used in Isomerization Process 16
2.7.1 Chlorided-Alumina Catalysts 17
IX
Contents
2.7.2 Zeolitic Catalysts 17

2.7.3 Sulphated Zirconia 18
2.8 Catalyst Contaminants 18
2.8.1 Sulfur 18
2.8.2 Water / Oxygenates 19
2.8.3 Nitrogen Compounds 19
2.9 Isomerization Operating Conditions 19
2.9.1 Temperature 19
2.9.2 Pressure 20
2.9.3 Liquid Hourly Space Velocity 20
2.9.4 Hydrogen to Hydrocarbon Mole Ratio 20
2.10 Modeling and Estimation of Isomerization 21
Kinetic Parameters
2.11 Isomerization Process Technologies 23
2.12 Pinch Technique 28
CHAPTER 3 – Mathematical Modeling of an Industrial

Isomerization Reactor
3.1 Introduction 30
3.2 Mathematical Model of Naphtha Isomerization 31
Reactor
3.3 Actual Data 31
3.4 The Model Equations of Isomerization Reactor 33
3.4.1 Mass Balance Equation of Compounds 33
3.4.2 Heat Balance Equation 34
3.4.3 Reaction Rate Equations 35
3.4.4 Reactions Scheme of Isomerization Process 37
3.4.5 Catalyst Activity 39
X
Contents
3.4.6 Flow Rate of Raw Material 39

3.4.7 Effectiveness Factor 40
3.4.8 Density of Mixture 46
3.4.9 Heat of Reaction Calculation 47
3.4.10 Calculation of Octane Number Model 48
3.4.11 Calculation of Isomerizate Yield 49
3.5 Estimation of Kinetic Parameters of the Model 49
3.6 Optimization Problems Formulations for Parameters 53
Estimation of Naphtha Isomerization Process
3.7 Summary 55
CHAPTER 4 – Results and Discussion
4.1 Introduction 56
4.2 Kinetic Model 56
4.3 Effect Of Different Variables On The Performance 65
of Isomerization Process
4.3.1 Effect of Temperature and Pressure 65
4.3.2 Effect of Hydrogen to Hydrocarbon Mole Ratio 67
4.3.3 Effect of LHSV 69
4.4 Summary 71
CHAPTER 5 – Isomerization Configurations
5.1 Introduction 72
5.2 Isomerization Technologies 73
5.2.1 Once Through Process 74
5.2.2 Deisopentanizer (DIP) Process 75
5.2.3 Deisohexanizer (DIH) Process 75
5.2.4 DIP and DIH Process 76
XI
Contents
5.2.5 Ipsorb Process 77

5.2.6 Hexorb Process 78
5.2.7 Total Isomerization Process (TIP) 79
5.2.8 Advanced Configuration (proposed in this Study) 80
5.3 Economic Cost Equations 81
5.3.1 Installed Equipment Capital Cost (IECC, $) 83
5.3.2 Fixed Unit Operating Cost (FUOC, $/yr) 90
5.3.3 Variable unit operating cost (VUOC, $/yr) 91
5.4 Energy Balance 93
5.5 Optimization Problem 100
5.6 Result and Discussion 101
5.6.1 Results of Once Through Process (Case study 1) 101
5.6.2 Results of Deisopentanizer (DIP) 103
Process (Case study 2)
5.6.3 Results of Deisohaxanizer (DIH) Process 104
(Case study 3)
5.6.4 Results of DIP and DIH Process (Case study 4) 105

5.6.5 Results of Isoporb Process (Case study 5) 106
5.6.6 Results of Hexorb Process (Case study 6) 107
5.6.7 Results of Total Isomerization Process (TIP) 108
(Case study 7)
5.6.8 Results of Advanced Configuration (proposed in 110
This Process)
5.7 Heat Integration of Advanced Configuration (Pinch 111
Technique)
5.7.1 Minimum Temperature Difference 112
Calculations
XII
Contents
5.7.2 The Heat Exchanger Network Design 113

5.7.3 Optimization Problem For Heat Saving Process 116
5.7.4 Optimal Economic Cost of the Modifying ACP 117
Flow Diagram
5.8 Summary 118
CHAPTER6- Conclusions And Recommendations
6.1 Conclusions 120

6.2 Recommendation 122
REFERENCES 123
APPENDIX A 131
A.1 Computational gPROMS Software 131

A.2 Advantages of gPROMS Software 131
A.3 Model Application on gPROMS 133
A.4 Model Entity 135
A.4.1 Defining Parameters 135
A.4.2 Defining Variables 135
A.4.3 Defining Equations 137
A.5 Process Entity 138
A.6 Optimization Entity 143
XIII
List of Tables
LIST OF TABLES
Table (1.1): Properties of normal and iso-paraffins 2

Table (2.1): Comparison among the catalysts types 16
Table (2.2): Maximum allowable contaminant levels in the 17
Feed
Table (2.3): The RON of the isomerization process obtained 26
by different technologies and catalysts
Table (2.4): Performance of operating isomerization units at different 27
refinery
Table (3.1): Chemical reactions equations for 38
isomerization processes
Table (4.1): Inlet and outlet composition (Wt%) of 57
isomerization reactor through test run days
Table (4.2): Operating condition of isomerization reactor 57
through test run days
Table (4.3): Values of physical properties of light naphtha 58
components used in the model
Table (4.4): Catalyst and feedstock properties 59
Table (4.5): Standard enthalpies of formation and constants 59
heat capacity
Table (4.6): Optimal values of per-exponential factor and 61
activation energy of every reaction
Table (4.7): Optimal orders of components concentration and 62
kinetic coefficient of intermolecular
interactions intensity
Table (4.8): Comparison between optimal and theoretical 63
orders values
XIV
List of Tables
Table (4.9): The comparison between the experimental 64

data and the mathematical model results
(predicted)
Table (5.1): Values of coefficients and constant parameters used 102
in this process
Table (5.2): Dimensionless factors values 102
Table (5.3): Economic and performance variables results of once 103
through process
Table (5.4): DIP variables 104
Table (5.5): Optimal operating conditions, cost and performance 104
variables results of process with DIP
variables results of process with DIH
variables results of isomerization process with DIP&
DIH
Table (5.8): Optimal operating conditions, cost and 107
performance variables results of Ipsorb
process
variables results of Hexorb process
Table (5.10): Values of coefficients and constant 108
parameters used in this process
performance variables results of TIP process
performance variables results of ACP
process
XV
List of Tables
Table (5.13): ACP, TIP and once through process comparison 111
Table (5.14): Data required for heat integration problem 112
Table (5.15): Optimal performance, cost and operating 118
conditions of optimization problem for
modify ACP
XVI
List of Figures
LIST OF FIGURES
Figure (2.1): Effect of temperature on the conversion of n- 11

paraffins
Figure (2.2): Flow diagram of Penex process 25
Figure (2.3): Flow diagram of Par-Isom process 25
Figure (2.4): Composite curves for the traditional thermal hydrolysis 29
processes
Figure (3.1): Available tools and required dates for light 32
naphtha isomerization modeling, simulation &
optimization process
Figure (3.2): Once through isomerization process flowsheet. 33
Figure (3.3): Scheme of formalized reaction for isomerization 37
Process
Figure (3.4): Algorithm of kinetic parameters estimation 52
Figure (4.1): Effect of temperature on the RON of product at 66
different pressure with constant LHSV equal to
1.489 , H2/HC equal to 3.22 mole ratio
Figure (4.2): Yield of isomerizate at different temperature and 67
pressure and at constant LHSV of 1.489hr-1 and
constant H2/HC at 3.22 mole ratio
Figure (4.3): Effect of H2/HC on the RON at different 68
temperature with constant LHSV equal to
1.489 and constant pressure equal to
24MPa
Figure (4.4): Yield of isomerizate at constant temperature of 69
523K, LHSV of 1.489hr-1 and pressure of
2.4MPa
XVII
List of Figures
Figure (4.5): Effect of LHSV on RON at constant temperature 70

of 523K, H2/HC at 3.22 and pressure equal to
2.4 MPa
Figure (4.6): Effect of LHSV on yield at constant temperature 70
of 523K, H2/HC of 3.236 and pressure equal to
2.4MPa
Figure (5.1): The procedure of isomerization configurations 74
optimization
Figure (5.2): Block diagram of process with DIP 75
Figure (5.3): Block diagram of isomerization unit with DIH 76
Figure (5.4): Block diagram of isomerization unit with DIH 77
and DIP
Figure (5.5): Block diagram of Ipsorb isomerization unit 78
Figure (5.6): Block diagram of Hexorb isomerization unit 79
Figure (5.7): Flow diagram of TIP isomerization unit 79
Figure (5.8): Flow diagram of advanced configuration 81
Figure (5.9): Heat exchanger E201 93
Figure (5.12): heat exchanger E204 and heat exchanger E205 98
Figure (5.13): Cold and Hot streams composite curves 113
Figure (5.14): Grid of the six streams 113
Figure (5.15): Proposed heat exchanger network 115
Figure (5.16): Modify flow diagram of ACP 116
Figure (A.1): An overview of the gPROMS environment at start up 133
Figure (A.2): An overview of gPROMS builder 134
Figure (A.3): Illustrated of parameters and variables in gPROMS 136
Figure (A.4): An overview of variable type in gPROMS program. 136
XVIII
List of Figures
Figure (A.5): illustrate of differential equation entry in gPROMS 137

Figure (A.6): Illustrate of energy balance equations entry in 138
gPROMS
Figure (A.7): Over view of unit and set sections 139
Figure (A.8): Over view of assign section 140
Figure (A.11): Optimization file in gPROMS for the kinetic model 143
of isomerization process
XIX
Nomenclatures
NOMENCLATURES
Symbol Description Unit
a Catalyst activity (-)
A Pre-exponential factor (mol/m3)1-nhr-1
As cross section area of vapor flow rate
At Total area of heat exchangers
At1 Area of heat of E201
AUCC Annual unit capital cost $/yr
AUOC Annual unit operating cost $/yr
Β is a total deviation of hydrocarbons octane number (-)

from additively
bhp horsepower required in the compressor Hp
CAd Adsorber capital cost ($)
CB Boltzmann constant (-)
Cco. Compressor Cost
Ccomp. Compression cost
Ccol. Column Cost
XX
Nomenclatures
Ccool. Cooling cost
CF Furnace cost
CH2 Hydrogen concentration mol/m3
CHE Heat exchanger cost
CHeat.. Heating cost
Ci Concentration of ith component mol/m3
Ci,in Initial (inlet) concentration of ith component mol/m3
Cpum. Pumping cost $/yr
Cpump Pump cost $
Cr Reactor capital cost $
Csep. Separator cost $
Cst Stablization Cost $
Csteam Steam cost $/yr
Ctray Tray Cost $
CH2 Hydrogen cost $/yr
Cp The heat capacity of streams kJ/(kg.ºC)
Cpi,p Heat capacity of reaction product components J/mol.K
Cpi,r Heat capacity of reaction reactant components J/mol.K
Cpm Heat capacity of mixture J/(kg. k)
CpH2 The specific heat capacity at constant pressure J/(kg. k)
Cph1,l heat capacity of hot stream as liquid in E201 kJ/(kg k)
Cpc1,l heat capacity of cold stream as liquid in E201 kJ/(kg k)
Cph1,v heat capacity of hot stream as vapor in E201 kJ/(kg k)
Cpc1,v heat capacity of hot and cold stream respectively as kJ/(kg k)
XXI
Nomenclatures
vapor in E201
CvH2 The specific heat capacity at constant volume J/(kg. k)
dpe Equivalent particle diameter m
dt Tube diameter m
DAd Adsorber diameter (m)
Dc column diameter (m)
De Effective diffusivity m2/hr
Di,k Binary diffusion coefficient of ith component m2/hr

through the other components
Dki Knudsen diffusivity coefficient of species i in the m2/hr
gas phase
Dgmi Molecular diffusivity coefficient of species i in the m2/hr
gas phase
Dr Reactor diameter
Dii Dipole moment of molecule i Debye
Dimax Maximum possible dipole moment of the Debye

hydrocarbons mixture
E Activation energy J/mol.K
f1 Maintenance Cost $
f2 Operating Labour Cost $
f3 Laboratory Cost $
f4 Supervision Cost $
f5 Plant Overhead Cost $
f6 Capital Charge Cost $
f7 Insurance Cost $
XXII
Nomenclatures
Fd Design dimensionless factors (-)
Fc , Fm , Fp Dimensionless factors that are function of the (-)

operating pressure and material construction
G raw material flow rate m3/hr-1
hv Vapor high m
hp the isentropic compressor horsepower Hp
i hydrocarbon components number (-)
j Reaction number (-)
k Apparent reaction rate constant (mol/m3)1-nhr-1
lt Tray spacing (m)
L Particle length m
LAD Adsorber length m
Lc Column length m
Lr Reactor length m
Ls Separator cost m
LHSV Liquid hourly space velocity hr-1
m Order of hydrocarbons concentration in (-)

dehydrogenation reaction
mr Mole ratio of hydrogen to light naphtha (-)
M Total moles interred the reactor mol
Miso. Moles of isomerizate mol
MH2 Total moles interred the reactor mol
Mln Moles of naphtha feed mol
MWi Molecular weight of hydrocarbon i kg/kmol
XXIII
Nomenclatures
MWH2 Molecular weight of hydrogen kg/kmol
MWln Molecular weight of light naphtha kg/kmol
n Order of hydrocarbons concentration (-)
Nt Number of tray (-)
o Order of hydrocarbons concentration in (-)

hydrogenation reaction
P Reactor pressure Pa
Pin , Pout Inlet and outlet pressure in the compressor Pa
Pns Naphtha stream pressure Pa
qF Furnace heat duty kJ/rh
qE201 rate of heat transfer through E201 kJ/rh
qj Heat of jth reaction kJ/mol
qp power of ith pump kJ/hr
Qin Flow rate of hydrogen at compressor section m3/hr
Qln Liquid Flow rate of light naphtha m3/hr
Qv Hydrogen volumetric flow rate m3/hr
rg Mean pore radius, m
R Gas constant J/mol.K
XXIV
Nomenclatures
RON Research octane number (-)
RONi ith pure component research octane number (-)
Sg Specific surface area of particle m2/kg
Sp Total geometric surface area m2
sp.gr Specific gravity (-)
T1b,c Boiling temperature of cold and stream in E201 K
T1b,h Boiling temperature of hot stream in E201 K
T1i,h The inlet temperature of hot stream into E201 K
T1i,c The inlet temperature of cold stream into E201 K
T1o,h The outlet temperature of hot stream from the E201 K
T1o,c The outlet temperature of cold from E201 K
To,F, Ti,F Outlet and inlet furnace temperature K
T* Dimensionless temperature (-)
ua settling velocity m/s
uv Vapor velocity m/s
U1 Heat transfer coefficient of E201 kJ/(m2.K.hr)
VAd Adsorber bed volume m3
Vb Liquid molar volume at normal boiling temperature m3/kmol
XXV
Nomenclatures
Vg Total pore volume m3/kg
Vp Total geometric volume of partical m3
Vw Maximum vapor rate kg/s
W5A Weight of 5A zeolite catalyst kg
Wcat. Weight of 5A zeolite catalyst kg
WH2 Weight flow rate of hydrogen inter to reactor kg/hr
WH2, C weight rate of hydrogen consumption kg/hr
WH2,in weight rate of hydrogen inlet to the reactor kg/hr
WH2,o weight rate of hydrogen out from the reactor kg/hr
WH2O Weight flow rate of cooling water kg/hr
Wln Weight flow rate of light naphtha kg/hr
Wsteam Weight flow rate of steam kg/hr
X Inert bed high m
y Mole fraction (-)
Z Compressibility factor (-)
XXVI
Greek Letters
GREEK LETTERS
Symbol Definition Unit
ɳ Effectiveness factor (-)

ⱷ Thiel Modulus (-)
Ρln Liquid (naphtha) density kg/m3
ΡH2 Vapor (hydrogen) density kg/m3
ρp Particle density kg/m3
ρbi Liquid density of component i at normal boiling kg/m3
Point
ρsv vapor density kg/
ρsl liquid density kg/
ЄB Bed porosity (-)
Φs Shape factor (-)
Єs Catalyst particle porosity (-)
σi,k Average collision diameter m
∩D Collision integral for diffusion (-)
σi Collision diameter of ith m
σk Collision diameter of kth components m
I,k Characteristic (minimum) energy K

∆ rxn,j Standard heat of jth reaction kJ/mol
∆Cpj Heat capacity of jth reaction kJ/mol.K
∆ fi,p Standard heat of formation of reaction product kJ/mol
components
∆ fi,r Standard heat of formation of reaction reactant kJ/mol.K
components
y Mole fraction (-)
XXVII
Greek Letters
ßi ,ßk Parameters showing the tendency of ith molecule to (-)

intermolecular interaction with kth molecule
γ, α Kinetic coefficients defining the intensity of intermolecular
(-)
interactions from dipole moment
Yield isomerizate yield, (-)
err Error function (-)
OBJ Objective function (-)
OAUC Overall annual unit cost $/yr
TUCC Total unit capital cost $
IECC Installed equipment capital cost $
M&S Marshal and Swift index (-)
τ Tortuosity factor
τa Required residence time hr
τr Actual residence time hr
ɳc isentropic compressor efficiency (-)
ω the specific heat ratio (-)
∆Tlm,1 Log mean temperature difference for E201 (-)
λc1 Latent heat of vaporization of cold stream in E201 kJ/kg
λh1 Latent heat of vaporization hot stream in E201 kJ/kg
∆T Temperature difference K
XXVIII
Abbreviations
ABBRIVIATIONS
Symbols Definitions
2,2-DMB 2,2-Dimethyl butane

2,3-DMB 2,2-Dimethyl butane
2-MP 2-methyl pentane
3-MP 3-methyl pentane
A-201 Air cooler equipment
ACP Advanced configuration process
AUOC Annual Unit Operating Cost
B Benzene
C5 Pentane components
C6 Hexane components
C-201 Column equipment
CH Cyclo hexane
CP Cyclo pentane
D-201 Vessel one
D-202 Vessel two
DIP Deisopentanizer
DIH Deisohexanizer
DP Depentanizer
E-201 Heat exchanger one
E-202 Heat exchanger two
E-203 Heat exchanger three
E-204 Heat exchanger four
E-205 Heat exchanger five
E-206 Heat exchanger six
E-207 Heat exchanger seven
XXIX
Abbreviations
F-201 Furnace one

F-202 Furnace two
FCCG Fluidized catalytic cracking gasoline
FUOC Fixed Unit Operating Cost
Ga Gallium
H2 Hydrogen
HC Hydrocarbons
i-C4 Iso-butane
i-C7 Iso-heptane
i-P Iso-pentane
IECC Installed Equipment Capital Cost
LHSV liquid hourly space velocity
M-201 Compressor equipment
MON Modern octane number
n-C4 Normal butane
n-C7 Normal heptane
n-P Normal pentane
n-H normal hexane
NLP Non-linear programming
O2 Oxygen
OAUC Overall Annual Unit Cost
P-201 pump one
P-202 pump two
ppm Part per million
Pd Palladium
Pt platinum
R-201 Reactor equipment
Re Radium
XXX
Abbreviations
RON Research octane number

RVP Reid vapor pressure
S-201 Adsorber one equipment
S-202 Adsorber two equipment
Si Silica
SIE Scientific industrial enterprise nefthim
SSE Sum of square error
SQP Consecutive quadratic programming
SZ Sulfated zirconia
TIP Total isomerization process
TUCC Total Unit Capital Cost
VUOC Variable Unit Operating Cost
Wt% weight fraction
XXXI
Chapter One Introduction
CHAPTER ONE
INTRODUCTION
Chapter One
Introduction
1.1 Introduction
The stringent environmental regulations have reported that the
concentration of aromatic and benzene compounds in the gasoline should
not be exceed. The Regulations Mobile Source Air Toxics (MSATII) limit
the benzene content in gasoline up to 0.62 % become operative (Palmer et
al., 2008). The benzene limits up to 0.96 % have already been introduced in
USA (Yasakova et al., 2010).
Contents of aromatics and olefins in the gasoline should be reduced
for environmental protection. The loss of octane number caused by
reduction of aromatics and olefins should be compensated by addition of
some compounds that have high octane numbers. One possible alternative
of aromatics and olefins is branched alkanes that have high octane
numbers. Accordingly, skeletal isomerization of alkanes is a key reaction
for producing environmentally benign gasoline (Moran et al., 2005).
Reforming process has been used to produce high octane compounds
and aromatic hydrogenation simultaneously, but this process is exclusively
used for treating of heavy naphtha (C7-C8). This limitation on the feed
components in addition to the presence of hexane leads to make benzene
component by dehydrogenation reaction. So the isomerization process is
confirmed to be a simple, economic and very attractive solution to produce
clean gasoline with high octane number, acceptable vapor pressure and
maintaining the gasoline pool without adding lead compounds (Parkash,
2003; Koncsag et al., 2011).
1
1.2 Isomerization Process

Light naphtha is desirable to be included in gasoline formulation to
meet the front-end distillation cat and octane number specs. However, the
normal paraffin's C5/C6 is difficult to be included in the gasoline pool
because they have low octane number, but converting them to equivalent
branched chain by isomerization process making them more favorable for
inclusion in gasoline due to their high octane number and high Reid vapor
pressure as stated in Table (1.1) (Parkash, 2003).
Table (1.1): Properties of normal and iso-paraffins (Parakash, 2003)

hydrocarbons BP(ºC) RVP(kpa) RON MON
Normal pentane 36 103.4 62 62
Iso-pentane 28 137.9 92 89.6
Normal hexane 69 34.47 25 26
2-Methyl pentane 60 48.26 73 73
3-Methyl pentane 63 41.37 75 73
2,2-Dimethyl butane 50 68.95 92 93
2,3-Dimethyl butane 58 48.26 102 94
According to global environmental concern, severe quality of gasoline

is desired. Therefore, in addition to the regulations for aromatic and
benzene content, the gasoline limitations for Reid vapor pressure (RVP)
and sulfur content have been determined, which are related to volatile
organic compounds. A certain change will occur in gasoline blend stoke
based on these regulations (Yasakova et al., 2010).
The isomerization process is a countermeasures solution for the losses

of the RON, which are caused by any regulation such as sulfur regulations,
limitations of olefins and aromatics compounds (which limit the using of
2
fluid catalytic cracking gasoline (FCCG)) and RVP regulations. All of these
situations can cause a lack of gasoline and a loss of its octane number.
Thus, the manufacturing of paraffin based a gasoline with high octane
number such as isomerizate by isomerization of light naphtha, could be a
key technology for gasoline equipping to meet a future gasoline limitation
(Watanabe et al., 2005).
1.3 Types of Isomerization Process

There are several isomerization processes, based on the catalyst system
and the separation technologies of product. The main isomerization
catalysts have been consisted of chlorided-alumina (at end of 1950s), while
zeolitic catalyst is later developments, then higher activity chlorided
alumina catalyst and metal oxide-based catalyst are developed (Chekantsev
et al., 2014).
Every catalyst system has a specific collections of operating condition
that can impact both product octane and the unit costs. Below the basic
three types of the isomerization process (Yasakova et al., 2010):
- High temperature process (250-300 oС) on zeolite catalysts.
- Medium temperature process on sulfated metal oxides (180-210 oС).
- Low temperature process on chlorinated alumina catalysts (120-180
o
С).
With each above catalyst system, many technologies are used to
separate and recycle low octane straight components such as depentanizer
(DP), deisohexanizer (DIH) and molecular sieves. Also, the branched
paraffins can be separated before inter the feed stock to the reactor by using
deisopentanizer (DIP).
Also, the adsorption on molecular sieves (in vapor or liquid phase) can
be used for the separation of normal paraffins. Normal paraffins is separated
and recycled based on pores with definite size capability to selectively
3
adsorb the normal paraffins molecules. Then the normal paraffins desorbed
from pores will be recycled to the feed stock. such cycles of adsorption and
desorption are repeated or pseudo-continuously is used. There are other
schemes of the isomerization process use iso-sieve techniques such Ipsorb,
Hexorb and total isomerization processes.
1.4 The Problem Statement

The reduction of benzene and limiting the aromatic and olefinic
components in gasoline cause losses of the octane number in gasoline
structure pool, thus the isomerization process is gained the attention to
produce high octane branched paraffin's. The isomerization reactions are
reversible reactions, so it is impossible to convert all low octane straight
hydrocarbons chain to high octane branched hydrocarbons chain without
using of isomerization technologies. The knowledge of the most benefit
technology is related to the feed stock composition, so the experimental
work or process simulation and optimization process of this technologies is
necessary before using one of them.
1.5 The Objectives

The main objectives of this study can be summarized as follow:
1. Revamping of isomerization process of fixed bed reactor at Baiji north
refinery. by applying an accurate mathematical model to describe the
behavior of such process. depending upon the experiments and
employing the modeling and optimization technique.
2. Analysis of the process conditions of the isomerization reactor operation
at Baiji refinery.
3. Finding the best scheme configuration from isomerization technologies
that maximize the RON and yield and minimizing the cost.
4. Minimizing the heating and cooling required for such process.
4
1.6 Scope
1. Applying an accurate mathematical model to describe the behavior of the
process. depending upon the experiments and employing the modeling and
optimization technique.
2. Calculate the RON and yield of isomerizate at different temperature,

pressure, LHSV and hydrogen to hydrocarbon mole ratio.
3. Applying the existing techniques of recycles and by-pass streams (IsoSiv,

DIP, DIH and DP) and studying the development of new scheme for the
isomerization process to get the best design for achieving maximum octane
number, yield and profit.
4. Using pinch technologies to find the minimum temperature difference

and obtain the optimal design of heat exchanger.
1.7 Thesis Organization

The structure of the thesis can be described as follow:
Chapter one: Introduction

The thesis begins with an introduction importance of the isomerization
process, types of isomerization processes. The problem statement,
objectives of this research and the structure of the thesis are also presented.
Chapter two: literature survey

This chapter will include the previous works related to the
isomerization process, reactions thermodynamic, catalyst types, effect of
different factors i.e. operating conditions and contaminate on the process.
5
Chapter three: Mathematical Modeling of isomerization process

This chapter involves the equations of the mathematical modeling used
here to describe the performance of fixed bed reactor of the isomerization
process in addition to the parameter estimation via optimization.
Chapter four: Results and discussion

An accurate kinetic parameters of isomerization reactions are
presented in this chapter. Also, the effect of operating conditions on the
RON and yield of isomerization are discussed.
Chapter five: Isomerization Configurations

In this chapter different schemes of the isomerization process will be
simulated and optimized using different separation technologies. Also, heat
integration for the best scheme of the process with minimum energy
consumption and maximum heat recovery will be investigated.
Chapter six: Conclusions and Recommendations

This chapter will involve the conclusions and what has been achieved
in this study with furthermore proposal for future work.
6
Chapter Two Literature Survey
CHAPTER TWO
LITERATURE SURVEY
Chapter Two
Literature Survey
2.1 Introduction
Isomerization process is the rearrangement of straight-chain
hydrocarbons components (low octane number) and convert it to branched
hydrocarbons components (high octane number) (Yasakova et al., 2010).
Due to the high content of straight chain normal paraffins, the light
naphtha has a low research octane number (RON). For this reason, the light
naphtha is undesirable component for gasoline blend of free lead. A small
amount of side reactions like naphthenic ring opening, naphthenic
isomerization, benzene saturation or hydrocracking can appear. The
stabilization of the product is necessary due to these reactions (Parkash,
2003).
Technologies of isomerization process can be used as a wide series of
refining applications. Today the applications used is the light normal
paraffins isomerization process. In this process, low octane paraffins is
isomerized to produce a flexible high octane, free of sulfur, benzene and
olefins feed stock. Also, the production of iso-butanes by isomerization
process of normal butanes is a further popular application to deliver feed
for alkylation process and chemical plants as well (Graeme et al., 2004)
2.2 Light Naphtha Isomerization Process

The light naphtha (C5-C6) is fractionated from heavy naphtha and it is
used as a feed to the isomerization process. This fractionation is necessary
for two reasons: First reason: The heavy hydrocarbon components tend to
hydrocrack in the isomerization process. Second reason: the hydrocarbon
components, which have six atoms that tend to make benzene components.
7
So that the isomerization product meets with gasoline specifications which

require a very low content of benzene because of its carcinogenic
influences (Parkash, 2003).
Branched isomers of pentane and hexane are necessary for production
of high-performance clean-burning transport fuels. The TEL elimination as
a compound of gasoline antiknock over the last decades, and more-recent
regulations on content of benzene, sulfur, and olefin has led the refiners to
select isomerization process where high-quality gasoline is produced
(Yasakova et al., 2010).
2.3 Fundamental reactions

The term of isomer refers to the compounds that have the same
molecular formula at different arrangement of atoms. In general, any
compounds that are linear or straight chain are termed normal's, if they are
in different arrangement, i.e branched, they are termed isomers (Anderson
et al., 2004).
For examples:
H H H H H H H H H
H C C C C C H H C C C C H (2.1)
H H H H H H H H
H C H
H
n-C5H12 i-C5H12
(RON=62) (RON=92)
As shown in equation (2.1), the normal pentane (n-C5H12) that has

research octane number (RON) of 62 is converted to iso-pentane having
research octane number (RON) of 93 through isomerization reaction. And
the same behavior with hexane that has more isomers.
8
H H H H H H H H H H H
HC C C C C C H H C C C C C H (2.2)
H H H H H H H H H H
H C H
H
n-C5H12 2-MP
(RON=62) (RON=72)
Other reactions than isomerization can take place here and having a negative
effect on the octane as follows (Parkash, 2003):
 Benzene hydrogenation
H2 (2.3)
C 6H 6 c-C6H12
(RON=120) (RON=84)
This reaction takes place readily in the first 10-15% of the catalyst
bed. It is accompanied by a large exothermal of approximately 640 Kcal/kg
and a high consumption of hydrogen as well as a negative octane effect is
noted, (i.e. benzene converting to its lower octane arrangements) (Parkash,
2003).
 Ring opening of naphthenes
H H H H H H
H2 H C C C C C C H (2.4)
H H H H H H
c-C6H12 C6H14
(RON=84) (RON=24)
9
The rate of this reaction (2.4) increases with increasing the reaction
temperature.
 Paraffin hydrocracking
H H H H H H H H H H H H
H C C C C C C H H2 H C C C H H C C C H (2.5)
H H H H H H H H H H H H
C6H14 C 3H 8
This reaction is catalyzed by the acidity of the catalyst and high

reaction temperature. The higher molecular weight (C7+), the greater of the
extent of hydrocracking is noticed. Hydrocracking is accompanied by an
exothermal and a high consumption of hydrogen can be occurred.
2.4 Thermodynamic of Isomerization Process

The main parameter where the octane number of produced isomerizate
depends on, is the process temperature and that‘s why the authors will
dwell on the issue of thermodynamic for isomerization reaction. First of all,
hydrocarbons isomerization reactions are balanced reactions, and
equilibrium yield of iso-paraffins increases with decreasing in the
temperature. However, it can be reached only after an ―infinite residence
time‖ of the feed in the reaction zone or an equivalent very small value for
LHSV as shown in Figure (2.1). On the other hand, an increase in
temperature always corresponds to an increase in reaction velocity. So that
at low temperature, the actual yield will be far below the equilibrium yield
owning to low reaction velocity. On the contrary, at higher temperature, the
equilibrium yield will be more easily reached due to a high reaction rate.
Consequently, at higher temperature, the yield of iso-paraffins is limited by
the thermodynamic equilibrium and opposite behavior can be observed at
11
lower temperature, which is limited by a low reaction rate (kinetic

limitation) (Anderson et al., 2004; Yasakova et al., 2010).
The
o
Iso-P concentration
retic
al c
onv
ersi
on (
equ
rs ion ilibr
ium
e
nv )
co
tu al
Ac Kinetik Thermodynamic
limitation limitation
Toptimal
Figure (2.1): Effect of temperature on the conversion of n-paraffins

(Chuzlov et al., 2014)
2.5 Primary Reactions Mechanism

Dual-function catalyst of an acid function and a noble metal (Pt)
having a most effect on the paraffins isomerization reactions. The reaction
mechanism is essentially the same for C4, C5 and C6 paraffins with all
types of the catalysts. The mechanism of the reactions can be summarized
as follow (Chekantsev et al., 2014; Hayati et al., 2015):
Paraffin dehydrogenation to produce intermediate olefin is the first step and
acquires on the noble metal site:
⇔ (2.6)
In the second step equation (2.7), the intermediate olefin converts to

carbonium ion on the strong acid site:
[ ][ ]→ (2.7)
The carbonium ion formation eliminate product of the reaction in step one
and permit the equilibrium to progress.
11
The carbonium ion produced from previous reaction undergoes a skeletal

isomerization as in equation (2.8):
→ (2.8)
The above reaction proceeds with difficulty, as it requires primary
carbonium ion formation at some points in the reaction.
In this step the iso-paraffinic ion is converted to olefin ion through proton
loss:
[ ]→ [ ][ ] (2.9)
Finally, the intermediate olefin ion is hydrogenated to form iso-paraffin:
↔ (2.10)
2.6 Reactors in Isomerization Process

Catalytic fixed-bed reactors are the most important type of reactor for
the synthesis of large scale basic chemicals and intermediates. In these
reactors, the reaction takes place in the form of a heterogeneously catalyzed
gas reaction on the surface of catalysts that are arranged as a fixed bed in
the reactor. With regard to application and construction, It is convenient to
differentiate between fixed bed reactors for adiabatic operation and those
for non-adiabatic operation. Since temperature control is one of the most
important methods of influencing a chemical reaction, adiabatic reactors
are used only where the heat of reaction is small; in these cases no adverse
effects on selectivity or yield due to the adiabatic temperature development
are expected (Rouger, 2013).
Continuously, catalytic isomerization of pentanes and hexanes
mixtures is conducted over a fixed bed of catalyst in an atmosphere of
hydrogen and at operating conditions that minimize hydrocracking
reactions and promoting the isomerization reactions. One or two reactors in
12
series can be used in this process, each one has an equal catalyst volume.
The reaction can be acquired in the liquid or gas phase according to the
catalyst used in the system. In this study, the catalyst used is the zeolitic
thus both the hydrogen and light naphtha in the gas phase (Parakash,
2003; Bartholomew and Farrauto, 2011).
Many authors studied the performances of the isomerization reactors
and the effect of different variables such temperature, pressure, H 2/HC
mole ratio, LHSV and feed composition with different catalyst types.
Summarize for previous works can be stat follow:
Watanabe et al. (2004) have studied the relations between the metal
and the catalytic activity in the isomerization reactors of sulfur-containing
light naphtha on Alumina-Sulfated Zirconia catalyst. They prepared the
isomerization catalysts in which the kinds of metal were different (Pt and
Pd), and they investigated the influence on the isomerization activity of the
sulfur content in the feed in detail. Furthermore, when they prepared the
catalysts, the methods of the Pd and Pt addition were different. Finally,
they reported a hybrid-type catalyst that works effectively in the
isomerization reactor of light naphtha, having a sulfur in high content. The
highest conversion of pentane is equal to 71% at 3.1 MPa, 468 K, 2 mol
H2/mol HC and LHSV equal to 1.5 hr-1.
Busto et al. (2008) studied the performance of isomerization reactor
with Pt/WO3-ZrO2 catalyst for the simultaneous hydro-isomerization of n-
hexane and benzene at varying values of total system pressure, fixed
reaction temperature (300 °C), and molar ratio H2/HC equal to 6. They
found the total pressure of 2 MPa was satisfactory for performing both the
hydrogenation of benzene and the isomerization of n-hexane at convenient
reaction rates (the conversion of hexane = 57%).
Tailleur and Platin (2008) investigated the effect of Pt loading on the
light naphtha isomerization reactions using PtGaZr/SiO2-type catalysts
13
using a fixed bed reactor. The reactions was studied in a radial plug flow-
type gas-phase reactor at three temperature levels (460, 470 and 480 K),
residence times (1, 1.5 and 2 hr-1) and H2/HC (2 and 3 mol/mol). A
mechanism consists of two isomerization acid sites and an apparent kinetics
model for light naphtha isomerization is used to predict the isomer yields in
a gas-phase radial reactor. The role of catalysts surface composition in
chemical reactions has also been discussed. The analysis of the reaction
product indicates that the reaction might proceed without Pt with slightly
lower activity and similar (but not identical) product distribution as those
observed in the presence of Pt. The highest temperature (480 K) and lowest
LHSV (1 hr-1) have given the highest conversion of pentane (58%) and
hexane (78%).
Watnabe et al. (2008) examined the effect of moisture and heptane
content, and developed the new isomerization process with Pt/SO42-/ZrO2
catalyst for isomerization of petrochemical raffinate (which is a by-product
from the ethylene-cracker) in a fixed bed reactor. In the commercial
operation of an actual isomerization unit, it was confirmed that the
isomerization product was stably obtained and the octane number of the
petrochemical raffinate was improved by 11 (the RON increased from 60 to
71).
Khurshid et al. (2009) have attempted to clarify the effects of
hydrogen pressure on the activity and selectivity in the heptane
isomerization reactor based on Pt/WO3-ZrO2 catalyst prepared under
optimum conditions. The optimization in catalyst preparation was
performed by varying the calcination temperature of WO3-ZrO2 and the Pt
content. It has been found that the cracking rate was markedly suppressed
by a high hydrogen pressure. Thereby, a high selectivity of 94% at a
conversion of 80% under a hydrogen pressure of 1.55 MPa may obtained. It
is suggested that the hydride ion species on the surface originating from
14
hydrogen molecules play a key role in the selective formation of branched

heptane.
Aboul-Gheit et al. (2014) have prepared two groups of modified
Sulfated Zirconia catalysts. The first group was modified by four different
concentrations of Pt metal loading (0.15, 0.30, 0.45 and 0.60 wt%),
whereas the second group contained Pt–Re combinations on Sulfated
Zirconia. The catalytic activity of the catalysts was examined for the
hydroisomerization of n-pentane to iso-pentane through a fixed bed reactor.
The catalytic activity was found to increase with increasing Pt
concentration in the monometallic catalysts. The combination of Re ion
with Pt on SZ results in a significant changes in the characters and
activities of the catalysts. 0.45 wt% Pt and 0.15 wt% Re/Sulfated Zirconia
catalyst exhibited the highest selective compared to other metal ratios
investigated.
Chuzlov et al. (2015) theoretically studied the effect of feed stock
composition, temperature, feed stock rate and through fixed bed reactor
with platinum oxide catalyst. They found that:
- The predicting calculations of the feedstock composition influence
on the isomerate quality showed that octane rating can vary by 2-2.5
points depending on the feed composition.
- The increase in the isomerization reactor temperature results in an
equilibrium displacement towards the hydrocracking side reactions
and reduces the yield of isomerate.
- The increase in feedstock charging reduces the feed contact time
with catalyst: the increase in feedstock charging for every 5000
tons / h results in isomerate RON reduction by 0.43 - 0.5 points
depending on the feedstock composition.
15
- The transition from once-through isomerization to scheme with

DIP and DIH technology will increase the isomerate octane
number by 10-12 points depending on the feedstock composition.
2.7 Catalyst Used in the Isomerization Process

The catalyst used for isomerization reactions is a combination of
Lewis and Bronsted acid sites, which promote of protonation activity that
are necessary for the proceed of isomerization reactions. Isomerization
catalysts should also be able to hydrogenolysis, which not only aid in the
protonation step, but also avail to saturate intermediate olefin and aromatic
hydrocarbons and to aid in the opening of cyclo-paraffins rings. platinum
metal is provided this function, also gives stabile activity to isomerization
catalysts and it is loaded to the support at varies percentages (0.3-0.4 wt%)
(Parkash, 2003).
There are three systems of different isomerization catalyst between their
activity and operating conditions and sensitivity to contaminate as shown in
Tables (2.1) and (2.2).
Table (2.1): Comparison among the catalysts type (Yasakova et al., 2010)
Parameter Pt/Zeolite Pt/Al2O3 Pt/ZrO2-SO4
Temperature, °С 244-280 120-180 120-190
Pressure, МPа 1.5-3 2-4 2.5-3.2
LHSV, h-1 1-2 1.5-2 2.5-3.5
Mole ratio Н2:СН (3-4):1 (0.3-0.5):1 2:1
Chlorine compound
Absent Is necessary Absent
Injection
Fire- heater Is necessary Absent Absent
Feed drying Absent Is necessary Absent
Compressor Is necessary Absent Is necessary
RON (once through) 78-80 83-86 81-83
16
Table (2.2): Maximum allowable Contaminant Levels

In the feed (Yasakova et al., 2010)
Allowable Contaminant Levels, ppm
Impurities
Zeolite Alumina Sulfated Zirconia
Water 50-200 0.1 20
Sulfur 50-100 0.1-0.5 1-5
Nitrogen 1 0.1 1
2.7.1 Chlorided-Alumina Catalysts

In 1950s, Platinum impregnated on Chlorided-alumina catalysts was
first used, it has the highest activity. Its high activity means that it operates
at the lowest allowable temperatures (120–180)ºC, so it achieves the
highest RON and yield. These non-regenerable catalysts are deactivated by
water and other oxygenate compounds. The units of this process operated
with Chlorided-alumina catalysts need a continuous chloride promoter
injection as well as a make-up gas drier to remove the oxygenated
components. Also scrubber of caustic is required to neutralize the HCl
formed in the reactors (Parakash, 2003; Yasakova et al., 2010).
2.7.2 Zeolitic Catalysts

Platinum impregnated on Zeolitic catalysts system type operates at the
highest temperatures (230-280 ºC) and the product RON and the yield is
thus the lowest due to their lowest activity. Zeolitic catalysts are
regenerable and having the highest relatively tolerance for contaminant
(oxygenated components and sulfur). There is no chloride promoter
required during such operation. Fired heater is required due to their high
operating temperature (Domergue and Watripont, 2005).
17
2.7.3 Sulfated Zirconia

Platinum-impregnate on sulfated zirconia system has an activity
advantage above the zeolitic catalyst activity. Product RON and yield for
these catalysts are higher than those for zeolitic catalysts and lower than of
Chlorided-alumina catalysts as shown in Table (2.1). Their oxygenated
components and sulfur tolerance are higher than Chlorided-alumina
tolerance and lower than those with zeolitic-based catalysts and there is no
promoter required. Comparable to procedure used for zeolitic catalysts,
these catalysts are fully regenerable by using a simple oxidation procedure
2.8 Catalyst Contaminants

The isomerization unit feed is dried and hydro-treated prior to contact
with the isomerization catalyst. These operations eliminate or reduce to an
acceptable level the contaminants naturally present in the feedstock.
However, it is possible that upstream unit upsets or disoperation could lead
to a contaminant breakthrough. The following discusses their impact on the
process. Table (2.2) shows the maximum allowable limit of impurities in
feedstock (Domergue and Watripont, 2005).
2.8.1 Sulfur
The presence of sulfur in the feed or make-up hydrogen will
immediately decrease the activity of the catalyst. Sulfur reacts with the
platinum to form platinum sulfide leading to reduce the metallic function of
the catalyst used and affecting the hydrogen transfer mechanism. Such
behavior decreases in activity of the catalyst is temporary and recovery is
normally rapid when the sulfur is removed by hydro-treated process.
However, an increase in reactor temperature and a higher make-up
18
hydrogen rate will assist in purging the sulfur from the catalyst more
rapidly (Parakash, 2003; Yasakova et al., 2010).
2.8.2 Water / Oxygenates

The deactivation resulting from water or other oxygenates
breakthrough is permanent. The oxygenated compounds react chemically
with the acidic sites of the catalyst. However, zeolite (IP-632) catalyst is
able to overcome the presence of the water (up to 200-300 ppm as peak
figure) (Yasakova et al., 2010).
2.8.3 Nitrogen Compounds

This refers to organic nitrogen or ammonia, not to molecular nitrogen
N2. Nitrogen compounds react to form ammonia which in turn reacts with
the acidic sites of the catalyst (Parkash, 2003).
2.9 Operating Conditions of Isomerization Process

The main operating conditions affecting the isomerization reaction are
as follow:
Inlet temperature, pressure, LHSV and H2/HC mole ratio.
The effect of temperature has explained in the section of reaction
thermodynamic. The effect of pressure, hydrogen ratio and LHSV is
presented below:
2.9.1 Temperature
Temperature is the most important variable that effect the RON and
yield of isomerizate. Decreasing the temperature increases the
isomerization reaction rate and decrease the cracking reaction rate. On the
other hand, decreasing the temperature cause decreasing of the catalyst
activity. So it is necessary to find the optimal inlet reactor temperature that
19
gives the maximum RON and isomerizate yield that differs with different
of catalyst and feed compositions
2.9.2 Pressure
Pressure has a weak indirect effect on the research octane number
(RON) of isomerizate, but it has a high effect on the yield of isomerizate
where increasing of pressure leads to increase the hydrocracking rate due to
increase the hydrogen partial pressure. On the other hand, pressure should
be high enough to prevent carbonization of the catalyst (Busto et al.,
2008).
2.9.3 Liquid Hourly Space Velocity

The liquid hourly space velocity (LHSV) is defined as the ratio of the
volumetric flow rate (hourly) of the liquid feeds to the catalyst volume.
LHSV is set through the design stage of any isomerization plant and
reflecting the compromise between the overall catalyst cost and the
residence time. The decrease of LHSV has a positive effect on the
conversion of normal paraffins due to the equilibrium behavior of the
isomerization reactions. On the other hand the decrease in LHSV leads to
decrease the yield of the isomerizate owning to the continuity of
hydrocracking reactions (Said et al., 2014; Hayati et al., 2015).
2.9.4 Hydrogen to Hydrocarbon Mole Ratio

The hydrogen to hydrocarbon mole ratio represents the ratio of the
total moles of hydrogen inter into the reactor to the moles of the feedstock.
This variable has a great importance, where at low mole ratio, rapid
deactivation of catalyst is noticed and a high mole ratio leads to high
hydrocracking rate. For Zeolite catalyst, this ratio is taken within the range
of 3-4 (Said et al., 2014; Hayati et al., 2015).
21
2.10 Modeling and Estimation of Isomerization Kinetic

Parameters
Mathematical modelling of industrial catalytic refining processes is an
important direction for technology improvement, as well as for the
preparation of highly qualified specialists. The problem of aggregation in
the kinetic description of multicomponent catalytic reactions is solved in
many studies. These studies have greatly contributed to the improvement of
the method of mathematical modelling of catalytic isomerization of light
naphtha, as one of the most common and high-tech industrial process.
Ono (2003) described the mechanism of the isomerization reactions
for each catalytic system in fixed bed reactor. Also, he discussed the
development of the mathematical modeling and quantum mechanical
computation on paraffins activation and their processing over zeolites
catalyst.
Tailleur and Platin (2008) studied the mechanism of light naphtha
isomerization based on new catalyst type (PtGaZr/SiO 2) using apparent
kinetics model to predict the isomer yields in a gas-phase radial reactor.
They discussed the effect of catalysts surface composition on the chemical
reactions mechanism. The highest temperature (480 K) and lowest LHSV
(1 hr-1) have given the highest conversion of pentane (58%) and hexane
(78%).
Barcia et al. (2010) studied the experimental and modeling of the
vapor-phase adsorption of C5-C6 paraffin fractions in a fixed bed of zeolite
beta and their effect on the RON of isomerizate. At the optimum
temperature of 583 K, an enriched high-octane molecule fraction of 2,2-
DMB, i-C5, and 2,3-DMB are selectively separated from the low-octane
equimolar C5-C6 isomerate feed. For the case of feed mixtures with the
typical composition of the hydroisomerization reactor product of the total
isomerization process, the enriched fraction contains low research octane
21
number (RON), which decreases the octane quality of the product obtained.
However, the use of a layered bed with zeolite 5A and zeolite beta can
displace the n-C5 from the enriched fraction, resulting in a maximum
octane number of about 92.5 points. They used Aspen Adsim to simulate
the dynamic behavior of the C5-C6 fraction in a non-isothermal and non-
adiabatic bed, and they got a good description of the set of experimental
data.
Chekantsev et al. (2014) provided a new universal mathematical
model of light alkanes isomerization process valid for different raw
materials composition and catalyst systems applied for industrial
isomerization units. The formalized reaction scheme components (having
more than seven carbon atoms) are considered as individual hydrocarbons,
because their reactivity and octane numbers differ a lot. Hydrocarbons have
more than seven carbon atoms are aggregated because usually just a trace
amount of these compounds can be found in the feed. The industrial
isomerization reactor is considered as an ideal plug flow reactor. They got
an absolute error between the experimental and predicted results about 5%.
Chuzlov et al. (2014) have proposed a method of intensification of
the combined fractionation and isomerization processes of pentane-hexane
fraction with the aim to improve the service durability of the catalyst. The
developed complex mathematical model takes into account the influence of
the feedstock composition, allows for assessment of the catalyst current
activity and it is also a powerful optimization tool. According to the survey
results, optimizing the feedstock composition will increase the octane
number of the isomerate at 1.6-2.2 points.
Hayati et al. (2015) suggested a new mathematical model for
isomerization processes of pentane and hexane fraction. Their work aimed
to improve the product RON of the isomerization unit and has taken into
account the effect of the feedstock composition. They also showed that the
22
isomerizate RON vary within 2-2.2 points due to feed stock composition.
They got maximum RON equal to 79.5 at 513 K, 1.6 mol H/HC and 1.2 hr -
1
.
2.11 Isomerization Processes Technologies
In 1970s the variants of hydrogenation of the benzene, contained in
the reformate, proceeding without the decrease of product octane number
have been offered. However, decreasing of the total aromatics content, the
dilution of reformate with high-octane nonaromatic components is
required. This situation is complicated by refusal from tetraethyl lead
(TEL) and deficit of butane-butylene fraction (because of the lack of FCC
duty), which is used for the production of high-octane alkylate in the world
practice. Thereby, the development of isomerization process is one of the
effective methods for solution of this problem. It allows the producing of
commercial gasoline which corresponds to the current and perspective
requirements to the fuels and provides necessary flexibility of processing
There are several isomerization processes, classified by the catalyst

system and the product separation system, to produce isomerate and the
choice of process that depends mainly on the required octane number. One-
through process without any recycle or by-pass can be used with minimum
investment in realization of isomerization process giving minimum RON.
The most common types of basic once through process are zeolitic process
(will explain in details in the next chapter), Penex process and Par-Isom
process.
Penex process; which has served as the primary isomerization

technology for upgrading C5/C6 light straight-run naphtha feeds since
Universal Oil Products (UOP) introduced it in 1958. This process has a
wide range of operating configurations for optimum design flexibility and
23
feedstock processing capabilities. The Penex process is a fixed-bed

procedure that uses high activity chloride-promoted catalysts to isomerize
C5/C6 paraffins to higher octane branched components. The reaction is
conducted in the presence of a minor amount of hydrogen. Even though the
chloride is converted to hydrogen chloride, carbon steel construction is
used successfully because of the dry environment. Typically, two reactors
in series are used to achieve high on-stream efficiency (as shown in Figure
(2.2)). The catalyst can be replaced in one reactor while operation
continues in the other. One characteristic of the process is that catalyst
deactivation begins at the inlet of the first reactor and proceeds slowly as a
rather sharp front downward through the bed. The adverse effect that such
deactivation have on unit on-stream efficiency is avoided by installing two
reactors in series. Each reactor contains 50% of the total required catalyst.
Piping and valving are arranged to permit isolation of the reactor
containing the spent catalyst while the second reactor remains in operation.
After the spent catalyst has been replaced, the relative processing positions
of the two reactors are reversed. During the short time when one reactor is
off-line for catalyst replacement, the second reactor is fully capable of
maintaining continuous operation at design throughput, yield, and
conversion. For typical C5/C6 feeds, equilibrium will limit the product to 83
to 86 RON on a single hydrocarbon pass basis (Graeme et al., 2004;
Yasakova et al., 2010).
Par-Isom process; shown in Figure (2.3) is another scheme developed

by UOP , which operated with a sulfated-zirconia catalyst has the lowest
capital cost of the paraffin isomerization technologies. Because these
catalyst systems are tolerant of contaminants, no special feed pretreatment
is required. Because there is no chloride promoter added to the process,
there is no need for a caustic scrubbing system to remove chloride from the
24
excess gas as it leaves the unit. The process requires only one reactor
because the catalyst is regenerable. The Par-Isom regeneration procedure is
a simple carbon burn and hydrogen reduction. The regeneration can be
performed in situ or ex situ. The Par-Isom unit operates at higher hydrogen
ratios so it requires a recycle compressor and a product separator
(Yasakova et al., 2010; Koncsag et al. 2011).
Off gas
Reactors
H2 Dryer
Make up
Scrubber
Separator
Separator
Steam
Light
Dryer
naphtha
isomreizate
Figure (2.2): Flow diagram of Penex process (Yasakova et al., 2010)
H2 Recycle Compressor
Make up
of H2
Off gas
Separator
Stablization
Light
naphtha
isomreizate
Figure (2.3): Flow diagram of Par-Isom process (Yasakova et al., 2010)
25
To achieve higher octane, UOP and Axens offer several schemes in

which lower octane components are separated and recycled back to the
reactors. These recycle modes of operation can lead to product octane as
high as 93 RON as shown in Table (2.3). The main technologies use to
separate low RON hydrocarbon are (Domergue and Matthews, 2001;
Yasakova et al., 2010):
Table (2.3): The RON of the isomerization process

obtained by different technologies and catalysts
Technology Pt/Zeolite Pt/Al2O3 Pt/ZrO2-SO4
Once through 78-80 83 81-83
DIP 82 84 82-84
DIH 86 88 86-87
DIP and DIH - 90-93 89-90
DIP, DIH and DP - - 91-92
TIP 87-90 - 91-92
Ipsorb 88 90 -
Hexorb 90 93 -
Deisohexanizer (DIH); it is located after the reactor and it is used to

separate and recycle methyl pentanes and normal hexane from the reactor
effluent to the feedstock.
Deisopentanizer (DIP); it is located before the reactor and it is used to
separate iso-pentane from feed stock in order to increase the conversion of
normal pentane.
Depentanizer (DP); it is located after the reactor and it is used to
separate and recycle normal pentane from the reactor effluent to the
feedstock.
All of the above technologies use the distillation column for
separation process and they can be used separately or simultaneously. The
total conversion for normal paraffins can be realized by using set of
distillation column (DIP, DIH and DP).
26
Also, the adsorption on molecular sieves (in vapor or liquid phase) can
be used for the separation of normal paraffins. Normal paraffins is
separated and recycled based on pores with definite size capability to
selectively adsorb the normal paraffins molecules. Then the normal
paraffins desorbed from pores will be recycled to the feed stock. such
cycles of adsorption and desorption are repeated or pseudo-continuously is
used. There are other schemes of the isomerization process use iso-sieve
techniques such Ipsorb, Hexorb and total isomerization processes.
Graeme et al. (2004) and Koncsag et al. (2011) have introduced the
review of existing isomerization processes technologies and their
performance, so a brief description of operating condition, catalyst, and
performance of isomerization unit at some refineries can be provided in
Table (2.4) depending on this review.
Table (2.4): Performance of operating isomerization units at different

refinery
Operating RON of Scheme
Refinery conditions company catalyst isomerizate modification
LUKOIL- 160ᵒC, 3.2 MPa UOP Sulfated 86-87 With DIP
zirconia
Nizhegorodne- and 2.5 hr-1
fteorgsintez
Komsomolsky 130 ᵒC, 3 MPa and Axens Pt/Cl Al2O3 86-88 With DIP
2 hr-1
Achinsky 132 ᵒC and 2.9 UOP Pt/Cl Al2O3 86-87 With DIH
MPa
LUKOLL - UOP Pt/Cl Al2O3 89-90 With DIP and
Volgogradnefte- DIH
pererabotka
Saratovsky - SIE Pt/zeolite 91-92 With DIP,
DIH and DP
Orsknefteor-Gsintez - SIE Pt/zeolite 80-82 One-through
Syzransky 240 ᵒC, 2.7 MPa Axens Pt/zeolite 89-90 With DIP and
and 3 hr-1 DIH
27
2.12 Pinch Technique

Also referred to as pinch technology, process integration and heat
integration, pinch analysis is a methodology, originally developed by
Linnhoff (1979), to minimize the energy consumption of industrial
processes. In broad terms, this approach follows two basic steps. The first
one is energy targeting, where the process energy flows are represented in
the so-called composite curves, of which Figure (2.4) act as an example.
These are graphical representations of two key thermodynamic variables:
temperature (i.e. the quality of the energy) and enthalpy (i.e. the quantity of
energy). The hot composite curve (blue line) is the combination of all the
streams that need to release heat, while the cold composite curve (red line)
groups all the process streams that require to pick up heat. With both the
heat sources and the heat sinks in the same plot, it is simple to assess the
maximum extent of energy that can be transferred from one to the other.
The remaining heat has to be provided or removed via utilities such as
steam or cooling water. In other words, for the given driving forces, or
temperature differences, thermodynamically feasible energy targets )i.e.
minimum utility requirements) are determined. The second step is the
design of the energy system and starts with the notion that the point of
closest temperature approach between the hot and the cold composite
curves, so-called pinch point, represents the area where the driving forces
are smallest in the process and thus the design is most constrained. By
starting the design of the energy recovery system there, and following
certain design rules in Linnhoff and Hindmarsh (1983), the pinch
methodology ensures that the identified energy targets can be achieved in
practice.
28
300
250
200
Pinch point
T, C
150
100
50
0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200
Enthalpy, KW
Figure (2.4): Composite curves for the traditional thermal hydrolysis

processes (Linnhoff and Hindmarsh, 1983)
29
Chapter Three Mathematical Modeling
CHAPTER THREE
MATHEMATICAL MODELING
OF AN INDUSTRIAL
ISOMERIZATION REACTOR
Chapter Three
Mathematical Modeling of an Industrial
3.1 Introduction
Due to the complicated physical-chemical phenomena occurs in
packed bed reactors, their perfect description is not a simple task. The
mathematical model of more detailing leads to more parameters contained
and causing more lack of accurate through the parameters estimations. The
complexity of the actual process happens through packed bed reactor not
only leads to doubts and difficulties with their mathematical model
description, but also to issue in the numerical treatments of the equations.
Therefore, the efficient software pack has been developed for modeling
description, the best model is chosen on the base of the properties of the
particular system under study. The system features is concerned in and the
parameters availability included in the model in addition to the probability
of effective numerical handling of the model equations (Iordanidi, 2002).
In this chapter, an adequate mathematical model for industrial packed

bed reactor of Baiji north refinery will be described intensively. Through
this model, the optimal values of all kinetic parameters will be estimated
and discussed here.
31
3.2 Mathematical Model of Naphtha Isomerization

Reactor
The use of continuum pseudo-homogeneous model of one
dimensional, which gives axial profile of average radial temperature and
concentration through the catalyst bed, is appropriate with the goal of this
study (Chekantsev et al., 2014).
Figure (3.1) shows the required dates, available tools and the
assumptions used in modeling (simulation and optimization) process for
catalytic naphtha isomerization.
3.3 Actual Data

All the experimental data including the feed stock and product
composition, operating conditions and catalyst specifications were taken
from the actual isomerization unit at Baiji north refinery.
Isomerization unit of Baiji north refinery operates by once through
mode by using zeolitic catalyst system. As shown in Figure (3.2) (Chen et
al., 1989), light naphtha from hydrotreating process is mixed with
compressed hydrogen before entering heat exchanger one (E-201), which
rises the temperature of the feed to 190ºC. The furnace F-201 provides the
proper level of temperature to the reactor R-201 inlet.
31
Operation Mode: Light Kinetic Data:

naphtha
H2
1-Co-current 1- Parameters
2-adipatic 2- Models of reaction
Reaction type:
Required Data:
1- two-phases
1- hydrocarbons and
2- Exothermic hydrogen components
density.
2- critical properties of each

component.
Processing and reactor type:
3- Diffusivities.
1- Steady-state
4-pure research octane
2- fixed bed reactor
number and molecular weight
3- Continuous .
Operation Variable: Tools Variables:

1- Temperature. 1- Mass & energy balance
equations.
2- Pressure.
2- Numerical Tools (gPROMS,
3-LHSV.
general process modeling
4- H2/HC mole rario system.
Isomerizate, gases
and H2
Figure (3.1): Available tools and required dates for light naphtha
isomerization modeling, simulation and optimization process
The isomerisation chemical reactions take place into the reactor R-

201 ( cylindrical with a height of 13.840 m and diameter of 2.9 m) loaded
with a bed of zeolite catalyst. The reactor effluent is partially condensed
through E-201, the air condenser A-201 and the trim cooler E-202 before
feeding the high pressure separator drum D-201 and the overhead stream
which is hydrogen is compressed and recycled to the reactor. The D-202
32
liquid bottom is heated through heat exchanger E-202 to provide inlet

column C-201 temperature. The head stream is partially condensed by
condenser E-204 then entering to the separator drum D-202. The
downstream of C-201 is cooled through E-202 and then by E-205 to
produce stabilized isomerizate.
H2
Make up
H2 recycle H 2O
M 201 E204
Off gas
A 201
D 201
D 202
R201 C Stabilizer
C E Heat exchanger
201 D Separator drum
P 202 P Pump
F 201 R Reactor
M Compressor
Light E E A Air cooler
naphtha P 201 202 203 F Furnace
E 201
E 205 isomreizate
Figure (3.2): Once through isomerization process flowsheet
3.4 The Model Equations of Isomerization Reactor

The model equations of isomerization reactor, are presented by a
system of equations of material balance and heat balance for each
component as shown below:
3.4.1 Mass Balance Equation Of Compounds

Equation (3.1) below is an ordinary differential equation used to
describe the concentration of every component through the catalyst bed.
However, solving this differential equation gives the concentration profile
of components with unit volume of catalyst bed (Chekantsev et al., 2014):
∑ … (3.1)
33
Where:
j: Reaction number, (-)
i: hydrocarbon components number, (-)
G: Raw material flow rate, m3/hr-1
Ci: Concentration of ith component, mol/m3
V: Volume of catalyst bed, m3
a: Catalyst activity, (-)
rj: Jth reaction rate, mol/m3hr-1
The initial conditions of this equation are:
At V=0, Ci = Ci,in
Ci,in: Initial (inlet) concentration of ith component, mol/m3
3.4.2 Heat Balance Equation

Solving the ordinary differential Equation (3.2) gives the temperature
profile over the unit volume of the catalyst bed (Chekantsev et al., 2014):
∑ … (3.2)
Where:
j: reaction number, (-)
T: Temperature, K
: Density of mixture, kg/m3
: Heat capacity of mixture, J/(kg. k)
Qj: Jth reaction heat, J/mol
The initial conditions can be written as:
34
At V=0, T=Tin
Tin: Initial (inlet) temperature, K
3.4.3 Reaction Rate Equations

According to the chemical reaction, power rate law non-elementary
reaction rate at the set temperature is proportional to the concentration of
reacting substances based on the order of n, m and o as shown below
(Chekantsev et al., 2014):
… (3.3)
… (3.4)
… (3.5)
Equation (3.3) represents the isomerization reaction rate, equation (3.4)

represents the hydrogenation reaction rate and equation (3.5) represents the
dehydrogenation reaction rate.
Where:
CH2: Hydrogen concentration, mol/m3
n: Order of hydrocarbons concentration, (-)
m: Order of hydrocarbons concentration in dehydrogenation reaction, (-)
O: Order of hydrocarbons concentration in hydrogenation reaction, (-)
: Effectiveness factor, (-)
kj: Apparent reaction rate constant,
Reaction rate constant ( can be described by Arrhenius equation as

follow:
35
( ) … (3.6)
Where:
A: Pre-exponential factor,
E: Activation energy, j/mol.K
R: Gas constant, J/mol.K
The concentration of each component can be described by real gas law

taken into account the compressibility factor:
… (3.7)
Where:
y: Mole fraction, (-)
P: Pressure,
Z: Compressibility factor, (-)
The commerciality factor for every species is given by the following

equation (Ahmed, 1989):
⁄
( ⁄ )
… (3.8)
⁄ ( )
( ⁄ )
Where:
Tc: Critical temperature of species i, K
Pc: Critical pressure of species i,
36
3.4.4 Reactions Scheme of Isomerization Process

Every component in the light naphtha mixture undergoes both
isomerization and hydrocracking reaction except cyclic hydrocarbons that
only undergo the hydrocracking reactions.
Based on the operating data of different isomerization process,

Chekantsev et al. (2014) have proposed a scheme of the isomerization
reactions process presented in Figure (3.3) which is employed in the
modeling of naphtha isomerization process according to the chemical
reaction equations presented in Table (3.1).
B MCP
3-MP
CH n-C6 2-MP 2,3-DMB 2,2-DMB
n-C4 Gas i-C7
i-C4 i-C5 n-C5 n-C7
c-C5
Figure (3.3): Scheme of formalized reaction for isomerization process

(Chekantsev et al., 2014)
37
Table (3.1): Chemical reactions equations for isomerization processes

(Chekantsev et al., 2014)
Reaction NO. Chemical reaction Reaction NO. Chemical reaction
(j) equations (j) equations
1 → 19 →
2 → 20 →
3 → 21 →
4 → 22 →
5 → 23 →
6 → 24 →
7 → 25 →
8 → 26 →
9 → 27 →
10 → 28 →
11 → 29 →
12 → 30 →
13 → 31 →
14 → 32 →
15 → 33 →
16 → 34 →
17 → 35 →
18 → 36 →
38
3.4.5 Catalyst Activity

The dependence of catalyst activity on time has been taken into
account where that can be represented by the following equation
(Chekantsev et al., 2014):
… (3.9)
Where:
: The rate constant of jth reaction on the fresh catalyst.
The rate constant of jth reaction on the catalyst at present time.
3.4.6 Flow Rate of Raw Material

The feed stock to the re‫ اكتب المعادلة هنا‬actor contains hydrogen gas and
light naphtha vapor that can be calculated as follow:
⁄ ⁄ … (3.10)
Where:
Wln ,WH2: Weight flow rate of light naphtha and hydrogen respectively,
kg/hr
Density of light naphtha vapor and hydrogen gas respectively,

kg/m3
… (3.11)
Where:
Qln: Liquid Flow rate of light naphtha at 20 , m3/hr
Specific gravity of light naphtha at 20 , (-)
39
Density of water at 20 , kg/m3
… (3.12)
LHSV: Liquid hourly space velocity, hr-1
V: Volume of catalyst, m3
… (3.13)
mr: : Mole ratio of hydrogen to light naphtha, (-)
Mln: Number of mole of light naphtha, kmol
MWH2: Molecular weight hydrogen, kg/kmol
… (3.14)
MWln: Molecular weight of light naphtha, kg/kmol
∑ … (3.15)
MWi: Molecular weight of ith hydrocarbon component, kg/kmol
3.4.7 Effectiveness Factor

The effectiveness factor of reactions represents the ratio of the
reaction rate into the particle to the rate of reaction at the surface of the
particle as submit by Bischoff, 1965 and can be estimated as a function of
Thiele Modulus valid for cylindrical particle as follow:
= … (3.16)
Where:
: Thiel Modulus, (-)
41
For -order reaction, the general Thiele Modulus ( ) can be evaluated

using the following relationship (Froment and Bischoff, 1979):
= √( )( ) … (3.17)
Vp: Total geometric volume of catalyst particle, m3
Sp: Total geometric surface area of catalyst, m2
: Particle density, kg/m3
: Effective diffusivity, m2/hr
The Particle density ( , is estimated using the following relation

(Tarhan, 1983):
= ... (3.18)
Catalyst density, ⁄
The Bed porosity ( ) of the catalyst can be estimated for undiluted

sphere packed catalyst from the following equation (Froment and
Bischoff, 1979):
= 0.38 0.073 ( ) ... (3.19)
Where:
dpe: Equivalent particle diameter,
dt: Tube diameter,
41
Equivalent diameter of particle (dpe) can be defined as the diameter of

the sphere having the same external volume as the real catalyst particle.
Such characteristic depends on the shape and the size of the particle. For
cylindrical particle, it can be estimated from the following equation can be
used for this purpose (3.22) (Cooper et al., 1986; Jarullah, 2012):
( ⁄ )
… (3.20)
Shape factor, (-)
… (3.21)
For cylindrical shape, the external volume (Vp) and the surface area
(Sp) of particle is calculated as shown below:
… (3.22)
… (3.23)
Where:
dp: Particle diameter, m
L: Particle length, m
The effective diffusivity of every component ( ), can be estimated

from (Mohammed et al., 2016) taking into account the tortuosity of the
pore network inside the catalyst particle considering the porosity in the
modeling.
= ... (3.24)
42
: Catalyst particle porosity, (-)
: Tortuosity factor, (-)
Knudsen diffusivity coefficient of species i in the gas phase, m2/hr
: Molecular diffusivity coefficient of species i in the gas phase, m2/hr
Catalyst particle porosity ( is calculated by using the equation below,

which depends on the particle density and pore volume:
= ... (3.25)
Vg: Total pore volume, m3/kg
The tortuosity factor ) can be estimated by the following equation:
… (3.26)
Knudsen diffusivity represents the diffusivity of components into

pores of the catalyst for each component, which can be calculated utilized
the following equation (Mohammed et al., 2016):
= 349200 √ ... (3.27)
Where:
Mean pore radius, m
Molecular weight of species i, kmol/kg
The mean pore radius can be calculated by the following equation:
... (3.28)
43
: Specific surface area of particle, m2/kg
The molecular diffusivity coefficient of species i in the gas phase can

be calculated from equation (3.31) depending on the binary diffusion
coefficient of component i through the other components (Wilke and
Chang, 1955):
∑ ... (3.29)
Where:
Binary diffusion coefficient of ith component through the other

components, m2/hr
The binary diffusion coefficient can be calculated from the following

equation (Anderson, 1967; Rackett, 1970):
188.2458* √ ( ) ... (3.30)
Average collision diameter, m
Collision integral for diffusion, (-)
The average collision diameter is calculated from the following equation:
... (3.31)
Collision diameter of ith and kth components respectively, (-)
The collision diameter of each component is calculated by the equation

bellow (Bird et al., 1954):
... (3.32)
44
Liquid molar volume at normal boiling temperature, m3/kmol
The molar volume can be calculated from the following equation:
... (3.33)
Liquid density of component i at normal boiling point, kg/m3
The diffusion collision integral for gases molecules can be calculated using
the equation below (Neufeld et al., 1972):
... (3.34)
Where:
Dimensionless temperature, (-)
The dimensionless temperature is calculated by equation (3.37) below:
⁄
... (3.35)
Where:
CB: Boltzmann constant, (-)
: Characteristic (minimum) energy, K
The energy ratio is calculated according the following equation (Bird et

al., 1954):
⁄ ... (3.36)
√ ... (3.37)
Average critical temperature, K
45
3.4.8 Density of Mixture

The density of mixture represents the light naphtha vapor density and
hydrogen gas density as follow:
… (3.38)
Where:
: Density of mixture, kg/m3
: Density of light naphtha vapor, kg/m3
Density of hydrogen gas, kg/m3
WtH2: Weight fraction of hydrogen, (-)
Wtln: Weight fraction of light naphtha, (-)
The density of light naphtha is estimated as a function of pure components

density and their weight fractions as follow:
∑ … (3.39)
Density of i hydrocarbon component vapor, kg/m3
Wti: Weight fraction of i hydrocarbon component, (-)
The density of hydrogen and of each hydrocarbon component in the

gas phase can be estimated as a function of temperature and pressure based
on ideal gas equation with taking into account the gas compressibility
factor where the gas at these condition has trend toward the reality state.
The equation can be written as shows:
... (3.40)
P: Pressure, pa
46
T:Temperature, K
Zi: The gas compressibility factor, (-)
Gas constant, J/mol. K

MWi: Molecular weight of ith component, kg/kmol
The density of the components at normal boiling point can be
calculated from the following equation (Rackett, 1970):
= ⁄ ... (3.41)
: The density at boiling point, kg/m3
Zc: Critical compressibility factor, (-)
Tr: Reduced temperature, (-)
Pc: Critical pressure, pa
Tc: Critical temperature, K
= ... (3.42)
Tc, Pc, Zc and MWi are taken from (Perry and Green, 1999).
3.4.9 Heat of Reaction Calculation

The heat of reaction as a function of temperature is calculated from
the following equation:
∫ ... (3.43)
Qj: Heat of jth reaction, j/mol
Standard heat of jth reaction, j/mol
47
Heat capacity of jth reaction, j/mol.K
∑ ∑ ... (3.44)
: Standard heat of formation of reaction product components, j/mol
: Standard heat of formation of reaction reactant components, ⁄
∑ ∑ ... (3.45)
Heat capacity of reaction product components, J/mol.K
Heat capacity of reaction reactant components, J/mol.K
The heat capacity of every component is calculated from the following

equation:
... (3.46)
A, B, C and D: constants are given in (Perry and Green, 1999).
The heat capacity of mixture can be calculated from following equation:
=∑ ... (3.47)
= heat capacity of mixture, J/mol.K
3.4.10 Calculation of Octane Number Model

The model of this study is taken in to account physicochemical nature
of mixing process and non-additive properties of gasoline. Thus, the model
of mixing octane number takes into account the deviation from additively
that can be written as (Gyngazova et al., 2011):
∑ ... (3.48)
∑ ∑ ... (3.49)
48
( ) ... (3.50)
Where:
Research octane number, (-)
ith pure component research octane number, (-)
Mole fraction, (-)
β is a total deviation of hydrocarbons octane number from additively, (-)
Parameters showing the tendency of ith molecule to intermolecular

interaction with jth molecule, (-)
: Dipole moment of molecule i, Debye
Maximum possible dipole moment of the hydrocarbons mixture,

Debye
Kinetic coefficients defining the intensity of intermolecular

interactions from dipole moment, (-)
3.4.11 Calculation of Isomerizate Yield

… (3.51)
Where:
Yield: isomerizate yield, (-)
Miso: moles of isomerizate, mole
Mln: moles of naphtha feed, mole
3.5 Estimation of Kinetic Parameters of The Model

Accurate estimations of some physiochemical processes described by
the model are very necessary to get an accurate behavior of the system.
Accurate unknown parameters estimations needs to difficult solutions of
many equations of both ordinary differential equations and simple
49
equations. Developing of new technologies and optimization of accurate

parameters calculations have increased owning to the developing of kinetic
models. So, the parameter estimation is a basic step in the models
development. This step can be achieved depending on experimental or
industrial data. The estimated values of kinetic parameters should
appropriate with minimum errors between the mathematical models data
predicted and industrial data, so the predicted values from the model have
to match the industrial data as closely as possible (Poyton et al., 2006).
In order to obtain the best kinetic parameters values in this study, a

non-linear approach is used utilizing the same data, operating condition
and weight fraction analysis of the hydrocarbons and hydrogen
components of isomerization unit at Baiji north refinery.
Non-linear regression is simultaneously used for determining the

reaction orders (order of hydrocarbons in every reaction (n), order of
hydrogen in cracking reactions (m), order of hydrogen in hydrogenation
reactions (o)), activation energies of ( ), pre-exponential constant of each
reaction ( ) and Kinetic coefficient of intermolecular interactions
intensity (γ & α). All these parameters are simultaneously calculated in this
approach by using optimization technique within gPROMS software. In
this approach, the activation energy and per-exponential factor are
estimated directly via Arrhenius equation.
The following objective function is used based upon the minimization
of the sum of squared errors (SSE) between the experimental weight
fraction of hydrocarbons and hydrogen components ( and predicted
( For parameter estimation, the objective function (OBJ) is given

below:
OBJ= ∑ ∑ ... (3.52)
51
– ... (3.53)
... (3.54)
... (3.55)
Where:
Error function of ith component, (-)
Error function of temperature, (-)
Error function of research octane number, (-)
The error functions between experimental and predicted values of T,

RON and have been taken as a constraint function. Figure (3.4)
presents the procedure of kinetic parameter estimation.
51
Start
Read T, P, LHSV
and mr
Calculate erri, errT,

and errRON
Calculate OBJ
Calculate n, m, o,kj,
Aj, α and γ that
minimize the OBJ
No Are erri, errT

and errRON
≤0.1?
Yes
Read n, m, o, kj, Aj,

α and γ
End
Figure (3.4): Algorithm of kinetic parameters estimation
52
3.6 Optimization Problems Formulations For Parameters

Estimation of Naphtha Isomerization Process
The optimization problem formulation of naphtha isomerization process
can be described as follows:
Give The reactor configuration, the initial hydrocarbons and

hydrogen concentration, the catalyst, reaction temperature
and pressure, liquid hourly space velocity and flow rate
Obtain The reaction orders of hydrocarbon (n), hydrogen (m, o), pre-
exponential constant ( ), activation energy ( ) of
each reaction and also kinetic coefficients ( )
So as to The sum of square errors (SSE)
minimize
Subjected to Constraints of process and linear bounds upon all
optimization variables in this process
Mathematically, the problem can be represents as shown below:
Min OBJ
s.t. F (v, (v), , u (v), z) = 0, [ , ] [model, equality constraint]
[Inequality constraints]
53
Where:
f(v, x(v), , u(v), v) = 0 : Represents the model of process which

presented in the previous sections.
V: the reactor bed volume.
U (v): Is the decision variables (n, m, , ).
X (v): Gives the set of all algebraic and differential variables ( , T, ,

….).
: Represents the differential variables derivative with respect to
volume of the reactor bed such as ( , , …).
V: volume (independent constants parameters) or variables of design such

as (R …).
[ , ], is the volume interval of interest.
The function f is supposed to be continuously differentiable with regard to

whole its arguments.
The solution method of optimization by gPROMS is completed by two

steps which can be showed as follows:
 Firstly, the simulation is performed to make all the equality

constraints which described through the function f converge and also
in order to make the inequality constraints satisfy.
54
 Secondly, the optimization is performed (updates the values of the

kinetic parameters).
The optimization problem is completed as a Non-Linear Programming

(NLP) issue and it is solved by using a Consecutive Quadratic
Programming (SQP) method within gPROMS computational technique.
All these steps of solution and presentation equations into gPROMS had
been explained in Appendix (A).
3.7 Summary
 A mathematical modeling has been characterized by a collection of
differential and ordinary equations which are used to develop a
catalytic isomerization of light naphtha process.
 The systems of two phase and fixed bed were used in this model
including light naphtha hydrogen (gas) and catalyst (solid).
 The mathematical model presented in this chapter have taken into

considerations the design factors as a function of operating conditions
which are ignored in the literature.
 Advance optimization technique has applied here to find the best

kinetic parameters of the relevant process with high accuracy
depending on the actual industrial data obtained from Baiji north
refinery.
 gPROMS (general Process Modeling System) programmer used to

solve the ordinary differential equations and algebraic equations.
55
Chapter Four Results and Discussion
CHAPTER FOUR
RESULTS AND
DISCUSSION
Chapter Four
Results and Discussion
4.1 Introduction
This chapter presents a comparison between the mathematical
modeling results and experimental results with showing the influence of
operating conditions (temperature, hydrogen to hydrocarbon mole ratio,
liquid hourly space velocity), on the isomerization of light naphtha. After
getting the accurate kinetic parameters by optimization technique, a
simulation technique for the fixed bed reactor of isomerization process is
applied via gPROMS program. The ranges of operating conditions used in
the optimization process are the same as that used in the actual
isomerization unit at Baiji north refinery. A non-linear approach is used to
get the best kinetic parameters of the model. The influence of different
variables process have also been discussed here and taken into
considerations.
4.2 Kinetic Model

The values of reactor‘s feedstock and product‘s composition and
operating conditions, which are presented in Tables (4.1) and (4.2), were
taken from Baiji north refinery in addition to the feed stock and product‘s
composition.
56
Table (4.1): Inlet and outlet composition (Wt%) of isomerization

reactor through test run days
Test run 1 Test run 2 Test run 3 Average

Hydrocarbon components
inlet outlet inlet outlet inlet outlet input outlet
n-Butane (nC4) 2.821 1.222 4.253 1.970 3.549 1.963 3.479 1.855
n-Pentane( nC5) 23.954 18.267 25.977 18.362 26.59 17.423 25.81 18.39
n-Hexane(nC6) 17.338 7.540 14.320 7.597 15.09 8.169 15.95 7.343
n-Heptane (nC7) 1.221 0.040 2.816 0.059 1.401 0.032 1.314 0.051
i-Butane (iC4) 0.216 0.517 0.353 0.963 0.259 0.735 0.287 0.950
i-pentane (iC5) 17.775 35.013 20.652 35.689 22.00 35.982 20.11 36.07
2,2 Di Methyl Butane 0.622 7.766 0.451 7.356 0.581 7.170 0.548 7.293
(2,2DMB)
2,3 Di Methyl Butane
2.180 3.567 1.472 3.092 1.748 3.029 1.911 3.390
(2,3DMB)
2 Methyl Pentane (2MP) 12.314 12.493 9.311 12.597 9.736 12.978 10.26 12.561
3 Methyl Pentane (3MP) 9.996 9.296 7.294 8.599 7.946 8.243 8.401 8.404
i-heptane (iC7) 3.764 0.412 5.084 0.250 3.483 0.298 3.556 0.273
Cyclo Pentane (CP) 1.529 1.138 1.312 1.369 1.175 1.054 1.174 1.054
Methyl Cyclo Pentane 2.973 1.450 2.574 1.072 3.078 1.144 2.873 1.144
(MCP)
Cyclo Hexane (CH) 1.137 0.436 1.270 0.316 1.101 0.353 1.240 0.353
Benzene (C6) 0.496 0.000 0.433 0.000 0.498 0.004 0.470 0.000
Table (4.2): Operating condition of isomerization reactor

through test run days
Liquid hourly Temperature Pressure Hydrogen mole
space velocity (K) (MPa) ratio ( / )
( )
First day 1.489 523.12 2.340 3.324
Second day 1.561 525.72 2.472 3.227
Third day 1.622 526.2 2.430 3.381
average 1.557 524.14 2.414 3.310
57
All physical properties and constant parameters used in the

mathematical modeling to obtain simulation results are given in Tables
(4.3), (4.4) and (4.5). Where the critical properties and molecular weight of
each component were taken from Perry and Green (1999), pure
components research octane number were taken from Chekantsev et al.
(2014) and dipole moment values were taken from Vogel and Mobius
(1988).
Table (4.3): Values of physical properties of light naphtha

components used in the model
Molecular Critical Critical Critical Dipole Research
Components Weight temperature Pressure compressibility Moment octane
(kmol/kg) (k ) ( MPa) Factor, (-) (depy) number
Normal butane 58.123 425.16 3.7963 0.2791 0.127 95
i-butane 58.123 407.85 3.6397 0.2780 0.132 100.2
Normal pentane 72.125 471.10 3.3550 0.2747 0.114 62
i-pentane 72.125 469.70 3.3812 0.2611 0.121 92
Cyclo-pentane 70.135 511.60 4.5057 0.2871 0.241 102.3
n-hexane 86.177 488.71 3.0068 0.2642 0.080 24
2-methyl pentane 86.177 497.50 3.0096 0.2669 0.097 74.4
3-methyl pentane 86.177 504.50 3.1240 0.2732 0.099 75.5
2,3-dimethyl butane 86.177 500.21 3.8163 0.3284 0.121 105
2,2-dimethl butane 86.177 488.71 3.0816 0.2704 0.124 95
Cyclo-hexane 84.162 553.40 4.0710 0.2791 0.320 84
n- heptane 100.25 540.206 2.7358 0.2624 0.0 0
i-heptane 100.25 530.30 2.7397 0.2597 0.0 84
Methyl cyclopentane 84.162 531.70 3.7845 0.2724 0.0 96
Benzene 78.114 562.16 4.8953 0.2713 0.0 120
Hydrogen 2.0160 33.200 1.3000 0.3050 (-) (-)
58
Table (4.4): Catalyst and feedstock properties

parameter symbol unit value
Gas constant R J/ ( . K) 8.314
Catalyst bed length L m 11.24
Catalyst bed diameter m 2.9
Catalyst bulk density ⁄ 741
length of catalyst particle m 3. 5*
Diameter of catalyst particle m 1.8*
Specific volume of particle Vg ⁄ 0.4
Specific surface area of particle Sg ⁄ 450
Specific gravity of naphtha Sp.gr (-) 0.647
API (-) (-) 87.9
Sulfur content (-) ppm 15
Aromatics content (-) mol% 0.49
RON (-) (-) 69
Table (4.5): Standard enthalpies of formation and constants of

heat capacity (Perry and Green, 1999)
Enthalpies of Constants of heat capacity (Cp)

Components
formation, A B C D
n-butane -146760 -3.6260 4.87E-01 -2.58E-04 5.30E-08
i-butane -153700 -9.5250 5.07E-01 -2.73E-04 5.72E-08
n-pentane -77030 -53.625 5.43E-01 -3.03E-04 6.49E-08
i-pentane -182800 -16.634 6.29E-01 -3.48E-04 6.85E-08
Cyclo-pentane -176800 -14.608 6.15E-01 -3.38E-04 6.82E-08
n-hexane -174550 -10.567 6.18E-01 -3.57E-04 8.08E-08
2-methy pentane -172550 -2.3860 5.69E-01 -2.87E-04 5.03E-08
3-methy pentane -166940 -4.4130 5.82E-01 -3.12E-04 6.49E-08
Continued
59
2,3-dimethyl butane -106200 -50.108 6.38E-01 -3.64E-04 8.01E-08
2,2-dimethl -82880 -33.917 4.74E-01 -3.02E-04 7.13E-08

Butane
Cyclo-hexane -187650 -5.1460 6.76E-01 -3.65E-04 7.66E-08
n-Heptane -194100 -39.389 8.64E-01 -6.29E-04 1.84E-07
i-heptane -134180 -1.3900 3.85E-01 -1.85E-04 2.90E-08
Methyl cyclo- -125790 9.4870 3.31E-01 -1.11E-04 -2.82E-09

pentane
Benzene -123300 -54.541 6.11E-01 -2.52E-04 1.32E-08
Hydrogen 0 27.143 9.27E-03 -1.38E-05 7.65E-09
The optimal kinetic parameters of an industrial light naphtha

isomerization model are estimated within gPROMS software. The optimal
values of activation energy ( ) and per-exponential factor ( ) for every
reaction in the process were directly calculated by using non-lineal
approach according to Arrhenius equation. Also, the optimal values of
components concentration orders (o, m & n) and kinetic coefficient of
intermolecular interactions intensity (γ & α) were simultaneously
calculated in this approach. Such parameters are presented in Tables (4.6a)
and (4.6b). These values of the optimal kinetic parameters have been
estimated based on the average compositions given in Table (4.1) and the
average operating conditions given in Table (4.2).
61
Table (4.6): Optimal values of per-exponential factor and

activation energy of every reaction
Reaction Activation energy Per-exponential Reaction Activation energy Per-exponential
number (j) ( ), J/mol factor (A) number (j) ( ), J/mol factor (A)
1 10359.1 30328.2 19 410171 1.20053E+37
2 10359.1 11973.8 20 382927 1.11887E+37
3 1779.64 8101.04 21 329776 6.71002E+31
4 1779.64 12237.8 22 342906 2.04715E+31
5 3098.58 34360 23 266712 6.27716E+26
6 3098.58 6149 24 264004 3.04961E+26
7 12499.3 36715.9 25 294374 6.36194E+26
8 12499.3 7720 26 277806 1.70425E+27
9 8551.55 8549.55 27 273965 6.77152E+26
10 8551.55 2516.07 28 220534 3.17332E+23
11 12410.4 246504 29 216658 3.51283E+23
12 12410.4 11903 30 128748 1.74229E+15
13 5888 4326.49 31 91332.9 283811864
14 5888 4610.34 32 98599.4 15238268830
15 7703 102328 33 97396.6 9654847240
16 7703 2806.19 34 91034.3 1400727929
17 185323 1.20775E+16 35 259025 2.92353E+29
18 180018 3.98326E+16 36 255393 2.90342E+26
61
Table (4.7): Optimal orders of components concentration and

kinetic coefficient of intermolecular interactions intensity
parameter symbol Unit value
Order of hydrocarbon concentration n (-) 0.9412
Order of hydrogen concentration in m (-) 0.935

cracking reaction
Order of hydrogen concentration in o (-) 3.279
hydrogenation reaction
(-) 1.463
Kinetic coefficient of intermolecular
interactions intensity (-) 0.8154
Chekantsev et al. (2014) have assumed that the orders of

concentration that used in the simulation isomerization process equal to
number of particles which enter the interaction, and they numerically
calculated the values of activation energy ( ) and per-exponential factor
( ). There was an absolute error above 5% between the industrial and
theoretical results.
Busto et al. (2008) and Volkova et al. (2007) have also considered
that every reaction in the system should be as an elementary reaction and
they used the reaction Gibbs free energy data to estimate the reaction rate
constants. They got an error higher than 5% between experimental and
predicted results. Table (4.7) presents a comparison between the
elementary reaction orders (gives an absolute error equal or high than 5%)
and the optimal orders values obtained in this study (with absolute error
less than 0.1%).
62
Table (4.8): Comparison between the optimal and theoretical

orders values
Theoretical value Optimal value
Orders
(Reported in the literature) (Obtained here)
Hydrocarbons concentration
1 0.9412
order (n)
Hydrogen concentration order
1 0.935
in hydrocracking reaction (m)
Hydrogen concentration order
3 3.279
1n hydrogenation reaction (o)
In this study, the optimal kinetic parameters have been estimated

based on a maximum error of 0.1% among all results between the
experimental and predicted results of average reactor output data. After the
kinetic parameter estimation process, a simulation process on the test runs
data were made. The composition of isomerizate components ( ),
research octane number of isomerizate (RON) and reactor outlet
temperature (T) have been presented in Table (4.8) that showed a
comparison of the results obtained by the mathematical model presented in
this study and the actual results.
63
Table (4.9): The comparison between the actual data and the
mathematical model results (predicted)
Hydrocarbon Test run 1 Test run 2 Test run 3

Absolute Absolute Absolute
components Exp. Theo. Exp. Theo. Exp. Theo.
Error (%) Error (%) Error (%)
n-Butane(nC4) 1.222 1.2208 0.0982 1.970 1.9681 0.0964 1.9611 0.0968

1.963
n-Pentane(nC5) 18.267 18.248 0.101 18.179 0.101 17.250 0.101

18.362 17.423
n-Hexane(nC6) 7.540 7.5329 0.094 7.597 7.5893 0.094 8.169 8.1606 0.094
n-Heptane(nC7) 0.040 0.4004 0.100 0.059 0.0591 0.1094 0.032 0.3203 0.0938
i-Butane(iC4) 0.517 0.5165 0.0967 0.963 0.9621 0.0934 0.735 0.7343 0.0953
i-pentane(iC5) 35.013 34.977 0.1028 35.653 0.1008 35.946 0.1005

35.689 35.982
2,2 Di Methyl
Butane 7.766 7.7589 0.0914 7.356 7.3487 0.0992 7.170 7.1629 0.0990
(2,2-DMB)
2,3 Di Methyl
Butane 3.567 3.5635 0.0981 3.092 3.0889 0.1002 3.029 3.0259 0.1023
(2,3-DMB)
2Methyl Pentane
12.493 12.469 0.1001 12.597 12.472 0.1001 12.965 0.1001
(2MP) 12.978
3Methyl Pentane
9.296 9.2867 0.1002 8.599 8.5903 0.1015 8.243 8.2345 0.1009
(3MP)
i-heptane(iC7) 0.412 0.4116 0.0990 0.250 0.2498 0.0992 0.298 0.2977 0.0979
Cyclo
1.138 1.1391 0.1007 1.369 1.3703 0.0981 1.054 1.0551 -0.0998
Pentane(CP)
Methyl Cyclo
1.450 1.4488 0.0832 1.072 1.0712 0.0786 1.144 1.1431 0.0720
Pentane (MCP)
Cyclo Hexane(CH) 0.436 0.4356 0.0910 0.316 0.3157 0.0879 0.353 0.3527 0.0728
Benzene(C6) 0.000 2.89E-6 1E+02 0.000 2.7E+02 1E+02 0.000 3.06E-6 1e+02
Temperature (T) 552.12 551.34 0.1012 550.72 551.67 0.097 554.2 553.4 0.1006
RON 79.33 79.374 0.0554 79.41 79.452 0.0528 79.26 79.317 0.0719
64
4.3 Effect of Different Operating Variables on the

Performance of Isomerization Process
After getting the accurate kinetic model, it is used to describe the
influence of operating conditions on the reactions occurring through the
bed of catalyst. Increasing the RON of the light naphtha and isomerizate
yield are the main goal of the isomerization process, therefore, the variables
are considered as an index for analyzing the performance of the reactor.
The most variables affecting the process are:
4.3.1 Effect of Temperature and Pressure

Figures (4.1) and (4.2) show the influence of the feed stock
temperature and pressure on the RON and yield of isomerizate respectively.
Feed stock NO.1 was used to describe the behavior of this process at
constant LHSV equal to 1.489 and hydrogen ratio equal to 3.22. It can
be observed that temperature has the most influence on the performance of
isomerization reactions. In Figure (4.1), at the beginning of the curve
(region one (500-524K)), the RON increases with increasing temperature
due to increase the reaction rates because the catalyst activity increases
with temperature according to Arrhenius equation. Such increases of RON
continue until the optimal temperature is achieved that represents the
thermodynamic equilibrium limit point. After this temperature, the second
region is beginning and decreasing the RON is observed in such region
(524-535K) that can be related to the thermodynamic properties of such
reactions and accelerated the hydrocracking of hydrocarbons containing
six carbon atoms such as 2,2-DMB, 2,3-DMB, MCP, and CH which have
high RON. Therefore, high octane number species are converted to lighter
ones such as methane, propane and butanes. These light species are
separated from the product in the form of fuel gas and the reduction of
octane number continues until hydrocarbon species containing six carbons
65
are hydrocracked. Finally, the upward trend of RON in the third region is
due to increase the percentage of pentane at higher temperatures (Hayati et
al., 2015).
Since hydrocracking reactions have a negative effect on the yield of the

gasoline production, it is concluded that the optimal isomerization
temperature is located in the first region in which RON and yield are both at
the optimal values. This figure also indicates that 0.2 MPa unit increment in
pressure increases the optimal temperature about 2oC. Figure (4.1) also
demonstrates the dependency of RON on pressure when hydrogen to
hydrocarbon molar ratio and LHSV are kept constant. The optimal reactor
inlet temperature depends on the pressure and the results showed that by
decreasing the reactor pressure, the optimal reactor inlet temperature is
decreased owing to the decrease in the rate of hydrocracking reactions,
which absorbs some of isomerization reactions emitted heat (Yasakova et
al., 2010; Said et al., 2014).
82
80
78
76
RON
2.1 MP
74 2.3 MP
72 2.5 MP
70
68
460 480 500 520 540 560
Temperature, K
Figure (4.1): Effect of temperature on the RON of product at

different pressure with constant LHSV equal to 1.489 ,
H2/HC equal to 3.22 mole ratio
66
Figure (4.2) presents the effect of inlet feed stock temperature and
pressure on the isomerizate yield at constant LHSV and hydrogen to
hydrocarbon mole ratio. The presented columns show that the yield of
isomerizate decreases with increasing the inlet temperature due to the
increase of hydrocracking reactions rate. Also, this figure showed that the
increase in pressure can decrease the isomerizate yield due to increasing the
partial pressure of hydrogen (Busto et al., 2008; Hayati et al., 2015).
100
98
96
94
92
yield
2.1 MPa
90
2.3 MPa
88
2.5 MPa
86
84
82
523 K 528K 533K
Temperature, K
Figure (4.2): Yield of isomerizate at different temperature
and pressure and at constant LHSV of 1.489hr-1 and constant
H2/HC at 3.22 mole ratio
4.3.2 Effect of Hydrogen to Hydrocarbon Mole Ratio

Hydrogen is desired to complete the reactions and decreasing
deposition the coke on the surface of the catalyst. Figures (4.3) and (4.4)
show the influence of the hydrogen to hydrocarbons mole ratio on the RON
and yield of isomerizate, respectively at constant temperature, pressure and
liquid hourly space velocity. It is has been observed from Figure (4.3), that
the product RON depends on the hydrogen over feed molar ratio. These
results show that at constant feed flowrate and by increasing hydrogen to
67
feed molar ratio, the RON of product decreases because the rate of
hydrocracking reactions (which considered endothermic reactions) increase
which cause decreasing the temperature within the reactor. (Said et al.,
2014; Hayati et al., 2015).
80
79.8
79.6
79.4
79.2
79
RON
78.8
78.6
78.4
78.2
78
77.8
3.1 3.2 3.3 3.4 3.5 3.6 3.7
H2/HC mole ratio
Figure (4.3): Effect of H2/HC on the RON at constant temperature

equal to 523K, LHSV equal to 1.489 and pressure equal to
2.4MPa
Figure (4.4) also shows the high negative impact of hydrogen to

hydrocarbon mole ratio on the isomerizate yield. Increasing of such ratio
leads to decrease the yield of isomerizate owing to the increase of hydrogen
partial pressure. This figure also indicates that 0.2 unit increments in
hydrogen-to-hydrocarbon molar ratio decreases the yield of isomerizate
about 1.3% at constant temperature.
68
98
97.5
97
yield
96.5
96
95.5
95
3.1 3.2 3.3 3.4 3.5 3.6 3.7
H2/HC mole ratio
Figure (4.4): Yield of isomerizate at constant temperature of

523K, LHSV of 1.489hr-1 and pressure of 2.4MPa
4.3.3 Effect of LHSV

Figures (4.5) and (4.6) present the LHSV on the RON and yield of
isomerizate at constant H2/HC mole ratio, temperature and pressure.
According to Figure (4.5), the RON of the product depends on the LHSV.
Indeed, the residence time decreases by increasing the LHSV, so that the
conversion of normal paraffin's decrease (Said et al., 2014).
The negative effect of increasing the LHSV on the RON can be

treated by increase the inlet temperature of reactor feed stock. This method
can be recommended for increasing the capacity of light naphtha
isomerization reactor, accordingly, increasing the reactor operating
temperature increases the capacity of gasoline production while the RON
of product remains at the desired value. This procedure is highly
appreciated when there is limitation in increasing hydrogen to hydrocarbon
molar ratio due to the process limitations such as the loading capacity of
hydrogen compressor (Hayati et al., 2015) .
69
80.5
80
79.5
79
RON
78.5
78
77.5
77
1 1.1 1.2 1.3 1.4 1.5 1.6 1.7
LHSV, hr-1
Figure (4.5): Effect of LHSV on RON at constant temperature

of 523K, H2/HC at 3.22 and pressure equal to 2.4 MPa
Figure (4.6) shows the impact of LHSV on the isomerizate yield.

Increasing of such ratio leads to increase the yield of isomerizate owing to
the decrease the contact time.
98.5
98
97.5
yield
97
96.5
96
1 1.1 1.2 1.3 1.4 1.5 1.6 1.7
LHSV, hr-1
Figure (4.6): Effect of LHSV on yield at constant temperature

of 523K, H2/HC of 3.236 and pressure equal to 2.4MPa
71
4.4 Summary
This work aimed to develop and recognized the optimal operation
conditions of the light naphtha isomerization process in Baiji refinery via
studying the effect of different variables on the operation of isomerization
fixed bed reactor (mainly, temperature, pressure, liquid hourly space
velocity and hydrogen to hydrocarbon mole ratio). After using the
optimization technique to get the best kinetic as presented in this chapter,
the simulation was used to predict the behavior of isomerization and
hydrocracking reactions. The effect of these variables on the performance
of reactor operation is summarized as:
 Reactor temperature having the most effect on the RON and

isomerizate yield. The RON increases with increasing inlet temperature
until gets the optimal temperature, which the RON decreases. So, the
operation temperature should not exceed the optimal temperature
because the rate of hydrocracking reactions increases with increasing
temperature.
 An increase in the operating pressure decreasing the yield and RON.
 The increasing of hydrogen to hydrocarbon ratio decreases the RON
and isomerizate yield at constant inlet temperature.
 Increasing of Liquid hourly space velocity can decrease the RON
and increasing the isomerizate yield.
The analysis of physical properties showed that the operation of
isomerization unit occurs within an optimal range of operating condition.
So to increase the unit performance, using the recycle and by-pass
isomerization technologies should be applied (as will be shown in the next
chapter).
71
Chapter Five Isomerization Configurations
CHAPTER FIVE
ISOMERIZATION
CONFIGURATIONS
Chapter Five
Isomerization Configurations
5.1 Introduction
The analysis of operating conditions can effect on the unit
performance. Previous chapter showed that the isomerization unit operates
in optimal range of operating conditions, so that changing the operating
condition will not give a significant improvement on the performance of
the unit.
The once through operation of zeolitic process (without any recycle or by-
pass) is economically efficient process and may be used with a minimum
finance to increase RON of light naphtha, but the maximum value of RON
obtained is 80. Thus, such issue can be exceeded by using recycle
technology, by-pass technology or combination of both. Using of these
technologies can increase the RON of light naphtha over 90 making an
excellent component in gasoline pool (Anderson et al., 2004; Yasakova et
al., 2010).
In this chapter, may technologies are applied, then the operating

conditions of these technologies are optimized by using the optimal kinetic
obtained previously. Also, the comparison of the performance of these
technologies (RON and yield) and technology economic cost are presented.
A novel configuration of the isomerization process is investigated here to
obtain the maximum yield of isomerizate and RON that has not been
reported in the literature with minimizing for economic cost. As well as the
heat integration for this configuration is studied here based on the optimal
configuration of isomerization process.
72
5.2 Isomerization Technologies

Low RON components such normal paraffin's are separated from the
isomerizate and returned to the reactor feed. Many technologies such
distillation process and molecular sieve adsorption process or combination
of them are used to separate normal paraffin's. Choosing of the separation
technique is an important issue that mainly depends on the feed
composition, desired RON and investment cost (Anderson et al., 2004;
Domergue and Watripont, 2005).
For all schemes, the optimization process is taken place by using the
same mathematical model presented in chapter three to get the optimal
operating conditions (temperature, pressure, LHSV, hydrogen ratio), which
give the maximum RON, maximum yield and minimum cost according to
Figure (5.1) and using the following equations:
OBJ1=RON …(5.1a)
OBJ2= YIELD …(5.1b)
OBJ3= OAUC …(5.1c)
: Objective function, (-)
: Research Octane number, (-)
: Isomerizate yield,
: Overall annual cost,
This equations is used to optimize all cases will be presented below:
73
Start
Read n, m, o, α and
γ
Calculate RON,
yield and OAUC
Calculate OBJ
Calculate P, T,
LHSV and mr that
minimize the OBJ
Read RON, yield,

OAUC, P, T, LHSV
and mr
End
Figure (5.1): The procedure of isomerization configurations optimization
5.2.1 Once Through Process

The once through process of Baiji isomerization unit is accomplished
by Axens company. It's flow diagram was presented and explained in
chapter three. The analysis of operating conditions of such technology has
already been shown in previous chapter.
74
5.2.2 Deisopentanizer (DIP) Process

In this isomerization scheme shown in Figure (5.2), distillation
column is located before the reactor to separate Iso-pentane component
from light naphtha feed to increase the normal pentane conversion. Bottom
stream of the distillation enters to the isomerization process, which is
followed by stabilization process to produce stabilized isomerizate and
mixing with iso- pentane stream. This scheme becomes reasonable for the
composition of iso-pentane in the feed with more than 13-15% (Anderson
et al., 2004; Yasakova et al., 2010).
i-C5
H2
Off gas
Light
naphtha
DIP Isomerization stabilization
isomerizate
Figure (5.2): Block diagram of process with DIP
5.2.3 Deisohexanizer (DIH) Process

To increase the conversion of 2,2-DMB (RON=94) and 2,3-DMB
(RON=105), n-H (RON=25), 2-MP (RON=74.4) and 3-MP (RON=75.5)
are separated and recycled to the reactor. As shown in Figure (5.3),
distillation column are used for separation process and 65% of the -
hydrocarbons are separated from reactor product stream and recycled to the
reactor inlet stream. The column is located after stabilization process. The
75
top product of distillation is stabilized isomerizate (Domergue and

Watripont, 2005; Yasakova et al., 2010).
H2 Off gas
Light
naphtha
Isomerization stabilization DIH isomerizate
N-C6 & MP recycle
Figure (5.3): Block diagram of isomerization unit with DIH
5.2.4 DIP and DIH Process

Using of DIP technology increases the conversion of normal pentane
and there is no effect on the hexane conversion has observed. Also, the use
of DIH increases the hexane conversion only. So, A combination between
DIP and DIH is used to get high RON and yield as shown in Figure (5.4).
Tow distillation columns are used, the first one is located before the
isomerization unit and working as DIP (explained in case 2). The second
column is located after the isomerization unit and working as DIH
(explained in case 3) (Domergue and Watripont, 2005; Yasakova et al.,
2010):
76
H2 Off gas
i-c5
Light
naphtha
DIP Isomerization stabilization DIH
isomerizate
N-C6 & MP recycle
Figure (5.4): Block diagram of isomerization unit with DIH and DIP
5.2.5 Ipsorb Process

In this case, shown in Figure (5.5) below, the adsorption of normal
paraffin's (pentane and hexane) is used by molecular sieve adsorbers,
followed by desorption from the pores and then they are recycled to the
feed stock and the stream of iso-pentane is used to recover normal
paraffins. This technology is developed by Axens and Zeolite 5A is used as
molecular sieve. This equipment is located after isomerization unit
consisting of two adsorber columns work alternately. Adsorption process
acquires the same temperature and pressure of the reactor exit stream
(Anderson et al., 2004; Barcia et al., 2004).
77
i-C5
Off gas
Light Molecular
naphtha
DIP Isomerization isomerizate
sieves
H2
i-C5 & n-C6 & n-C5
Figure (5.5): Block diagram of Ipsorb isomerization unit
5.2.6 Hexorb Process

In the case 6, as shown in Figure (5.6), the scheme combines between
the molecular sieve and DIH technology, also in the Hexorb process all
normal paraffins adsorbs and converts to isomers. Here, methyl pentanes
(RON 74.4 and 75.5) are recycled with normal paraffins due to add DIH
after molecular sieve system. After isomerization process, reactor outlet
stream enters into the adsorber column to separate normal paraffins.
Branched paraffins pass through adsorber bed and enter to DIH to separate
methyl pentane components that are recycled to the reactor. Before entering
the reactor, stream of methyl pentane is used to recover the normal
paraffins from adsorber bed and recycle to the reactor (Graeme et al.,
2004; Domergue and Watripont, 2005).
78
MP i-C5,DMB
Off gas
Light
naphtha Molecular isomerizate
Isomerization DIH
sieves
H2
MP, n-C5, n-C6 MCP,CH,C7
Figure (5.6) block diagram of Hexorb isomerization unit
5.2.7 Total Isomerization Process (TIP)

UOP offers the isomerization process with molecular sieves
adsorption system to separate and recycling the normal paraffins. In this
scheme (Figure (5.7)), after heating light naphtha stream, the stream is
interred to the isomerization reactor. The product of the reactor is interred
to the adsorption towers to separate the normal paraffins and recycled it to
the reactor. The stream of hydrogen is used to recover the normal paraffins
from adsorber column (Holcombe, 1980).
H2 Off gas
Light
natptha Molecular isomerizate
Isomerization Isomerization
sieves
H2 & n-C6 & n-C5
Figure (5.7): Flow diagram of TIP isomerization unit
79
5.2.8 A New Configuration (proposed in this study)

The high economic cost of molecular sieve technologies due to their
high recycle rate, leads to make a suitable modification on schemes of these
technologies under reducing the economic cost with the same performance
and to maximize RON. According to the specifications of naphtha feed
stock at Baiji isomerization unit, the separation process can be made firstly
owning to the content of benzene component, which is less than the
operative percentage (0.62%).
This new advanced configuration process (ACP) has been applied on

the scheme of TIP as shown in Figure (5.8). As firstly seems in this figure,
the light naphtha stream heated through heat exchanger (E201) and mixed
with the reactor product stream and then heated through the furnace
F201befor interring to the adsorber S201. There are two adsorber columns
work alternately. Through the adsorber S201, the normal paraffins are
adsorbed by the molecular sieve and only branched paraffins leave the
column. The normal paraffins remaining within adsorber S202 are
desorbed by hydrogen stream (which is heated through the furnace F202
after compressed by Co201). The bottom stream of the adsorber S202
interred to the reactor R201. The reactor product stream are condensed
through E206 to separate the hydrogen from isomerizate stream within
separator drum D201. Top product (hydrogen stream) of D201 is interred
to Co201and the bottom product (isomerizate) is heated through E206
before mixing with light naphtha stream. The top stream of S201 is
condensed through E201 and then interred to stabilization zone. After
interring to the stabilizer, branched paraffins are partially vaporized
through E202 by heat exchange with bottom product of the stabilizer. Light
hydrocarbons (methane, ethane, propane and part of butane) are separated
81
from the isomerizate as a top product. The bottom product of the stabilizer
(isomerizate) cooled through E202 and E204 before the storage.
This process is optimized based on the Figure (5.8) that has a design
of heat exchangers network similar to TIP process. It is optimized
according to equations (5.1a, b and c) after making the energy balance. The
heat integration to improve the heat exchangers design of network and
reducing the OAUC, is completed.
E 205
Gas
D202
S201 S202 F R201

202
C201
F
201 C Stabilizer
feed E Heat exchanger
E
201
Co E E D Separator drum
201 E
206 202
R Reactor
203 Co Compressor
E D201 A Air cooler
F Furnace
206
E204 isomerizate
Figure (5.8): Flow diagram of advanced configuration
5.3 Economic Cost Equations

The cost estimation equations are necessary to complete the objective
function of the optimization process for each unit (are applied for all
isomerization technologies including the advanced technology proposed in
this study). The overall annual cost of process are calculated by using the
following relation (Douglas, 1988, Jarullah, 2012):
81
Overall Annual Unit Cost (OAUC, $/yr)= Annual Unit Capital

Cost (AUCC, $/yr) Annual Unit Operating Cost (AUOC, $/yr)
...(5.2)
The annual unit capital cost (AUCC, $/yr) are estimated from the total unit
capital cost (TUCC, $), which represents the of main equipments cost in the
unit process such as reactor, heat exchanger, compressor, furnace,
separator and pumps, as the following:
Annual Unit Capital Cost (AUCC, $/yr) = Total Unit Capital
Cost (TUCC, $) ...(5.3)
The total unit capital cost (TUCC, $) can be estimated from the following
equation (Towler and Sinnott, 2012):
Total Unit Capital Cost (TUCC, $) = Installed Equipment Capital

Cost (IECC, $) 1.45 ...(5.4)
The installed equipment capital cost (IECC, $) is different from unit to

another due to separation technology that are used. The following equation
represents the installed equipment capital cost (IECC, $) for once through
unit:
Installed Equipment Capital Cost (IECC, $) = Reactor Cost ( )

Compressor Cost ( ) Heat exchanger Cost ( ) (1, 2, 3,
4 & 5) Pumps Cost ( ) Furnace Cost ( ) Stabilizer Cost
( ) ) + separator cost ) ...(5.5)
Annual unit operating cost (AUOC, $/yr) for each unit is calculated from
the following equation:
82
Annual Unit Operating Cost (AUOC, $/yr) = Variable Unit

Operating Cost (VUOC, $/yr) Fixed Unit Operating Cost
(FUOC, $/yr)
...(5.6)
Variable Unit Operating Cost (VUOC, $/yr) = Heating Cost

( ) + Compression Cost ( ) + Cooling Cost ( )+
Catalyst Cost ( ) + hydrogen consumption Cost ( ) +
Pumping Cost ( + Steam Cost ( ) ...(5.7)
Fixed Unit Operating Cost (FUOC, $/yr)= Maintenance Cost

( ) Operating Labour Cost ( ) Laboratory Cost ( )
Supervision Cost ( ) Plant Overhead Cost ( ) Capital
Charge Cost ( ) Insurance Cost ( ) ...(5.8)
5.3.1 Installed Equipment Capital Cost (IECC, $)

The economic cost of each equipment is estimated based on Marshal
and Swift index as follow (Douglas, 1988; Smith, 2005; Rosales-
Quintero and Vargas-Villamil,2009):
a) Reactor Cost (Cr)

The reactor cost is calculated as a function to the length and
diameter of the reactor, which are related to the liquid hourly space
velocity (LHSV), as follow:
=( )101.9 (2.18 ) ...(5.9)
= ...(5.10)
83
Where:
($): Reactor capital cost, ($)
: reactor length, (m)
: reactor diameter, (m)
M&S: Marshal and Swift index, (-)
M&S is taken equal to 1622 (Mohammed et al., 2016).
, and dimensionless factors that are function of the operating

pressure and material construction (Douglas, 1988).
...(5.11)
Bed length, (m)
Inert bed high, (m)
√ ⁄ ...(5.12)
⁄ : length to diameter bed ratio, (-)
: bed volume, (
...(5.13)
light naphtha flow rate,
b) Stabilization Cost (Cs)

The total distillation column cost is estimated as follow:
= Column Cost ( ) + Tray Cost ( )
84
=( )101.9 (2.18 ) ...(5.14)
Where:
column length, (m)
column diameter, (m)
( ) ...(5.15)
...(5.16)
are calculated from the following equations (Sinnott, 1999):
...(5.17)
√ ...(5.18)
* + ...(5.19)
Where:
maximum vapor rate, Kg/s
vapor density, kg/
liquid density, kg/
: tray spacing, (m)
: tray number, (-)
85
c) Compressor Cost
The compressor cost, related to the reactor pressure, is calculated as follow:
( ) ...(5.20)
The compressor horsepower calculated as follow (Bouton and Luyben,

2008; Mohammed et al., 2016):
⁄ ...(5.21)
( ) *( ) + ...(5.22)
( )
...(5.23)
( )
...(5.24)
...(5.25)
Where:
bhp: horsepower required in the compressor, hp
: the a cost correction factor, (-)
Hp: the isentropic compressor horsepower, hp
isentropic compressor efficiency, (-)
: the specific heat ratio, (-)
: the volumetric flow rate of hydrogen at compressor section,
the specific heat capacity at constant volume, ⁄
86
the specific heat capacity at constant pressure, ⁄
Pin, Pout: are the inlet and outlet pressure in the compressor, Pa
reactor pressure, Pa
naphtha stream pressure, Pa
d) Separator Cost ( )
=( ) 937.63 ...(5.26)
& are the diameter and length of separator, which can be estimated as
follows (Sinnott, 1999):
To design the horizontal separator vessel, the estimation of the settling

velocity of the liquid droplets is necessary.
For satisfactory separation, the required residence time = actual

residence time ) ...(5.27)
Required vapor residence time to settle the droplets to liquid surface is

calculated as follow:
...(5.28)
vapor high, m
settling velocity, m/s
...(5.29)
= 0.0105√ , (without demister) ...(5.30)
: Liquid (naphtha) density, ⁄
87
: Vapor (hydrogen) density, ⁄
...(5.31)
vapor velocity, m/s
...(5.32)
...(5.33)
Hydrogen volumetric flow rate, ⁄
cross section area of vapor flow rate,
...(5.34)
e) Pumps Cost ( )
Due to process flow sheet, there are two pumps, their cost are calculated, as
related to naphtha mass rate, as follows:
=( ) 9.84 ( ) ...(5.35)
power of ith pump, kW
f) Heat Exchangers Cost

The cost of heat exchanger, related to reactor inlet and outlet temperature is
calculated as follow:
=( ) 210.78 (2.29 ) ...(5.36)
= ( ) ...(5.37)
88
Area of heat exchanger,
The heat exchanger area are estimated from energy balance that will be
shown in the next section.
f) Furnace cost
=( ) 5.52 (1.27 ) ...(5.38)
= ...(5.39)
: Furnace heat duty, W
The furnace heat duty is calculated from energy balance in the

next section.
g) Adsorber Cost (Cad)

Economic cost of adsorber column is calculated (for only process that
use molecular sieve technology) as follow:
=( )101.9 (2.18 ) ...(5.40)
= ...(5.41)
Where:
($): Adsorber capital cost, ($)
: Adsorber length, (m)
: Adsorber diameter, (m)
, and dimensionless factors that are function of the operating

pressure and material construction (Douglas, 1988).
89
√ ⁄ ...(5.42)
⁄ : length to diameter bed ratio, (-)
: bed volume, (
…(5.43)
The ratio of equal to 1.25 according to Holcombe (1980).
The amount of catalyst (M5A) is calculated by scaling down of the beds

used in the scheme designed as shown below (Holcombe, 1980):
Original This case
33000 (kg of 5A) 18450(kg/hr of n-paraffins received)
M5A (kg of 5A) Mnp (kg/hr of n-paraffins received)
The rate of normal paraffins received (Mnp) is obtained by simulation

process for each technology.
5.3.2 Fixed Unit Operating Cost (FUOC, $/yr):

Each variable of fixed unit operating cost (FUOC) are estimated as follow
(Douglas, 1988, Jarullah, 2012):
 Maintenance Cost ( ): It includes the cost of equipment spares and the

cost of labour needed for the unit maintenance. Typically, the annual
maintenance cost is taken (5-15%) of the installed capital cost.
 Operating Labour Cost ( ): It includes the cost of the person needed to
operate the plant. The value is taken 15% of the total annual operating
cost.
91
 Laboratory Cost ( ): It includes the desired laboratory analyses for

process quality control. The value of laboratory cost is about 20 to 30%
of the operating labour cost.
 Supervision Cost ( ): It involves the direct supervision of operation
and the management directly linked with operating the plant. The value
is about 25% of the labours cost.
 Plant Overhead Cost ( ): It involves all the general costs linked with
operating the plant that are not involved with other headings (such as
,plant, offices, security, canteen, medical, safety and staff). This value
are about (50-100%) of the labours cost.
 Capital Charge Cost ( ): It is recovered as a depreciation charge. The
value can be taken as 10% of the total unit capital cost.
 Insurance Cost ( ): This value is often taken as (1-2%) of the total unit
capital cost.
5.3.3 Variable unit operating cost (VUOC, $/yr):

The VUOC is calculated use the following equations:
a) Compression Cost ( )
The compressor can be estimated as follow based on the motor efficiency
at 90% (Bouton and Luyben, 2008) with a power price of 0.062$/kWh
(Mohammed et al., 2016):
⁄ =( )( )( )( )( ) ...(5.44)
b) Heating Cost ( )
⁄ = ( )( )( ) ...(5.45)
91
c) Pumping Cost ( )
($/yr)= ( )( )( )( ) ...(5.46)
d) Cooling Cost ( )
It's calculated by the following equation with a price of cooling water
(0.0035 $/kg) (Mohammed et al., 2016):
⁄ =( ( )) ( )( )( ) ...(5.47)
e) Hydrogen consumption cost ( )

It can be calculated by the following equation with a price of hydrogen at
0.49 $/ (Weinert et al., 2007):
⁄ ( )( )( )( )( ) ...(5.48)
weight rate of hydrogen consumption, (
...(5.49)
total moles interred the reactor, mol
...(5.50)
...(5.51)
& : weight rate of reactor inlet and outlet hydrogen, (
f) Catalyst cost
$/yr ( )( )( ) ...(5.52)
The catalyst price is taken 96$/kg (alibaba, 2017a), is the catalyst life
time taken by 10 years (Yasakova et al., 2010).
g) Zeolite-5A cost
The price of 5A Iso-sieve Zeolite is equal to 2$/kg (Alibaba, 2017b)
92
…(5.53)
h) Steam Cost ( )
It's calculated by the following equation with a price of steam equals to
0.018 $/kg (Bless et al., 2017):
⁄ =( ( )) ( )( )( ) ...(5.54)
5.4 Energy Balance

Energy balance on heat transfer equipment is essential to estimate the area
of heat transfer ( ) and heat duty ( ) as a function of temperatures.
a) Energy balance of heat exchanger E201

Through this equipment, cold light naphtha is heating and vaporized as a
result of the heat transfer from the hot stream of isomerizate as shown in
Figure (5.9).
Th,in
Tc,out
Th,out
Tc,in
Figure (5.9): Heat exchanger E201
The area of heat transfer is calculated as a function of outlet reactor

temperature, by the following equation:
...(5.55)
Where:
93
rate of heat transfer, kW
heat transfer coefficient, kW/(
Log mean temperature difference for heat exchanger1,(-)
calculated according to figure (5.1) as follow:
= ...(5.56)
( )
= ...(5.57)
= ...(5.58)
Where:
: The inlet temperature of hot stream into E201,
: The inlet temperature of cold stream into E201
: The outlet temperature of hot stream from the heat exchanger E201,
: The outlet temperature of cold from heat exchanger1 (HE1),
...(5.59)
T: The outlet reactor temperature, K (calculated from reactor energy

balance equation (3.3).
are given as constant values.
is calculated as a function reactor outlet temperature T as follow:
Heat loss from hot stream = heat absorbed by cold stream
94
( ( ( ) )
) ) ...(5.60)
( ( ) )
...(5.61)
For TIP process (case7) equations (5.57), (5.58) and (5.59) are written as
follow:
( ( ( ) ))
...(5.62)
( ( ) )
...(5.63)
In this case (case 7) doesn‘t equal to T.
Where:
Boiling temperature of cold and hot stream respectively, K
Latent heat of vaporization of cold and hot stream respectively,

kj/kg
heat capacity of hot and cold stream respectively as liquid,

kj/(kg k)
heat capacity of hot and cold stream respectively as vapor,

kj/(kg k)
95
b) Energy balance of heat exchanger E202

This equipment is located before the stabilizer where the hot stream is
stabilized the isomerizate and the cold stream is unsterilized isomerizate.
Condensation of hot stream and vaporization of the cold stream are
occurred based on heat exchanger1.
The area of heat transfer is calculated as follow:
...(5.64)
= ...(5.65)
( )
= ...(5.66)
= ...(5.67)
( ( ) )
...(5.68)
All parameters above are given as constant.
Th,in
Tc,out
Th,out
Tc,in
96
c) Energy balance of heat exchanger E203

The objective of energy balance is to obtain the heat transfer area
( and the amount of steam ( which can be described as follow:
...(5.69)
= ...(5.70)
( )
= ...(5.71)
= ...(5.72)
...(5.73)
...(5.74)
...(5.75)
...(5.76)
This equipment is used to rise the bottom stream temperature of stabilizer

by steam condensing as shown Figure (5.10).
Th,in
Tc,out
Th,out
Tc,in
97
d) Energy balance of heat exchangers E204 & E205

These equipments work as coolers for stabilizing the isomerizate as
E204, and light product of stabilizer (E205). Bellow, the equations of
( and cooling water rate for heat exchanger4 (E204):
...(5.77)
= ...(5.78)
( )
= ...(5.79)
= ...(5.80)
...(5.81)
( ) ...(5.82)
The same equation are used for E205.
Th,in
Tc,out
Th,out
Tc,in
Figure (5.12): heat exchanger E204 and heat exchanger E205
98
e) Energy balance of heat exchanger E206

For the TIP process and advanced configuration, as shown in Figure (5.7),
heat exchanger E206 is used in addition to heat exchangers that are
explained above.
...(5.83)
= ...(5.84)
( )
= ...(5.85)
= ...(5.86)
( ( ( ) ))
) ...(5.87)
( ( ) )
...(5.88)
...(5.89)
f) Energy balance of furnace (

The light naphtha stream is interred to the furnace in order to achieve
the required reactor inlet temperature. Calculation of the furnace heat duty
( as a function of reactor inlet temperature is required to complete the
cost model.
( ) ...(5.90)
Outlet and inlet furnace temperature, K
...(5.91)
99
...(5.92)
g) Energy balance of furnaces (F1 & F2)

As shown in the TIP flow sheet (Figure (5.17)) instead of one
furnace, there are two furnace. Their heat duty ( ) are calculated as
follow:
( ) ...(5.93)
...(5.94)
( ) ...(5.95)
5.5 Optimization Problem For Isomerization Technologies

According to the equations (5.1a, b and c) utilizing the mathematical
model presented previously and applying the optimal kinetic parameter
obtained in the last chapter, the optimization problem are stated as:
Given Initial concentration, kinetic parameters, reactor

configuration, process specifications
Determine initial temperature, pressure, LHSV and hydrogen to
hydrocarbon mole ratio.
So as to OBJ (RON& yield maximize, OAUC minimize)
maximize
Subjected to Process constraints and linear bounds on all decision
variables.
111
The optimization problem for each isomerization technology are written as:
max
P, T, LHSV,
s.t f(x(z),u(z), v) = 0 (model equation, equality constraint)
(inequality constraints)
5.6 Results and Discussion

Results and discussion of each case studied here and comparison between
theme are separately presented below:
5.6.1 Results of Once Through Process (case study 1)

The model of cost calculations (presented in this chapter) is used with
the model equations (presented in chapter three) to simulate the behavior of
the once through process, which is required to make a comparison among
the units.
The streams temperatures (presented in Table (5.1)) are the same with
those used in the isomerization unit at Baiji refinery, heat capacities of
liquid naphtha were taken from Gary et al. (2007), heat transfer coefficient
and the dimensionless factors were taken from Douglas (1988). All these
parameters are presented below:
111
Table (5.1): Values of coefficients and constant parameters used in this

process
Parameter unit Value Parameter unit Value
K 60 KW/ 0.387
K 43 KW/ 0.942
K 40 KW/ 0.4
K 169 Kj/kg 274
K 132 Kj/kg 268
K 200 Kj/kg 317
K 20 Kj/ (kg.k) 2.531
K 16 Kj/ (kg.k) 2.522
K 450 Kj/ (kg.k) 2.481
K 386 Kj/ (kg.k) 2.388
KW/ 0.432 Kj/ (kg.k) 2.388
m 0.45 (-) 26
Kg/S 0.6329
Table (5.2): Dimensionless factors values

Dimensionless factors
equipments
Reactor 3.67 1.275 - - - -
Stabilizer column 3.67 1.12 - - - -
Pump1 1 1.5 - 1 - -
Pump2 1 1.5 - 1 - -
Cooler1 &2 3.75 0.1 0.85 - - -
Heat exchanger1 3.75 0.25 0.85 - - -
Heat exchanger2 3.75 0.1 0.85 - - -
Heat exchanger3 3.75 0.1 0.85 - - -
Furnace 0.75 0.0 1 - - -
Pressure vessel 1 1.275 - - - -
Tray (stabilizer) 1.7 - - - 0.0 1.4
Compressor 1 - - - - -
112
The results presented in Table (5.3) have obtained by using the feed
compositions and of test run two and the optimal operating conditions
which give the maximum RON and minimum OAUC are 524.314K,
2.406MPa, 1.507hr-1. The lowest RON (79.709) have been obtained from
once through process because there is no normal paraffins recycle or
branched paraffins by-pass is used which increase the equilibrium
conversion. Also, its cost (OAUC=10654036$) is low because there is no
increase in equipment capacity and utilities due to the recycle used
(Anderson et al., 2004).
Table (5.3): Economic and performance variables results of once through

process
variables Unit Value
OAUC $/yr 10653807
RON (-) 79.709
Yield (-) 97.552
5.6.2 Results of Deisopentanizer (DIP) Process (Case study 2)

OAUC cost of this scheme is calculated by the model presented in
section 5.3, taken into considering DIP cost which consists of the column
cost that is calculated used equations (5.14) to (5.19), heat exchanger cost
(is calculated by equation (5.36) and equations from (5.60) to (5.64)) and
reflux tank cost (is estimated by equations from (5.26) to (5.34)).
Maximum vapor rate ( ), tray spacing ( ) tray number ( ) are presented
in Table (5.4), and they are calculated by McCabe–Thiele method (Sinnott,
1999).
113
Table (5.4): DIP variables

Parameters Unit value
Kg/S 4.643
(-) 22
M 0.45
From the results presented in Table (5.5) and in comparison with case
one, addition of DIP to the base unit increases the RON (81.647) by 4.64%
due to increasing of normal pentane conversion, and OAUC (9390270$)
was decreased by 11.83% owing to reduce the equipments sizes, hydrogen
make up, catalyst amount, power and energy required.
Table (5.5): Optimal operating conditions, cost and performance variables

results of process with DIP
variables unit Value
OAUC $/yr 9390270.0
RON (-) 81.647
Yield (-) 97.78
T K 522.83
P MPa 22.61
LHSV 1.402
(-) 3.29
5.6.3 Results of Deisohexanizer (DIH) Process (Case study 3)

According to Domergue and Matthews (2001) with 65% recycling,
the installed equipment capital cost (IECC) of this process is equal to
2.4*IECC of the base once through process, and the operating cost as
mentioned previously.
114
Based on the results shown in Table (5.5) and comparison with case
one, increasing the RON (86.21) in this case leads to increase the OAUC
(17249371$) due to increase the capital and operating cost as a result of
increasing the feed stock by 26.36% in comparison with those in once
through process, beside the cost of DIH process.

results of process with DIH
variables unit Value
OAUC $/yr 17249371
RON (-) 86.21
Yield (-) 96.827
T K 524.65
P MPa 23.71
LHSV 1.429
(-) 3.21
5.6.4 Results of DIP and DIH Process (Case study 4)

As mentioned previous, the optimization process is completed
according to equation (5.1). The annual unit operating cost is estimated by
the same model presented previously, taking into account the change of the
feed flow rate and the composition. The same percentage of recycling in 3 rd
case is used here.
As proven and explained in case two and shown in Table (5.7), the use
of DIP has a positive effect on the maximum RON and minimum cost.
Using of DIP can reduce the OAUC (16184704$) by 6.19% in comparison
with case 3. Also the RON(88.292) increased by 2.082 compared with case
3 due to use DIP, so this feed stock composition and using of isomerization
115
process with DIP and DIH technologies is preferred in comparison the

isomerization process with DIH.

results of isomerization process with DIP& DIH
OAUC $/yr 16184704

RON (-) 88.292
Yield (-) 97.51
T K 523.4
P MPa 23.73
LHSV 1.493
(-) 3.847
5.6.5 Results of Ipsorb Process (Case study 5)

Total paraffin recycled is acquired with recycling 50% of the total
normal paraffin in the feed stock leading to increase the reactor feed stock
by 33% in comparison with once through process.
As shown in Table (5.8) bellow and in comparison with once through
process (case 1), the use of molecular sieve technique increases the RON
(88.273) of isomerizate by 8.81, but such increases is associated with high
OAUC (17641911$) due to high recycle rate although using of DIP that
decreases the recycle rate of normal paraffins.
116
Table (5.8): Optimal operating conditions, cost and performance

variables results of Ipsorb process.

OAUC $/yr 17641911
RON (-) 88.273
Yield (-) 97.27
T K 524.2
P MPa 23.5
LHSV 1.419
(-) 3.39
5.6.6 Results of Hexorb Process (Case study 6)

The results is accomplished using the mathematical model presented
in chapter three where the change of the rate and the composition of the
feed stock is taken into accounts. The total recycle of -hydrocarbons is
65% from the total -components in the feed stock at normal-pentane
recycling and the total recycling hydrocarbon recycling is 47.5% from total
feed stock.
As shown in Table (5.9), the RON (90.04) has increased by 1.767 in
comparison with previous case due to use DIH technique instead of DIP
that increases the recycle rate increasing the required capacity of molecular
sieve due to increasing of normal hexane recycle.
Due to the high increasing in the feed stock as a result of methyl
pentanes recycling, this scheme having the highest operating and capital
cost. Although having the highest optimized RON, such scheme exclusives
to laboratory scale owing to its high OAUC (22886940$) (Domergue and
Matthews, 2001).
117

results of Hexorb process.
OAUC $/yr 22886940

RON (-) 90.04
Yield (-) 96.89
T K 522.9
P MPa 23.82
LHSV 1.51
(-) 3.412
5.6.7 Results of Total Isomerization Process (TIP) (Case

study 7)
The streams temperatures were taken from Holcombe (1980), heat
capacities of liquid naphtha were taken from Gary et al. (2007), heat
transfer coefficient and the dimensionless factors were taken from
Douglas (1988). All these parameters are shown in Table (5.10) bellow,
which are necessary for this case.
Table (5.10): Values of coefficients and constant parameters used in this

process
Parameter unit Value Parameter unit Value

K 333 KW/ 0.432
K 313 KW/ 0.387
K 505 KW/ 0.913
K 537 KW/ 0.4
K 442 Kj/kg 274
Continued
118
K 405 Kj/kg 268

K 463 Kj/kg 317
K 288 Kj/ (kg.k) 2.531
K 313 Kj/ (kg.k) 2.522
K 333 Kj/ (kg.k) 2.481
K 298 Kj/ (kg.k) 2.388
K 603 Kj/ (kg.k) 2.388
Kg/S 0.6329 Kj/ (kg.k) 2.388
m 0.45 (-) 26
As noticed from the results presented in Table (5.11) bellow, it has

been observed that recycling 22 ton/hr of normal paraffins lead to increase
the value of RON (88.17). This scheme has an economic cost
(OAUC=19786370$) higher than Ipsorb process (17641911$) and lower
than Hexorb process (22886510$). This behavior is attributed as follows: In
Ipsorb process, the presence of DIP reduces the amount of recycled normal
paraffins, while in Hexorb process, the presence of DIH increases the
amount of recycled normal paraffins in addition to methyl pentanes recycle
by DIH.

results of TIP process

OAUC $/yr 19786370
RON (-) 88.17
Yield (-) 97.06
T K 521.72
P MPa 23.17
LHSV 1.498
(-) 3.18
119
5.6.8 Results of the Advanced Configuration (proposed in

this study)
The results of this new process suggested in this work are presented in
Table (5.12). The highest RON and highest yield are obtained by using
such advanced configuration process (ACP) in comparison with those
obtained by traditional method. Increasing in RON (90.72) ( belong to the
presence of benzene component in the final product that hydrogenated in
others technologies. While, increasing the yield (99.16) belong to decrease
the reactor feed stock rate by 48.34% weight percent than of once through
process.

results of ACP process.
Variables Unit Value

OAUC $/yr 15212319
RON (-) 90.72
Yield (-) 99.16
T K 520.8
P MPa 21.47
LHSV 1.526
(-) 3.34
Also, the minimum OAUC required (15212319$) in comparison with

others molecular sieve technologies is the lowest owning to reduce the feed
rate with leads to decrease the hydrogen make up, heating required, catalyst
and all equipments capacities as shown in Table (5.13).
111
Table (5.13): ACP, TIP and once through process comparison
ACP (this
variables TIP Once through
study, 2017)
Reactor feed rate (Ton/hr) 40.6 101.27 75.841
Heating required (kW) 5033.5 7099.1 5652.38

Reactor bed volume ( ) 39.25 89.64 74.20
Hydrogen make up (Ton/hr) 0.762 1.621 1.378
5.7 Heat Integration of the Advanced Configuration Using

a Pinch Technique)
For further optimal results for purpose of reducing the overall cost and
energy consumption in addition to maximizing the heat recovery, the heat
integration of the technical proposed related to the industrial isomerization
process is investigated here base on a pinch technology.
The heat integration for the advanced configuration is studied here to find
the optimal design of the heat exchanger network and minimum
temperature deference to get maximum heat recovery.
The process energy requirements can be reduce by using process
integration. In order to develop a method of energy recovery and the best
rearrangement of heat exchangers network, several efforts have been done
in recent decay (Gundepsen and Naess, 1988).
Linnhoff and Hindmarsh (1983) and other workers have developed
a pinch technology considering the most useful and successful technique.
When the temperatures are plotted various heat transferred of hot and cold
systems, a pinch often happen between the two stream curves. For
minimum requirements of energy, there is no heat that should be
transferred across the pinch.
111
5.7.1 Minimum Temperature Difference Calculation

In case 8 and according to pinch theory, there are six streams three hot
streams need to cool and three cold streams need to heat. Each stream starts
from temperature of source ( ) and then cooled or heated to target
temperature ( ) as shown in Table (5.14). The heat capacity CP (kW/ºC)
of each stream is given as follow:
CP=W*Cp …(5.96)
Where:
Cp: The heat capacity of stream, kJ/(kg.ºC)
W: mass flow rate of stream, kg/s
Table (5.14): Data required for heat integration problem
Stream CP (kW/ ºC) Heat

Type ,ºC ,ºC
number vapor / liquid load
1 Hot 60.95 32.66 57.42 305 40 21446.4

2 Hot 48.09 - - 305 250 2645
3 Hot 46.08 16 44.65 280 40 13877
4 Cold 60.32 32.66 57.2 40 305 23271
5 Cold 43.71 16 42.31 40 305 11703
6 Cold 13.98 - - 70 305 3284
By using the data in Table (5.14) and following the procedure presented by
Linnhoff and Hindmarsh (1983), Figure (5.11) is plotted.
112
50000
45000
40000
35000
enthalpy kw 30000
25000
hot curve
20000
cold curve
15000
10000
5000
0
0 100 200 300 400
temperature °C
Figure (5.13): Cold and Hot streams composite curves
From plot of composite streams in Figure (5.12) above, the pinch

acquires between 190ºC on the hot stream and 177ºC on the cold stream
with minimum temperature difference equals to 13ºC.
5.7.2 The Heat Exchanger Network Design

The analysis carried out in Figure (5.12) has shown that the pinch
occurs where the cold streams are at 177ºC and the hot 190ºC. Figure
(5.13) is shown the grid representation of the six streams, the dotted
vertical lines represent the pinch and they separate the grid into two regions
below and above the pinch (Linnhoff and Hindmarsh, 1983).
190 177 CP(,W/ºC
305 40
150.1
1
305 250
48.09
2
280 40
106.7
3
305 40
149.9
4
305 40
104.8
5
305 70
13.98
6
Figure (5.14): Grid of the six streams
113
The maximum recovery of energy is obtained if no cooling is utilized

above the pinch. This mains that the heat capacity of hot stream should be
equal to or less than heat capacity of the cold stream above the pinch, and
equals to or high than heat capacity of the cold stream below the pinch.
According to values of heat capacities, stream 1 is matched with stream 4,
stream 2 is matched with stream 6 and stream 3 is matched with stream 5.
Due to the equality of CP values for stream 1 with stream 4 and stream 3
with stream 5, same network design is used below and above the pinch.
The heat duty is calculated by following equation:
…(5.97)
i: N.O. stream.
* The matching of steams 1 and 4:
 The heat required to rise temperature of stream 4 from 40ºC to 305ºC
equal to 21922.2kW
 The transferring heat required to bring stream 1 to 40ºC is equal to
21308.28kW.
20461.40kW.
 Heating required for stream 4 =21922.2-20461.4=1460.8kW.
 Cooling required for stream 1=21308.28-20461.4=846.88kW.
 The full amount of heat transferring from stream 2 to stream 6 is equal to
1883.64kW.
 The heat required to bring stream 6 to target temperature is equal to
3284.96 kW.
 Heating required for stream 6 =1401.36 kW.
114
 The heat required to rise temperature of stream 5 from 40ºC to 305ºC

equal to 14974.8 kW.
13976.23 kW.
13395.78 kW.
 Heating required for stream 5 =14974.8-13395.78=1579.02 kW.
 Cooling required for stream 3 =13976.23-13395.78=580.45 kW.
The results above are represented by the network presented in Figure
(5.13).
847kW
305 40 CP,(W/ºC)
1 150.1
305 250 48.09

2
580 kW
280 40 106.7
3
1460 kW
305 40 149.9
4
1579 kW
305 40 104.8
5
1401kW
305 70 13.98
6
Figure (5.15): Proposed heat exchanger network
According to the network shown above, the flow diagram of ACP

((Figure (5.7)) is modified by adding a heat exchanger equipment before
the second furnace (F2) that re duce the heat duty supply to 6 th stream in
Figure (5.14). Figure (5.15) presents the modifying flow diagram of ACP.
115
E 205
Gas
E E-11
207
S201 S202 F
202
E-18
F
201
feed
E
E-17
E-16 E-15
E-14 E
201 E 202
E
206
E-19 203
E E-20
206 E202&204
isomerizate
Figure (5.16): Modifying flow diagram of ACP
5.7.3 Optimization Problem For Heat Saving Process

According to the equations (5.1) utilizing the mathematical model
presented previously and applying the optimal kinetic parameter obtained
in the last chapter, also using modifying flow diagram, the optimization
problem are stated as:
Given Initial concentration, kinetic parameters, reactor

configuration, process specifications
Determine initial temperature, pressure, LHSV and hydrogen to
hydrocarbon mole ratio.
So as to OBJ (RON& yield maximize, OAUC& minimize)
maximize
Subjected to Process constraints and linear bounds on all decision
variables.
116
The optimization problem for each isomerization technology are written as:
max
P, T, LHSV,
s.t f(x(z),u(z), v) = 0 (model equation, equality constraint)
5.7.4 Optimal Economic Cost of the Modifying ACP Flow

Diagram
After getting the best design of heat exchanger network, the OAUC is
estimated by optimization technique using equation (5.1) and the same
procedure used in the case 8. The optimization process is accomplished
with a minimum temperature difference got from the heat integration
process and taking into account the addition of heat exchanger E207.
Table (5.15) presents the results of optimization problem that showing

positive effect of heat exchanger E207 add and where temperature
difference has reduced by minimizing the OAUC owning to minimize the
heating and cooling amount required in comparison with the results without
heat integration. Also, the RON due to slightly increases in the temperature
and decreasing the LHSV. The cost saving owning to use heat integration is
2.905% as a result to reduce the total heating required by 11.465% and total
cooling required by 8.94%. The new design achieved heat saving of 25.2%
in comparison with the advanced configuration before make heat saving.
117
Table (5.15): Optimal performance, cost and operating conditions of

optimization problem for modify ACP
Value
variables Symbol unit With heat Without heat
integration integration
OAUC OAUC $/yr
14770103 15212319
Total heating required QH kW 4449.83 5027.4
Total cooling required QC kW 2736 3007
RON RON (-) 90.93 90.72

Isomerizate Yield Yield (-) 99.03 99.27
Initial temperature T K 520.84 520.8
Reactor pressure P MPa 21.09 21.47
LHSV LHSV 1.460 1.526
H2/HC mole ratio mr (-) 3.37 3.34
Energy saving Es (-) 25.2
5.8 Summary
1- Once through process gives the lowest RON due to low conversion of
normal paraffins and its OAUC is the lowest in comparison with other
schemes.
2- Adding DIP to once through process leads to increase RON by 1.94 due
to increase the conversion of normal pentane. This scheme has the lowest
OAUC due to high percentage of Iso-pentane by-pass.
3- Addition of DIH to once through process increases RON by 6.38 due to

increase the yield of 2,2-DMB and 2,3-DMB, and such increasing of RON
is accompanied by high OAUC due to high recycle of C 6 components.
118
4- Addition of DIP and DIH together increases RON by 9.2 in comparison

with once through process and by 2.58 in comparison with DIP, this
increasing of RON is accompanied by decreasing in OAUC due to DIP
adding.
5- Ipsorb process has RON and OAUC almost as the same as for the
scheme with DIH and DIP because the two schemes having almost the
same recycle rate.
6- Total isomerization process (TIP) has RON is almost equal to RON of

Ipsorb process but its OAUC is higher due to use of DIP in Ipsorb process.
7- Hexorb process has the highest RON until this research and the highest
OUAC due to high recycle of normal paraffins and methyl pentane.
8- Advanced configuration process proposed here via employing only

naphtha containing benzene less than 0.62wt% giving the highest RON and
yield and lowest OAUC has obtained.
9- The heat integration of ACP has improved the process suggested and can
reduce the OUAC using minimum energy consumption and maximum heat
recovery.
119
Chapter Six Conclusions And Recommendations
CHAPTER SIX
CONCLOSIONS AND
RECOMINDATIONS
Chapter Six
Conclusions and
Recommendations
6.1 Conclusions
This work can briefly be described by the following conclusions:
 Isomerization process of light naphtha has been simulated and

optimized via a complete mathematical model using continuum type
to predict the performance of the isomerization fixed bed reactor at
Baiji north refinery. The operating variables of the reactor, with
Zeolite catalyst and gases feed stocks, are as same as those of
isomerization reactor at Baiji north refinery with the following
ranges: temperature (523-527 K), pressure (2.3-2.5 MPa), liquid
hourly space velocity (1.489-1.622 hr-1) and hydrogen to
hydrocarbons mole ratio (3.2-3.4 mol H2/mol HC).
 An accurate values of the kinetic parameters has been estimated via
optimization technique and a non-linear approach based on the
experimental results was employed from Biji north refinery. The
kinetic parameters was estimated based on minimize the square
between the predicted and experimental results with absolute error
less than 0.1% among all results.
 The analysis of operating variables showed that the isomerization
unit operates with an optimal ranges of temperature, pressure, H2/HC
mole ratio and LHSV for such feed stock composition and the type of
catalyst used.
121
 The optimal zone of isomerization reactor operations is affected by

the feed stock composition, (ratio of n-C5/i-C5 increases the
temperature within the catalyst bed will rise) and such situation
requires decreasing of the inlet feed stock temperature to reach the
new optimal operation temperature.
 The isomerization technologies was optimized based on maximizing
the RON and isomerizate yield, and minimizing of economic cost. It
is found that the addition of DIP for with each scheme has a positive
effect on the RON and yield maximize and cost minimize.
 A new configuration process (ACP) has proposed in this study all has
given the maximum RON and isomerizate yield and minimum
economic cost in comparison with other molecular sieve technologies
for such feed stock and catalyst.
 Advanced configuration process (ACP) is only used the feed stock
content of the benzene lees than 0.62 Wt%.
 It is important issue to use pinch technique to find the minimum
temperature difference for heat transfer equipments and design of
heat equipment network for farther optimal design of such process.
121
6.2 Recommendations
 Optimize other technologies of separation.

 Applying other types of the catalyst with the advanced
configuration process proposed here.
122
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(2006). Parameter estimation in continuous-time dynamic
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Rackett, H. G. (1970). Equation of state for saturated liquids. Journal of

Chemical and Engineering Data, 15, 514-517.
Rosales-Quitero, A. & Vargas-Villamil, F. (2009). On the multiplicities

of a catalytic distillation column for the deep
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Optimization for an Industrial Penex Isomerization Unit: A Case
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Heinemann.
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Volkova, G., S. Reshetnikov, et al. (2007). "n-Hexane skeletal

isomerization over sulfated zirconia catalysts with different
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Watanabe, K., Kawakami, T., Baba, K., Oshio, N. & Kimura, T. 2004.
Simultaneous isomerization and desulfurization of sulfur-
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Watanabe, K., Kawakami, T., Baba, K., Oshio, N. & Kimura, T. (2008).
Effect of metals on the catalytic activity of sulfated zirconia for
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24.
Weinert, J. X., Shaojun, L., Ogden, J. M. & Jianxin, M. (2007). Hydrogen

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131
Appendix A gPROMS Software
APPENDIX A
A.1 Computational gPROMS Software

Many of softwares have advantages a large application in operation
industry, such as modeling, simulation and optimization. Advanced
languages of simulators have advanced and formalisms to enhance the
model used, which allow the description of difficult differential and
algebraic models.
A process simulator has the ability to input and modify the
configuration of the process flow sheet and to perform design evaluations
considering the complete process flow sheet before they are tried on the
real plant. This way is possible to model and predict the behavior of the
process flowsheet and to study different operation scenarios (such as
various feed stocks, high flowrates, modified operating conditions, etc.).
Examples of commercially available operation simulators, which can be
employed for modeling chemical operations, are: ASPEN PLUS by Aspen
Technology, CHEMCAD by Chem. Stations, HYSYS by hyprotech ltd.,
gPROMS by Process Systems Enterprise ltd., etc. (Jarullah, et al., 2011).
A.2 Advantages of gPROMS Software

In this model gPROMS software was used to solve and optimize
equations that described in CHAPTER THREE and CHAPTER FIVE due
to the advantages of this software in estimating kinetic parameters of the
model, that can be summarized as follow:
 gPROMS program software can handles a large number of algebraic,
differential, and partial differential equations (approximately more
than 100,000 algebraic and differential equations).
 gPROMS simulator can handles the reversible-irreversible,
continuities, discontinuities and direct systems.
 Equations of physical system can be written as they appear or books
i.e. without reformulation.
131
 gPROMS allows using a single equipment model(described several

equations) for multiple operating procedures (process) and single
process used for several optimization tasks.
 gPROMS can describes single or multi- dimensional arrays of both
variables and equations either implicitly or explicitly. All variables,
other than those that are functions of time only, can be featured as
distributions over one or more continuous and/or discrete domains.
 gPROMS allows simultaneous optimization of equipment sizes and
operating procedures that saves capital and operational cost in long
run.
All these advantages of gPROMS mentioned above can reduce time
and numerical expertise to perform model-based activities and assist the
user. It can easily link to external components, for example, physical
properties packages or control system software.
132
A.3 Model Application on gPROMS

An overview of the gPROMS environment at start up is shown in
Figure (A.1).
Figure (A.1): An overview of the gPROMS environment at start up
There are number of entries as shown in the left hand pane of the
Figure (A.1) are:
 Variable Types
 Stream Types
 Models
 Tasks
 Processes
133
 Optimizations
 Parameter Estimations
 Experiments
 Saved Variable Sets.
Any one of these entries represents a group of gPROMS entities. Only
four of these sections were used in this work which, are VARIABLE
TYPES (In this entity the type and range of the variables used in the
oxidation model are specified). MODELS entity (isomerization of light
naphtha model are written in this entity, which described previously by a
set of differential and algebraic equations). PROCESS entity (This entity
contains specification for the simulating oxidation process)
OPTIMIZATION entity (optimizing the oxidation process is written in this
entity). Figure (A.2) represents an overview of gPROMS:
Figure (A.2): An overview of gPROMS builder
134
A.4 Model Entity

As mentioned previously, the model section is where a process model
(set of differential and algebraic equations are written). In gPROMS a
model file can be divided into three sections: PARAMETERS,
VARIABLES and EQUATIONS. A brief description of these sections are
shown below.
A.4.1 Defining Parameters

Three types of parameters, which are REAL, INTEGER and LOGIC.
In this section where the parameters of model are declared. The values of
these parameters are constant, unchanged and cannot be evaluated by the
simulation. Below are some examples of the parameters used in the model
and declared in gPROMS model file as:
L AS REAL
L is the parameter used in this model in gPROMS that, refer to the

length bed of catalyst and universal gas constant respectively. The word
REAL means the real value of the parameter and the word INTEGER refers
to the integer values. This can be showing in gPROMS as illustrated in
Figure (A.3).
A.4.2 Defining Variables

All the variables of the model can be declared in this section. The
values of these variables may be assigned or calculated by the simulation
and, this depend on the model. All variables types must declare and define
in the variable type section. Temperature and concentration as an example
used in trickle bed reactor model which, has been declared in the model
entity as:
135
T AS TEMPERATURE
C1, C2, C3, C4 AS CON
This can be describe in gPROMS as shown in Figure (A.3).
Figure (A.3): Illustrated of parameters and variables in gPROMS
Other variables used here in gPROMS language such as E1, A1, K1, m and
n which, describe activation energy, per-exponential factor, effectiveness
factor, Thiele Modulus, order of hydrocarbons and hydrogen concentration
respectively. The variable type is defined in the Variable Types folder as
shown in Figure (A.4)
Figure (A.4): An overview of variable type in gPROMS program.
136
A.4.3 Defining Equations

In gPROMS code all the model equations are written (which are sets
of differential and algebraic equations). An example of differential
equation illustrated in this model is the mass balance equation for normal
pentane in gas phase (mentioned by equation (3.1)) with energy balance of
heat exchanger 1 are shown in Figures (A.5) and (A.6):
Figure (A.5): illustrate of differential equation entry in gPROMS
137
Figure (A.6): Illustrate of energy balance equations entry in gPROMS
A.5 Process Entity

In the Processes entity, all the characteristics needed in the
isomerization model are defined for running the simulation. Process entity
consist of sections that contain necessary information to define simulation
activity. The major sections of the process entity used to carry out
simulation of this work are:
 UNIT
 SET
 ASSIGN
 INITIAL
 SOLUTION PARAMETERS
 SCHEDULE
138
In each part of these sections mentioned above a specific role is used to run
the simulation of the model, a brief description of each section can show
below:
 The Unit Section

In the unit section, the specific item of equipment to which the process
files refers to is indicated. Equipment items are declared as instances of
MODELs.
 Set Section
In this section, the values of the parameters declared under the
PARAMETERS section in the model file are assigned. For example, the
value of the universal gas constant (R), is assigned under the SET section as
shown in Figure (A.7).
Figure (A.7): Over view of unit and set sections
 The Assign Section

In the ASSIGN section, degrees of freedom, the input parameters to
the model are specified. In a typical model, the number of variables is
generally more than the number of equations. In order to make the number
of equations equal to the number of variables to avoid over or under
139
specifying the system, some the further variables are assigned in this part.
For example, in the kinetic model for the isomerization process, the
variables assigned in the ASSIGN section are the order of the hydrocarbons
concentration, order of oxygen concentration, pre-exponential factor and
activation energy as shown below and other parameters as shown in Figure
(A.8).
Figure (A.8): Over view of assign section
 The Initial Section:

A model is used to describe the oxidation process that consist of a sets
of differential and algebraic equations. So, it is known every differential
equation needs to specify an initial value to solve it. In the models of
isomerization reaction used in this work, the initial conditions are the values
of the differential variables at volume v = 0. In gPROMS to specify an
initial condition the INITIAL Section considered apart used to specify
141
initial Conditions for the differential equations. Actually, the initial

condition is assigned a as fixed value, it is not easy to do this condition in
gPROMS. INITIAL Section a part used for this purpose, which treats an
initial condition as general equation used to evaluate an initial state rather
than assigned a fixed value.
 The Solution Parameters Section:

The SOLUTION PARAMETERS section of the PROCESS allows the
specification of parameters of the results and mathematical solvers for each
type of activity (simulation, optimization and parameter estimation). As the
number of solvers and sub solvers available in gPROMS for the solution of
simulation, optimization and parameter calculation activities for both steady
state and dynamic models are enormous. The model developer defines
141
mathematical solver and output specifications for the process output.

Output specifications are utilized for display results in EXCEL and
gPROMS using the keyword gExcel Output and gPROMS, respectively.
The gExcel Output opens a Microsoft Excel file that displays the results of
the simulation, whereas in the gPROMS, the results are sent to the internal
gPROMS results management system.
There are three standard mathematical solvers for the solution of sets
of nonlinear algebraic equation in gPROMS, mainly BDNLSOL, NLSOL
and SPARSE:BNDLSOL (Block Decomposition Non Linear solver).
NLSOL is nonlinear solver, with and without block decomposition.
SPARSE is sophisticated implementation of Newton-type method block
decomposition. Two mathematical solvers (DASOLV and SRADAU) solve
mixed sets of differential and algebraic equations in gPROMS. A SRQPD,
which employs a Sequential Quadratic Programming (SQP) method for the
solution of the Non Linear Programming (NLP) problem that has been used
in this work for isomerization reactions mode. An example the SOLUTION
PARAMETERS section represented as shown in Figure (A.10):

142
A.6 Optimization Entity

In the optimization entity, the parameters for steady state or dynamic
optimization problems are specified. In several cases, the values are
expressed in the form: [guessed value, lower bound, upper bound]. Some of
the specifications for the optimization process involve the length horizon or
time horizon for the process, the number of intervals, the numerical values
of the intervals, the values of the control variables within the intervals and
the end point constraints. The objective function to be maximized or
minimized is also specified within the optimization file. A part of the
gPROMS optimization file for the kinetic model of isomerization reactions
is shown in Figure (A.11).
Figure (A.11): Optimization file in gPROMS for the kinetic model of

isomerization process
143
‫الخالصت‬
‫بغبب انًحذداث انب‪ٛ‬ئ‪ٛ‬ت انصبسيت انًفشٔضت عهٗ ٔصٕد كم يٍ انعطش‪ٚ‬بث ٔ االٔنف‪ُٛ‬بث ٔ سابع‬
‫ار‪ٛ‬الث انشصبص ف‪ ٙ‬انبُض‪ ٍٚ‬نٕحع ف‪ ٙ‬انغُٕاث االخ‪ٛ‬ش ص‪ٚ‬بدة االعخًبد عهٗ انبُض‪ ٍٚ‬انُبحش يٍ‬
‫عًه‪ٛ‬ت االصيشة‪ .‬ح‪ٛ‬ذ حعخبش حكُهٕص‪ٛ‬ب االصيشة بغ‪ٛ‬طت ٔيضذ‪ٚ‬ت اقخصبد‪ٚ‬ب إلَخبس ٔقٕد َض‪ٛ‬ف ٔ رٔ‬
‫عذد أكخبَ‪ ٙ‬عبن‪.ٙ‬‬
‫ف‪ْ ٙ‬زا انبحذ‪ ,‬حى دساعت اخخ‪ٛ‬بس انخصً‪ٛ‬ى االيزم نعًه‪ٛ‬ت االصيشة اعخًبداً عهٗ يٕد‪ٚ‬م س‪ٚ‬بض‪ٙ‬‬
‫حذ‪ٚ‬ذ قبئى عهٗ اعظ انُٓذعت انك‪ًٛ‬بٔ‪ٚ‬ت يشخًال عهٗ كم يٍ يٕاصَت انًبدة ٔانطبقت‪ .‬نخحغ‪ ٍٛ‬اداء‬
‫يفبعم ٔحذة االصيشة ف‪ ٙ‬يصفٗ ب‪ٛ‬ض‪ .ٙ‬كًب اٌ انظشٔف انخشغ‪ٛ‬ه‪ٛ‬ت انًغخخذيت ْ‪ ٙ‬ضًٍ انًذ‪ٚ‬بث‬
‫انًعًٕل بٓب ف‪ٔ ٙ‬حذة االصيشة نًصفٗ ب‪ٛ‬ض‪ ٙ‬أنشًبن‪ ٙ‬دسصت انحشاسة (‪ 527-523‬كهفٍ)‪ ,‬انضغظ‬
‫(‪ 25-23‬ي‪ٛ‬ضب ببعكبل)‪ ,‬عشعت انغبئم انفشاغ‪ٛ‬ت (‪ 1.622-1.489‬عبعت‪َ ٔ )1-‬غبت انٓ‪ٛ‬ذسٔص‪ٍٛ‬‬
‫انٗ انٓ‪ٛ‬ذسٔكشبَٕبث (‪ ٔ .)3.4-3.2‬ببعخخذاو انض‪ٕٚ‬ال‪ٚ‬ج كعبيم يغبعذ‪.‬‬
‫حى ا‪ٚ‬ضبد افضم انًعبيالث انحشك‪ٛ‬ت ٔ انخ‪ ٙ‬ححقق َغبت خطبء اقم يٍ ‪ %0.1‬ب‪ ٍٛ‬ب‪ٛ‬بَبث انُغب‬
‫انٕصَ‪ ٛ‬ت ٔ دسصبث انحشاسة انعًه‪ٛ‬ت انًأخٕرة يٍ انٕحذة االصيشة نًصفٗ ب‪ٛ‬ض‪ ٙ‬انشًبن‪ٔ ٙ‬انب‪ٛ‬بَبث‬
‫انُظش‪ٚ‬ت انُبحضت يٍ عًه‪ٛ‬ت االعخًزبل‪.‬‬
‫كًب حى دساعت ك‪ٛ‬ف‪ٛ‬ت سفع عذد األٔكخبٌ ٔ ص‪ٚ‬بدة االَخبص‪ٛ‬ت ببعخخذاو حقُ‪ٛ‬بث انفصم كأبشاس انخقط‪ٛ‬ش‬
‫ٔانًُبخم انضض‪ٚ‬ئ‪ٛ‬ت ‪ ,‬ح‪ٛ‬ذ ‪ٚ‬خى عًم ايخزبل نغبع حصبي‪ٛ‬ى ٔيقبسَت َخبئضٓب يٍ ح‪ٛ‬ذ انعذد االٔكخبَ‪ٙ‬‬
‫ٔ االَخبص‪ٛ‬ت ٔانخكهفت أالقخصبد‪ٚ‬ت‪ .‬ا‪ٚ‬ضب حى اعخحذاد حصً‪ٛ‬ى صذ‪ٚ‬ذ نعًه‪ٛ‬ت االصيشة خالل ْزِ انذساعت‬
‫‪ًٚ‬كٍ حطب‪ٛ‬قّ ارا كبَج َغبت انبُض‪ ٍٚ‬انحهق‪ ٙ‬اقم يٍ ‪ %0.62‬ف‪ ٙ‬خظ انخغز‪ٚ‬ت‪ْ .‬زا انخصً‪ٛ‬ى اعطٗ‬
‫اَخبص‪ٛ‬ت اعهٗ (‪ٔ )99.3‬عذد أكخبَ‪ ٙ‬اعهٗ (‪ٔ )90.93‬بخكهفت اقم يٍ بق‪ٛ‬ت انخصبي‪ٛ‬ى‬
‫االخشٖ )‪ 14770103‬دٔالس\عُت) ٔانخ‪ ٙ‬حخضًٍ اعخخذاو انًُبخم انضض‪ٚ‬ئ‪ٛ‬ت‪ .‬كًب حى عًم حكبيم‬
‫حشاس٘ نهٕحذة نخحق‪ٛ‬ق اقم اعخٓالك ٔ اعهٗ اعخشداد نهطبقت ٔيٍ اصم انحفبظ عهٗ انب‪ٛ‬ئت‪.‬‬
‫وزارة التعليم العالي والبحث العلمي‬
‫جامعت تكريت‬
‫كليت الهندست‬
‫التصميم والتشغيل االمثل لعمليت االزمرة‬
‫سعبنت يقذيت انٗ‬
‫صبيعت حكش‪ٚ‬ج ‪ /‬كه‪ٛ‬ت انُٓذعت‬
‫كضضء يٍ يخطهببث َ‪ٛ‬م دسصت انًبصغخ‪ٛ‬ش‬
‫ف‪ ٙ‬عهٕو انُٓذعت انك‪ًٛٛ‬بٔ‪ٚ‬ت‬
‫يٍ قبم‬
‫احًذ يحًذ احًذ‬
‫بكبنٕس‪ٕٚ‬ط ف‪ ٙ‬انُٓذعت انك‪ًٛٛ‬بٔ‪ٚ‬ت‬
‫بأششاف‬
‫أ‪.‬و‪.‬د‪ .‬ا‪ٚ‬غش طبنب صبس هللا‬
‫أ‪.‬د‪ .‬ف‪ٛ‬بض يحًذ عبذ‬
‫‪2017‬و‬ ‫‪ْ1473‬‬

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Ministry of Higher Education and Scientific Research

Optimal Design and Operation of

A THESIS SUBMITTED TO THE

Ahmed Mohammed Ahmed

‫َ‬ ‫َّ‬ ‫ُ ْ َ َْ ْ َ‬ ‫َ َ َ َ ْ ُ َ ْ َ َ َ ِّ‬ ‫ْ‬

We certify that this thesis entitled "Optimal Design and Operation of

Asst. Prof. Dr. Aysar T. Jarulla Prof. Dr. Fayad M. Abed

In view of the available recommendation, I forward this thesis

is adequate for the award of degree of (Master of Science in Chemical

Asst. Prof. Dr. Aysar T. Jarullah Prof. Dr. Fayadh M. Abed

Prof. Dr. Ammar S. Abbas

Approved by the Council of the College of Engineering/ University of

Prof. Dr. Fayadh M. Abed

Dean of College of Engineering

Owing to the strict environmental regulations that request lower

The optimal isomerization process of naphtha is studied here by a

The optimal values of the kinetic parameters of the relevant process is

Based on the analysis of the operating variables, the results indicated

Increasing the research octane number (RON) has also been

The heat integration of the advanced configuration process of the

very thankful for them.

I'd like to thank all my lecturers and professors in Chemical Engineering

Department, College of Engineering at Tikrit University for their patience

and continuous support.

On a personal side, my appreciation to my parents. They are always

I dedicate this thesis to my parents

CHAPTER2 – Literature Review

2.7.2 Zeolitic Catalysts 17

CHAPTER 3 – Mathematical Modeling of an Industrial

3.4.6 Flow Rate of Raw Material 39

CHAPTER 4 – Results and Discussion

CHAPTER 5 – Isomerization Configurations

5.2.5 Ipsorb Process 77

5.6.4 Results of DIP and DIH Process (Case study 4) 105

5.7.2 The Heat Exchanger Network Design 113

CHAPTER6- Conclusions And Recommendations

6.1 Conclusions 120

A.1 Computational gPROMS Software 131

Table (1.1): Properties of normal and iso-paraffins 2

Table (4.9): The comparison between the experimental 64

Figure (2.1): Effect of temperature on the conversion of n- 11

Figure (4.5): Effect of LHSV on RON at constant temperature 70

Figure (A.5): illustrate of differential equation entry in gPROMS 137

Symbol Description Unit

a Catalyst activity (-)

A Pre-exponential factor (mol/m3)1-nhr-1

As cross section area of vapor flow rate

At Total area of heat exchangers

At1 Area of heat of E201

At2 Area of heat of E202

At3 Area of heat of E203

At4 Area of heat of E204

At5 Area of heat of E205

At6 Area of heat of E206

At7 Area of heat of E207

AUCC Annual unit capital cost $/yr

AUOC Annual unit operating cost $/yr

Β is a total deviation of hydrocarbons octane number (-)

CAd Adsorber capital cost ($)