2560

Report on Best Available Techniques (BAT)
in
Copper Production
FINAL DRAFT
Deutsch-Französisches Institut für Umweltforschung (DFIU)

French-German Institute for Environmental Research
University of Karlsruhe (TH)
o. Prof. Dr. O. Rentz
Dipl.-Ing. Martin Krippner, Dipl.-Ing. Stephan Hähre,
Dr. Frank Schultmann
Karlsruhe, March 1999
On behalf of the German Federal Environmental Agency, Berlin (UBA)

in the frame of the Research Project 109 05 006
Contents 221
CONTENTS
0 PREFACE ....................................................................................................................................................... 231
1 GENERAL INFORMATION........................................................................................................................ 233

1.1 PRODUCTION AND USE OF COPPER ............................................................................................................. 233
1.2 FIRST INDICATION OF ENVIRONMENTAL CONCERNS REGARDING THE PRODUCTION OF COPPER .................. 235
1.2.1 Emissions into the atmosphere.......................................................................................................... 235
1.2.2 Potential releases into water............................................................................................................. 236
1.2.3 Solid materials generated ................................................................................................................. 237
2 APPLIED PROCESS TECHNOLOGY AND ABATEMENT TECHNIQUES IN COPPER

PRODUCTION.................................................................................................................................................. 239
2.1 INTRODUCTION AND SCOPE OF THE STUDY................................................................................................. 239
2.2 BASIC DESCRIPTION OF COPPER PRODUCTION ............................................................................................ 240
2.2.1 Primary copper production............................................................................................................... 240
2.2.2 Secondary copper production ........................................................................................................... 252
2.2.3 Further processing of copper cathodes ............................................................................................ 262
2.2.4 Plants for copper production and further processing of copper cathodes........................................ 266
3 PROCESS TECHNOLOGY, ABATEMENT TECHNIQUES AND PRESENT

CONSUMPTION/EMISSION LEVELS IN GERMAN COPPER PRODUCTION ................................... 270
3.1 COPPER PRODUCTION AT NORDDEUTSCHE AFFINERIE AKTIENGESELLSCHAFT........................................... 270
3.1.1 Primary smelting plant ..................................................................................................................... 272
3.1.2 Secondary smelting plant.................................................................................................................. 277
3.1.3 Electrolysis plant for primary and secondary copper....................................................................... 283
3.1.4 Characteristics of fabrics filters at NA ............................................................................................. 285
3.1.5 Further processing of copper at NA ................................................................................................. 287
3.1.6 Waste water treatment plant ............................................................................................................. 289
3.1.7 Summarised data on outputs and environmental concerns at NA .................................................... 290
3.2 SECONDARY COPPER PRODUCTION AT HÜTTENWERKE KAYSER AG.......................................................... 293
3.2.1 Blast furnaces ................................................................................................................................... 294
3.2.2 Scrap converters (Pierce-Smith type) ............................................................................................... 298
3.2.3 Reverberatory anode furnaces .......................................................................................................... 299
3.2.4 Electrolysis plant .............................................................................................................................. 300
3.2.5 Electrolyte purification ..................................................................................................................... 301
3.2.6 Tin-lead alloy plant........................................................................................................................... 302
3.2.7 Characteristics of fabric filters at HK............................................................................................... 303
3.2.8 Waste water treatment ...................................................................................................................... 304
3.2.9 Summarised data on outputs and environmental concerns at HK .................................................... 304
3.3 COPPER PRODUCTION AT MANSFELDER KUPFER UND MESSING GMBH, HETTSTEDT ................................ 306
3.3.1 Blast furnace ..................................................................................................................................... 307
3.3.2 Converter .......................................................................................................................................... 310
3.3.3 Anode plant....................................................................................................................................... 312
3.3.4 Electrolytic plant............................................................................................................................... 315
3.3.5 Characteristics of fabric filters at MKM........................................................................................... 315
3.3.6 Further processing of copper at MKM ............................................................................................. 316
3.3.7 Summarised data on outputs and environmental concerns at MKM ................................................ 316
3.4 FABRICATION OF WIRE ROD AT FRIEDRICH KEMPER GMBH & CO KG, DUISBURG AND LACROIX & KRESS
GMBH, BRAMSCHE ......................................................................................................................................... 318
222 Contents
3.5 FABRICATION OF SEMI-FINISHED PRODUCTS FROM COPPER AND COPPER ALLOYS ...................................... 320
3.5.1 Melting .............................................................................................................................................. 321
3.5.2 Casting .............................................................................................................................................. 325
3.5.3 Fabrication of Sheet and Strip.......................................................................................................... 326
3.5.4 Fabrication of Copper and Copper Alloy Tubes, Rods and Sections ............................................... 330
3.5.5 Waste water treatment ...................................................................................................................... 333
3.5.6 Summarised data on outputs and environmental concerns of the fabrication of semi-finished products
................................................................................................................................................................... 334
4 GERMAN CANDIDATE BEST AVAILABLE TECHNIQUES (BAT) FOR INTEGRATED

POLLUTION PREVENTION AND CONTROL IN THE COPPER PRODUCTION ............................... 340
4.1 GENERAL PROVISIONS AND REQUIREMENTS FOR THE PREVENTION AND CONTROL OF ENVIRONMENTAL
POLLUTION....................................................................................................................................................... 341
4.1.1 Monitoring of emissions.................................................................................................................... 341
4.1.2 Techniques to prevent and control emissions into the atmosphere................................................... 344
4.1.3 Water management ........................................................................................................................... 348
4.1.4 Management of by-products and wastes........................................................................................... 350
4.1.5 Energy aspects .................................................................................................................................. 352
4.1.6 Noise aspects/abatement techniques ................................................................................................. 353
4.1.7 Plant safety aspects........................................................................................................................... 354
4.1.8 Plant operation and decommissioning.............................................................................................. 355
4.2 ................................................................................................................................................................... 356
4.2 CANDIDATE BAT FOR COPPER PRODUCTION ............................................................................................. 356
4.2.1 Smelting and converting (primary plant).......................................................................................... 359
4.2.2 Fire refining including anode casting (primary plant) ..................................................................... 359
4.2.3 Smelting of sulphur containing raw materials (secondary plant)..................................................... 360
4.2.4 Converting (secondary plant) ........................................................................................................... 360
4.2.5 Smelting of oxidic raw materials (secondary plant) ......................................................................... 361
4.2.6 Converting of scrap (secondary plant) ............................................................................................. 361
4.2.7 Fire refining (secondary plant)......................................................................................................... 362
4.2.8 Electrolytic refining (primary and secondary plant) ........................................................................ 363
4.2.9 Auxiliary plants................................................................................................................................. 363
4.2.10 Fabrication of semi-finished products from copper and copper alloys .......................................... 366
5 REFERENCES ............................................................................................................................................... 368
6 ANNEX............................................................................................................................................................ 374
6.1 INFORMATION ON CURRENT LEGISLATION RELEVANT TO THE COPPER PRODUCTION INDUSTRY.................. 374
6.1.1 Introduction ...................................................................................................................................... 374
6.1.2 Regulations on a German level......................................................................................................... 374
Contents 223
LIST OF FIGURES
Figure 1-1: Main fields of application of copper products in Germany............................................................... 234
Figure 1-2: Average service life of copper materials in various applications ...................................................... 235
Figure 2-1: Primary copper production route ...................................................................................................... 242
Figure 2-2: Pierce-Smith converter...................................................................................................................... 247
Figure 2-3: Double absorption contact plant ....................................................................................................... 248
Figure 2-4: Reverberatory furnace plant for anode production (example for a plant having a tiltable furnace) .. 249
Figure 2-5: Flowsheet for secondary copper production ..................................................................................... 253
Figure 2-6: Treatment of blast furnace off-gas (secondary copper production)................................................... 256
Figure 2-7: Wire rod plant ................................................................................................................................... 262
Figure 2-8: Basic concept of the CONTIROD process........................................................................................ 263
Figure 2-9: General flowsheet of semi-finished product fabrication ................................................................... 264
Figure 2-10: Principle of continuous or discontinuous casting............................................................................ 265
Figure 2-11: Locations of copper producing plants in Germany ......................................................................... 268
Figure 3-1: Copper production at Norddeutsche Affinerie Aktiengesellschaft.................................................... 271
Figure 3-2: Treatment of Outokumpu flash smelting furnace and Pierce-Smith converter off-gas at NA ........... 273
Figure 3-3: The Contimelt process for fire refining of secondary copper............................................................ 281
Figure 3-4: Energy flows in the Contimelt process.............................................................................................. 282
Figure 3-5: Secondary hood system of the primary smelter................................................................................. 285
Figure 3-6: Southwire copper wire rod plant at NA ............................................................................................ 287
Figure 3-7: Copper recycling at Hüttenwerke Kayser AG................................................................................... 293
Figure 3-8: Schematic view of a blast furnace at HK .......................................................................................... 295
Figure 3-9: Off-gas treatment from blast furnaces at HK .................................................................................... 297
Figure 3-10: Copper Production at MKM GmbH, Hettstedt ............................................................................... 306
Figure 3-11: Blast furnace process ...................................................................................................................... 308
Figure 3-12: Schematic view of converter process .............................................................................................. 310
Figure 3-13: Flow sheet of the new anode plant .................................................................................................. 312
Figure 3-14: Basic concept of the dip forming copper wire rod plant ................................................................. 318
Figure 3-15: General flowsheet of semi-finished product fabrication ................................................................. 320
Figure 3-16: Simplified flow diagram of an upcast process ................................................................................ 326
Figure 3-17: Fabrication of sheets and strips of copper and copper alloys.......................................................... 327
Figure 3-18: Fabrication of copper tubes............................................................................................................. 331
Figure 3-19: Fabrication of copper alloy tubes and rod/sections from copper and copper alloys ....................... 331
Figure 4-1: Primary copper production plant....................................................................................................... 357
Figure 4-2: Secondary copper production plant................................................................................................... 358
224 Contents
LIST OF TABLES
Table 1-1: Copper production in Germany.......................................................................................................... 233
Table 1-2: Industrial use of copper in Germany (1996)....................................................................................... 234
Table 2-1: Composition of matte and slag from smelting operation.................................................................... 243
Table 2-2: Technical data for different copper smelting processes ..................................................................... 245
Table 2-3: Energy consumption of the primary copper production by use of different production processes..... 245
Table 2-4: Current copper smelting processes..................................................................................................... 246
Table 2-5: Typical composition of copper smelting slags ................................................................................... 246
Table 2-6: Potential sources of stack and fugitive emissions from primary copper producing plants ................. 251
Table 2-7: Potential sources of water pollution from primary copper production ............................................... 251
Table 2-8: Outputs from primary copper producing plants ................................................................................. 252
Table 2-9: Major copper-containing external recycling materials ....................................................................... 255
Table 2-10: Potential sources of stack and fugitive emissions from German secondary copper producing plants260
Table 2-11: Potential sources of water pollution from secondary copper production ......................................... 261
Table 2-12: Outputs from secondary copper producing plants............................................................................ 261
Table 2-13: Outputs from the further processing of copper................................................................................. 265
Table 2-14: Copper production and recycling plants in Germany ....................................................................... 266
Table 2-15 : Main plants for the further processing of copper ............................................................................ 267
Table 3-1: Input/output data from NA (1996) ..................................................................................................... 272
Table 3-2: Process parameter of the Outokumpu flash smelting furnace at NA .................................................. 272
Table 3-3: Concentrations of main constituents in the cleaned off-gases from the anode furnace (primary plant)275
Table 3-4: Concentrations of main constituents in the cleaned gas from the sulphuric acid plant....................... 276
Table 3-5: Data for the formerly used blast furnaces and the new electric furnace ............................................. 278
Table 3-6: Particulate matter content and its main constituents in the raw off-gases from the scrap converter
(secondary plant)........................................................................................................................................ 279
Table 3-7: Concentrations of main constituents in the cleaned off-gases from the scrap converter (secondary
plant) .......................................................................................................................................................... 279
Table 3-8: Concentration of the main constituents in the cleaned furnace off-gas from the tin-lead alloy plant . 280
Table 3-9: Concentrations of the main constituents in the cleaned furnace off-gases from the Contimelt process
(secondary plant)........................................................................................................................................ 283
Table 3-10: Accompanying metals in anodes and cathodes at NA ...................................................................... 284
Table 3-11: Concentrations of the main constituents in the cleaned gas from the central fabric filter ................ 285
Table 3-12: The main constituents in the dust content of the off-gas after treatment in a fabric filter ................ 286
Table 3-13: Continuous casting plant data........................................................................................................... 289
Table 3-14: Concentrations of the main constituents in the untreated waste water at NA ................................... 290
Table 3-15: Total emissions from copper production at NA (primary and secondary plant), 1996..................... 290
Table 3-16: Pollutants in the three separately discharged waterstreams at NA (primary and secondary plant)
based on measured values from 1996......................................................................................................... 291
Table 3-17: Authorised pollutant concentrations in the three separately discharged waterstreams at NA (primary
and secondary plant), 1996 ........................................................................................................................ 291
Table 3-18: Overall pollutant rate of waste water discharges from NA based on measured values from 1996... 291
Table 3-19: The main intermediates, by-products and residues from copper production at NA ......................... 292
Table 3-20: Input/output data from Hüttenwerke Kayser AG (1997).................................................................. 294
Table 3-21: Chemical composition of blast furnace slag from HK...................................................................... 295
Table 3-22: Process parameters of the blast furnace ........................................................................................... 296
Table 3-23: Particulate matter content and its main constituents in the raw off-gases from the blast furnace..... 297
Table 3-24: Concentrations of main constituents in the cleaned off-gases from the blast furnace ...................... 298
Table 3-25: Particulate matter content and its main constituents in the raw off-gases from the scrap converter. 298
Table 3-26: Concentrations of the main constituents in the cleaned off-gases from the scrap converter............. 299
Contents 225
Table 3-27: Particulate matter content and its main constituents in the raw off-gases from the reverberatory anode
furnace ....................................................................................................................................................... 300
Table 3-28: Concentrations of main constituents in the cleaned off-gases from the reverberatory anode furnace300
Table 3-29: Accompanying metals in anodes and cathodes at HK ...................................................................... 301
Table 3-30: Concentrations of main constituents in the cleaned off-gases from the TLA plant .......................... 302
Table 3-31: Main constituents in the dust content of the off-gas after treatment in a fabric filter ....................... 303
Table 3-32: Stack emissions from secondary copper production at HK, measured values.................................. 304
Table 3-33: Total emission from copper production at HK, calculated values.................................................... 304
Table 3-34: Pollutants (based on measurements) from HK ................................................................................. 305
Table 3-35: Main intermediates, by-products and residues from copper production at HK ................................ 305
Table 3-36: Input/output data from Mansfeld Kupfer und Messing GmbH (1996)............................................. 307
Table 3-37: Input materials for blast furnace....................................................................................................... 307
Table 3-38: Chemical composition of blast furnace slag from MKM ................................................................. 308
Table 3-39: Concentrations of main constituents in the cleaned off-gas from the blast furnace.......................... 309
Table 3-40: Metallic components of filter-oxide from blast furnace ................................................................... 309
Table 3-41: Input materials for converter ............................................................................................................ 310
Table 3-42: Accompanying metals in the converter slag ..................................................................................... 311
Table 3-43: Emissions in clean gas of the converter............................................................................................ 311
Table 3-44: Metallic accompanying metals in filter-oxide of the converter ........................................................ 312
Table 3-45: Input materials of anode hearth shaft furnace................................................................................... 313
Table 3-46: Emission values in the clean gas of anode furnace and poling furnace ............................................ 314
Table 3-47: Main constituents in the dust content of the off-gas after treatment in a fabric filter ....................... 315
Table 3-48: Stack emissions (max. measured values) from secondary copper production at MKM ................... 316
Table 3-49: Specific stack emissions of different process units at MKM............................................................ 316
Table 3-50:Main intermediates, by-products and residues from copper production at MKM............................. 317
Table 3-51: Typical data of an Electric furnace based discontinuous casting plant ............................................ 322
Table 3-52: Typical data of an ASARCO shaft furnace based plant ................................................................... 324
Table 3-53: Typical data of a facility to roll brass strips ..................................................................................... 330
Table 3-54: Emissions from the fabrication of semi-finished products (annual average concentration) ............. 334
Table 3-55: Specific emissions from the fabrication of semi-finished products (annual average loads) ............. 334
Table 3-56: Main constituents in the dust content of off-gas cleaned in a fabric filter ........................................ 335
Table 3-57: Specific emissions of the main constituents in the dust content of the off-gas cleaned in a fabric filter
(annual average loads) ............................................................................................................................... 336
Table 3-58: Pollutants in the different waste water streams from the fabrication of semi-finished products (annual
average)...................................................................................................................................................... 336
Table 3-59: Contaminants discharged per year with the process water of a semis fabrication plant (example) .. 337
Table 3-60: Solids and oil discharged per year with the surface water of a semis fabrication plant (example)... 337
Table 3-61: Main residues from the fabrication of semi-finished products ......................................................... 338
Table 4-1: VDI guidlines on emission measurements.......................................................................................... 342
Table 4-2: Selection of gas cleaning devices....................................................................................................... 347
Table 4-3: Techniques to remove gaseous contaminants..................................................................................... 348
Table 4-4: Devices for waste water treatment...................................................................................................... 350
Table 4-5: Overview of section 4.2 ..................................................................................................................... 356
Table 4-6: German candidates BAT for the primary copper production ............................................................. 357
Table 4-7: German candidates BAT for the secondary copper production.......................................................... 358
Table 4-8: Proposed emission guide values for the cleaned off-gases from fire refining plants (primary plant). 360
Table 4-9: Proposed emission guide values in the cleaned off-gases for the smelting of oxidic raw materials
(secondary plant)........................................................................................................................................ 361
Table 4-10: Proposed emission guide values in the cleaned off-gases from a scrap converter (secondary plant)362
Table 4-11: Proposed emission guide values for the cleaned off-gases for the fire refining (secondary plant) ... 362
226 Contents
Table 4-12: Proposed emission guide values for the off-gases after treatment in a fabric filter .......................... 364
Table 4-13: Proposed emission guide values for the cleaned off-gases from a sulphuric acid plant ................... 365
Table 4-14: Proposed emission guide values for the cleaned off-gases from a tin-lead alloy plant..................... 366
Table 4-15: Proposed emission guide values for the cleaned off-gases from secondary hood systems............... 366
Table 4-16: German BAT for melting and casting in the fabrication of semi-finished products ......................... 366
Table 4-17: Proposed emission guide values for pollutants in discharged waste waters (primary and secondary
plant) .......................................................................................................................................................... 367
Table 6-1: Legal basis and main regulations alongside the production line ........................................................ 375
Table 6-2: Emission control requirements laid down in the TA Luft .................................................................. 377
Table 6-3: Limit values for discharges into water for copper production plants ................................................. 379
Table 6-4: Requirements for discharges from cooling circuits of industrial processes........................................ 380
Table 6-5: Thresholds according to the waste water levy act .............................................................................. 381
Contents 227
Glossary
BAT Best Available Techniques HMIP Her Majesty´s Inspectorate of
Pollution (UK)
BImSchV BundesImmissionsschutzgesetz IPPC/ Integrated Pollution Prevention
IPPC-D and Control/ IPPC-Directive
DIN Deutsche Industrie Norm pH pH-value
EN European Norm TA Technical Instructions
(Technische Anleitung)
ESP Electrostatic precipitator TBRC Top Blown Rotary Converter
EU European Union
Chemical Symbols
Ag Silver MgO Magnesium oxide, magnesia
Al2O3 Aluminium oxide MnO Manganous oxide
As Arsenic Ni Nickel
CO Carbon monoxide NO2 Nitrogene dioxide
CO2 Carbon dioxide NOx Nitrogen (x) oxide
Ca Calcium Pb Lead
CaO Calcium oxide, lime PCDD/ Dioxine/Furane
PCDF
Cd Cadmium S Sulphur
Cu Copper Sb Antimony
F Fluorine SiO2 Silica, silicon oxide
Fe Iron SO2 Sulphur dioxide
FeO Iron oxide Zn Zinc
H2SO4 Sulphuric acid ZnO Zinc oxide
Units
µg Microgramme t Ton
a Year °C Degrees Celsius
DM Deutsche Mark d Day
GJ Gigajoule g Gramme
kg Kilogramme h Hour
l Litre kWh Kilowatt hour
m Metre Mio. Million
2
m Square metre MWh Megawatt hour
3 3
m Cubic metre Nm Norm cubic metre (STP)
3
Nm Norm cubic metre rpm Rotations per minute
mg Milligramme wt.-% Weight-percent
ng Nanogramme vol.-% Volume-percent
PPM Parts per million
228 Contents
Definitions 229
Definitions
Off-gas: For the purpose of this report, off-gas is the carrier gas emitted from a
plant or from an off-gas purification plant and containing gaseous or
solid emissions or emissions in aerosol form. Carrier gases may be off-
gases, for example from smelting units, or even air.
Aluminium bronze: Alloys of copper and aluminium.
Anode copper: Impure raw copper which has been cast to form anode plates and which
is suspended in the electrolyte as the anode in the electrolytic copper
production.
Blister copper: Raw copper originating from the converter process in the primary
extraction of copper and containing 96 - 99 % by mass of Cu.
Bronze: Copper alloys which do not contain zinc as a major alloying.
ITE: Total value for PCDD and PCDF calculated by a method specified in
the appendix to the 17th Regulation on the Implementation of the
Federal Law on Air-borne Pollution Prevention (ITE = international
toxicity equivalent).
Burden: Feedstock for blast furnace without coke, sometimes also referred to as
charge.
German silver: Copper-zinc-nickel alloy.
PCDD/PCDF: Gaseous or dust bound emissions or aerosol emissions of
polychlorinated dibenzodioxins (PCDD) and polychlorinated
dibenzofurans (PCDF), whose presence and concentration are
determined as specified in VDI 3499 Part 2.
Poling: Refining method for deoxidizing oxygen-containing copper melts using
wood or natural gas.
Clean gas: For the purpose of this report, clean gas is the purified gas emitted at the
last stage in an off-gas purification plant.
Red brass: Copper alloys containing tin, zinc and lead.
Black copper: Raw copper produced by reduction in a blast furnace, the Cu content is
70 - 80 % by mass.
Tombac: Obsolete collective term for copper alloys containing 5 to 28 % by mass
of zinc, modern term: brass. Tombac can be severely deformed by
forging. Finely forged Tombac is referred to as fake gold foil.
White metal: Tin-antimony-lead-copper alloy.
ITE: Total value for PCDD and PCDF calculated by the method specified in
the appendix to the 17th Regulation on the Implementation of the
Federal German Law on Air-Borne Pollution Prevention (ITE =
international toxicity equivalent)
Fugitive emissions: For the purpose of this report, fugitive emissions arise from gases or
particulate matter emitted to the surrounding air without being captured,
purified or treated in any other way.
230 Definitions
Stack emissions: For the purpose of this report, stack emissions arise when captured off-
gases are emitted after purification (clean gas).
Preface 231
0 Preface
On September, 24th, 1996 the Council of the European Communities issued the Directive
96/61/EC on Integrated Pollution Prevention and Control (IPPC-D). This directive aims to
achieve a high level of protection of the environment taken as a whole. It was enacted
especially considering the common environmental goals of the EC, laid down in article 130r,
EC-treaty (conservation and protection of the environment and improvement of environmental
quality (i), protection of human health (ii), sustainable use of resources (iii), promotion of
measures on an international level to handle regional or global environmental problems (iv)),
and being aware of the fact that the implementation of an integrated concept of pollution
prevention needs to be addressed by measures on a community level.
Annex I of directive 96/61/EC contains an extensive list of industrial activities to which the
directive applies. According to this list, also industrial activities related to the production and
processing of metals are subject to the measures within the IPPC (N° 2). The directive
provides a general framework with principles for integrated pollution prevention and control.
The goal of this integrated concept is to protect the environment taken as a whole by
preventing and controlling emissions into all environmental media: air, water, and land. The
necessity for drawing up information on best available techniques (BAT) for certain industrial
activities is constituted by some of the measures laid down within the directive to attain the
above mentioned goal:
- the definition of basic obligations, that operators of industrial activities have to comply with
(art 3, esp. 3 a)).
- the requirement for the EC-member states to ensure compliance with these basic obligations
by the operators (art 3, 4, 5).
- the definition of an approval procedure according to which permits should be granted, only if
operators fulfil a number of requirements, further specified in the directive (art 3, 6, 7, 8).
- the reminder to the competent authorities, that a permit has to include emission limit values
for at least a minimum number of substances explicitly named in Annex III. These emission
limit values, or possibly equivalent parameters or technical measures, should be based on
reference values derived from so-called Best Available Techniques (BAT, art 9(3)). The IPPC
specifies explicitly, that BAT themselves are not binding, but only derived reference values.
- the specification of the term BAT in the IPPC as „the most effective and advanced stage in
the development of activities and their methods of operation which indicate the practical
suitability of particular techniques for providing in principle the basis for emission limit
values designed to prevent and, where that is not practicable, generally to reduce emissions
and the impact on the environment as a whole" (art 2.11).
232 Preface
- the obligation for the member states to provide the EC-commission with representative data
and possibly information about BAT for the categories of industrial activities listed in Annex I
(art 16.1). Furthermore the EC-commission is urged to maintain an information exchange
between the member states and the concerned industries about BAT, related control measures,
and developments in these fields (art 16.2). Additionally the member states have to ensure that
the competent authorities follow or are informed of developments in BAT (art 11).
In particular the articles dealing with the definition of BAT and requiring an exchange of
information on BAT are the motive for this document (esp. art 16.2). The goal of this study is
to provide background information on BAT for environmental protection within the German
primary and secondary copper production industry that serve as possible candidates BAT on
an EU level. It gives information on environmental protection techniques but also production
techniques on this performance. The further processing of copper is not included in this study.
The paper is based also on literature study, but mainly on technical discussions with the
experts of the German "Abstimmungsgruppe" co-ordinated by Mrs Dr. Pertersen,
Umweltbehörde Hamburg.
The document is structured as follows:

Chapter 1 provides general information about the copper industry, including first indications
of environmental concerns regarding the production of copper. Then basic information about
the applied processes and techniques in the primary and secondary copper industry follows,
and the main outputs and their sources are investigated (chapter 2). In Chapter 3, German
copper production plants are described, including input/output levels and emission levels.
Chapter 4 contains a list of German candidates BAT, i.e. techniques that are possibly
candidates for being BAT on an EU level. Additionally, an overview of relevant legislation in
Germany is provided in the Annex.
This study is being supported by the German Umweltbundesamt, Berlin as part of the research
project "Exemplarische Untersuchung zum Stand der praktischen Umsetzung des integrierten
Umweltschutzes in der Metallindustrie und Entwicklung von generellen Anforderungen". The
authors wish take this opportunity to express their thanks for the support received, especially
to the members of the co-ordinating group (alphabetical order):
Mr Albrecht, Landesamt für Umweltschutz des Landes Sachsen-Anhalt

Mr Jörß, Umweltbundesamt Berlin
Mr Dr. Meyer-Wulf, Hüttenwerke Kayser AG
Mr Dr. Mezger, Ministerium für Umwelt und Verkehr BVV
Mrs Dr. Müller, Umweltbehörde Hamburg
Mrs Dr. Petersen, Umweltbehörde Hamburg
Mr Dr. Traulsen, MCT GmbH
Mr Dr. Velten, Norddeutsche Affinerie Aktiengesellschaft
Mr Dr. Zierock, Umweltbundesamt Berlin
General Information 233
1 General information
1.1 Production and use of copper

Germany is one of the main producers and users of non-ferrous metals in the European
Community. Other important producers and users are France, Belgium, Italy, Spain, the
Netherlands and the United Kingdom. Especially in copper production, Austria, Finland and
Sweden also have an important share. In the following, information on production, use and
recycling is given for the copper branch. The production of zinc and lead is dealt with in a
separate report. The production of aluminium, other light metals or heavy metals is not in the
scope of this study.
With a world-wide annual use of about 12 million tons, copper is the most important metallic
material after steel and aluminium1. According to predictions for the coming years, the use of
copper will retain an increasing tendency. In Europe, more than 3 million tons of copper per
year are used. Germany is one of the most important copper producing and using countries in
Europe and even in the world. In 1996, the production of copper amounted to about 671,000
tons of which 355,000 tons came from secondary raw materials [10]. The reported use in
Germany amounted to about 955,000 tons of copper in 1996 [10], the calculated use
amounted to 1,066,000 tons in 1995 [9]. Table 1-1 and Table 1-2 show the data for German
copper production and use for different products and fields of application in Germany.
Table 1-1: Copper production in Germany
1992 1993 1994 1995 1996
[t] [t] [t] [t] [t]
Total refined Cu (Σ) 581,682 632,079 591,859 616,387 670,790
Fire refining 111,139 91,794 87,694 78,915 78,374
Electrolytic refining 470,543 540,285 504,165 537,472 592,361
Cu cast alloys 58,805 52,542 57,502 58,047 53,916
Semi-finished products, Cu and Cu alloys 1,470,411 1,340,371 1,456,476 1,530,288 1,460,761
Conducting material 606,948 521,103 516,469 549,302 582,645
Castings, Cu and Cu alloys 89,427 71,988 81,068 86,842 73,768
Cu powder 10,490 9,414 10,416 11,130 11,158
Source: Bundesamt für Wirtschaft [10]
1
Detailed information on physical and chemical properties as well as the industrial uses of copper can be
found elsewhere (c.f. [25], [86]).
234 General Information
Table 1-2: Industrial use of copper in Germany (1996)

User [t/a]
Semi-finished plants 934,695
Powder industry 10,006
Foundries 4,588
Alloy producers 2,754
Iron and steel industry 1,524
Chemical industry 1,159
Total 954,726
Source: Bundesamt für Wirtschaft [10]
The main fields of application for copper products are power supply, telecommunications, the
building industry, mechanical engineering, transportation and consumer goods. Figure 1-1
shows the different fields of application of German copper consumers.
Others
Transport 2%
9%
Precision
mechanics, optics
9%
Construction
47 %
Electrical /
electronics
15 %
General engineering
18 %
Figure 1-1: Main fields of application of copper products in Germany

Source: Wirtschaftsvereinigung Metalle [87]
Copper can be recycled without loss of quality. As Germany has almost none of its own ore
resources of sufficient quality, the recycling of copper has always been of great importance.
The recycling rate of copper world-wide is about 40 %. In Germany a recycling rate of about
46 % is achieved [64]. Figure 1-2 shows the average service life of various copper products
and applications.
[a] 80
70
60
50
40
30
20
10
0
Cars Electro motors Wires Buildings
Figure 1-2: Average service life of copper materials in various applications

Source: Langner [49]
The average lifetime of copper products ranges from 6 - 8 years for cars and up to 60 - 80
years for buildings. If an average service life of copper products of 33 years is assumed, the
recycling rate amounts to about 80 % [49].
1.2 First indication of environmental concerns regarding the production of

copper
Plants producing non-ferrous metals such as copper are a source for certain emissions into the
atmosphere and for discharges into water as well as for solid residues. A short description of
relevant pollutants will be given in the following sections as a first indication. Emissions
causing odours or noise have to be taken into account according to the IPPC-Directive.
However these emissions have to be looked at on a plant by plant basis. Therefore they are not
covered by the following sections.
1.2.1 Emissions into the atmosphere

The processing of non-ferrous metals is a source of different kinds of air polluting substances
above all for gases and particulate matter. Depending on their origin two kinds of atmospheric
emissions can be distinguished: stack emissions and fugitive emissions. Stack emissions arise
mainly from furnaces and can usually be captured and cleaned by appropriate gas cleaning
devices. Fugitive emissions are caused by open handling and storing of materials. Other
sources are roofs and openings of production buildings as well as inadequately enclosed
transport systems and leakages. Fugitive emissions should be avoided by hoods, closed
transport systems and good housekeeping.
Osparcom [56] defines the following atmospheric contaminants to be taken into consideration
for the (primary) production of non-ferrous metals:
- particulate matter,
- antimony, arsenic, cadmium, cobalt, copper, lead, mercury, nickel, selenium, tin, zinc, and
- chlorine, fluorine, nitrogen oxides, sulphur, sulphur dioxide and sulphuric acid mists.
Particulate matter arises during all smelting operations used in the non-ferrous metal industry.
The precipitated flue dusts contain various metals and are treated internally or externally to
recover the metal content. Sulphur dioxide emissions arise from the processing of sulphur
containing raw materials and fuels in different production routes. According to the German
Umweltbundesamt2, the estimated emissions of sulphur dioxide in the German non-ferrous
metal industry amounted to about 4,400 t/a in 1994, which accounts for 5.2 % of the sulphur
dioxide emissions from the industrial processes3 and for 0,15 % of the overall sulphur dioxide
emissions in Germany. The estimated emissions of nitrogen oxides4 amounted to about 1,200
t/a in 1994, which accounts for 5.1 % of the nitrogen oxide emissions from the industrial
processes and for 0,05 % of the overall nitrogen oxide emissions in Germany. Copper plants
covered by this study are a source of heavy metal emissions; different heavy metals and heavy
metal compounds may be emitted [88]. Some processes in copper production are potential
sources of dioxines and furanes (PCDD/PCDF). Different measures are available to control
the PCDD/PCDF emissions from the copper plants, as shown, e.g. for secondary copper plants
[75].
1.2.2 Potential releases into water

In the non-ferrous metal industry, water is used for different purposes mainly dependent on
process specific constraints (see also [34], [56]). Controlled discharges, such as process
effluent or cooling water take place through well defined ducts. They are usually treated in a
waste water treatment plant before being released. In order to prevent uncontrolled discharges
that may arise due to leakages or accidents measures such as collecting basins are applied. In
general, surface run-off from the plant site is captured and treated either in a waste water
treatment plant or in a special run-off water treatment plant. In non-ferrous metal plants,
effluents may arise at different sources [24], mainly:
2
These calculations are based on estimated emission factors for sulphur dioxide (nitrogen oxides) which
results from the processing of raw materials and the usage of different energy sources. The validity of
these emission factors should be checked.
3
Emissions caused by energy generation processes are not included in the figure for the industrial
processes.
4
NOx given as NO2.
- wet gas cleaning,

- slag granulation,
- hydrometallurgical treatment,
- electrolytic processes,
- cooling water, and
- surface run-off.
Osparcom [56] gives a list of potential contaminants into water and soil which could arise in
the production processes of the (primary) non-ferrous metal industry:
- suspended solids,
- arsenic, cadmium, chromium, cobalt, copper, lead, manganese, mercury, nickel, thallium,
tin, tungsten, zinc, and
- sulphate and sulphite.
In addition, the pH-value should be taken into account. Cooling water for indirect cooling
from open cooling circuits and once-through systems is not contaminated and therefore does
not have to be cleaned. Cooling water for slag granulation is led through a closed circuit
without a conditioning agent and normally does not have to undergo demineralisation.
Effluents from the demineralisation of closed cooling circuits are treated in a waste water
treatment plant.
1.2.3 Solid materials generated

Besides the main products, solid materials generated in the non-ferrous metal industry are:
- slags,
- precipitates,
- residues from the production,
- dusts and sludges from gas cleaning, and
- sludges from the waste water treatment.
Residues for recovery are recycled in a production process, either in the same plant or in an
external plant at a different location. In general, only a few residues arise in non-ferrous metal
plants as the traditional aim of the process techniques is to close production loops to recover
the metals contained and to generate marketable by-products. In the copper production
industry only a minor amount of non-usable residues has to be disposed of.
Applied Process Technology And Abatement Techniques 239
2 Applied process technology and abatement techniques in copper

production
Due to the large number of applied process technologies and abatement techniques in copper
production and the existing site specific differences, in this technical study only brief
descriptions of relevant processes and techniques are given.
2.1 Introduction and scope of the study

Integrated pollution prevention and control require the consideration and prevention and/or
minimisation of all harmful impacts on the environment caused by industrial activities at the
same time. Also the transfer of pollution from one environmental media to another has to be
taken into account.
The goal of the IPPC-Directive (IPPC-D) is to prevent or control pollution caused by certain
industrial activities, including primary and secondary production of copper (cf. Art 1 and
Annex I). As mentioned in the preface of this paper, it therefore requires the member states of
the EU, inter alia, to exchange information about BAT for these activities. Within the IPPC-D
pollution is defined as "the direct or indirect introduction as a result of human activity, of
substances, heat or noise into the air, water or land which may be harmful to human health or
the quality of the environment, result in damage to material property, or impair or interfere
with amenities and other legitimate uses of the environment" (cf. art 2.2). To achieve its goal
the Directive lays down measures "to reduce emissions in the air, water and land from the
above-mentioned activities, including measures concerning waste" (cf. art 1). „Best available
techniques“ should be applied, in which „available techniques should mean those developed
on a scale which allows implementation in the relevant industrial sector, under economically
and technically viable conditions“. Summarising the provisions of the IPPC-D it can be
concluded, that the identification of BAT for copper production requires an investigation of
the underlying production systems and its economic context with particular respect to the
emission of substances, heat, and noise caused by the system into the environmental media
air, water, and land. Furthermore the considerations of Annex IV, IPPC-D, have to be taken
into account, in particular the requirements of Annex IV.9 (consumption and nature of raw
materials and energy efficiency of the processes).
Chapter 2 of the study gives a short description of processes and techniques applied in the
production of copper and the most common inputs, outputs and emissions. Due to the high
level of integration in copper production, a distinction between primary and secondary
processing is difficult and cannot always be maintained. Furthermore, this report deals only
with those steps of copper production which are normally carried out at the plant site: the
preparation and handling of raw materials, the smelting or the hydrometallurgical treatment of
240 Applied Process Technology And Abatement Techniques
the input charge and the refining of the raw metal produced5. In addition, the production of
wire rod from copper cathodes using a cathode shaft furnace and the production of semi-
finished cathodes from copper and copper alloys is covered.
2.2 Basic description of copper production

Copper is produced from various primary and secondary raw materials. The primary process
uses sulphidic concentrates or sulphidic/oxide mixed ores, while secondary processes employ
recycled oxidised or metallic products. The industry can be divided into two sections,
secondary copper production and primary copper production with the additional use of
secondary material. In the following, a general overview is given on the most common
primary and secondary processes for copper production. To follow the scope of the study,
emphasis is placed on processes operated in German plants.
2.2.1 Primary copper production

Primary copper can be produced by hydro-metallurgical processes or pyro-metallurgical
processes. Approximately 10 % of the primary copper is produced by direct leaching of ores
(hydro-metallurgical process). The pyro-metallurgical production of copper from primary
material consists of several steps, which are summarised below6:
Smelting operations
- roasting
- smelting
- converting
Refining operations
- fire refining
- casting into anodes
- electrolytic refining
Preceding processes such as mining, crushing, grinding and concentrating steps, which
normally take place at the mining location, are not in the scope of this study. Apart from the
production of copper, the further processing following the electrolytic refining such as the
fabrication of wire rod and the fabrication of semi-finished products is subject of this report.
After a general process description (c.f. 2.2.1.1), typical outputs to the different environmental
media are described in section (c.f. 2.2.1.2).
5
Mining and processing of ores are no longer carried out in Germany. Furthermore, these processes are
applied at only very few sites in the EU.
6
Detailed information on copper production can be found elsewhere (c.f. [8], [25], [86]).
2.2.1.1 General process description

Copper concentrates are today processed almost exclusively by pyrometallurgical methods7.
Figure 2-1 shows a schematic overview of the primary copper production route. In the
following first the raw materials, then the different production steps and process units of the
primary copper production are described. The underlined terms refer to Figure 2-1.
Inputs for primary copper production

Nowadays sulphidic concentrates (copper content: 15 - 45 %) are the most important raw
materials for the pyro-metallurgical primary copper production with a share of more than 85
%. To a small extent oxidic/sulphidic mixed ores and, more seldom, bituminous ores are
processed. The sulphidic concentrates consist of complex copper/iron sulphides; they are
obtained from ores containing 0.5 - 2 % copper by flotation. Further inputs used for primary
copper production are fluxes (silicate, lime, sands, etc.), additives/reactants (iron, carbon, etc.)
and recycled materials (scrap, drosses, lime sludges, used abrasive materials, slags, dusts,
etc.).
Production units in primary copper producing plants

The roasting step, which is a heating process in an oxidising atmosphere, is applied to break
down the complex sulphides to cuprous and ferrous sulphides and to convert the iron sulphide
into iron oxide. The most common method is partial roasting, where 10 % of the iron and
sulphur is oxidised. It is used as a preliminary stage of the smelting process only. Sulphating
roasting is applied as a preliminary stage of a leaching process and is only in use in one plant
[67]. During both roasting methods sulphur dioxide is formed and carried out with the furnace
process gas. This roaster gas (SO2-content of 10 - 14 % on average) is processed in a sulphuric
acid plant after having been cleaned by electrostatic precipitators [56]. In Europe only partial
roasting is used. The most common device for roasting is the fluidized bed roaster.
In the smelting step, roasted and unroasted8 materials as well as slag forming fluxes (silica,
limestone) are mixed and smelted under oxidising conditions into silicate slag and sulphidic
copper matte. The produced slag contains the iron oxides and silicates as well as the gangue
and the ash from the combustibles. The copper matte (copper content: 30 - 80 %) contains
copper sulphide and iron sulphide in various portions as well as the precious metals and other
accompanying elements.
7
Hydrometallurgical processing covers just a small part of the world-wide copper production and is not
used in Germany. Therefore it is not discussed in this report.
8
When unroasted raw material is smelted, a drying step can be necessary prior to smelting. Sludges from
waste water treatment can be recycled via the drying process as well. Off-gases from drying are treated in
electrostatic precipitators and wet scrubbers or fabric filters.
Concentrate
Air / oxygen
Silica Slag
Roasting / Flue dust
smelting
Copper matte
(30 - 80 % Cu) SO2-containing Desulphurization Sulphuric
off-gas (Sulphuric acid plant) acid
Air / oxygen
Converting Slag
Flue dust
Blister copper
(96 - 99 % Cu)
Reductant
Fire
refining
Copper anodes
Electric (> 99 % Cu)
current
Nickel sulphate
Electrolytic Arsenic trioxide
refining Precious metals
Selen,Tellur
Cathodes
Wire rod production
- cathode shaft furnace
- continuous casting
- wire rod plant
Wire rod
Figure 2-1: Primary copper production route

A furnace process gas, containing sulphur dioxide, is formed during smelting and further
processed, after treatment for dust removal, in a sulphuric acid plant. If the copper content of
the slag is too high, the recovery of copper e.g. in an electric furnace is possible. Otherwise
the decopperised slag is marketed for e.g. road construction, hydraulic engineering or as a
blasting media. Table 2-1 shows a typical composition of copper matte and slag produced in
the smelting process.
Table 2-1: Composition of matte and slag from smelting operation

Copper matte Slag
Components [wt-%] [wt-%]
S 20 - 25 -
Fe 6 - 40 -
Cu 29 - 70 0.3 - 0.8
SiO2 - 29 - 40
FeO - 32 - 50
Fe3O4 - up to 10
CaO - up to 10
Al2O3 - up to 10
Source: Winnacker-Küchler [86]
The main types of furnaces applied for smelting of roasted raw materials are reverberatory
furnaces and electric furnaces. In 1994 reverberatory furnaces were used for about 25 % of the
world-wide copper concentrate smelting [8]. Electric furnaces produce less off-gas, due to the
fact that no additional fuel for heat production is added. Therefore it reaches a higher
concentration of sulphur dioxide, which is favourable from an environmental point of view.
But they can only be used economically, if cheap electric energy is available. In Europe,
reverberatory furnaces are not used for primary smelting anymore.
Processes for combined roasting and smelting can be divided into bath smelting processes
and flash smelting processes, these being the most widely adopted devices for the smelting of
copper. Flash smelting accounts for most of the copper smelting in Japan, the United States
and the European Community. Since 1970, about 30 new furnaces have been installed in
addition to those already existing 7 [8].
The Outokumpu process is the standard process for smelting and is used most frequently
today; about 30 furnaces are in operation world-wide. It is used for processing dry
concentrates which are fed via a concentrate burner into the top of an upright reaction shaft
together with the fluxes and the hot air. The molten particles are separated from the gas flow
and fall into the molten bath at the bottom of the furnace. There the matte separates from the
slag and is further processed in a converter. The slag is decopperised in a different process.
Although the Outokumpu process is basically autogeneous, supplementary heating is needed
in the settler. The advantages of the Outokumpu process are basically the high throughput rate
achievable with one furnace, the high sulphur dioxide content in the off-gases, the good
energy efficiency, which results in a reduction in fuel consumption in context with tonnage
oxygen utilisation, and - as a result of the high matte grade - the reduced blowing time of the
converters[56]. The Inco process (International Nickel Co.) processes a mixture of copper
concentrate, which has been dried in a fluidised bed dryer, and oxygen, which is blown
horizontally into the furnace from both ends. No additional heat is needed since the heat
generated by the roasting of the concentrate is sufficient to support an autogeneous smelting
process. In combination with the application of pure oxygen, the specific off-gas rate is very
low and reaches a sulphur dioxide content of 75 – 80 vol.-%. Slag is removed continuously at
the one end of the furnace whilst matte is discharged periodically from a side wall. Four Inco
furnaces were in operation world-wide in 1994 [67]. In Europe, this process is not used [88].
The Mitsubishi process is a bath smelting process which combines roasting, smelting and
converting in one continuously carried out process employing three interconnected furnaces.
In the first furnace, dried concentrates, fluxes and air are charged, and a matte and a slag are
produced. Slag and matte flow continuously into an electric furnace where they are separated.
The matte flows into the converting furnace and is continuously processed into blister copper.
This process is used in Japan and Canada [56] and is currently under construction in Indonesia
and Korea [67]. The Noranda process, which is a cylindrical converter-type smelting furnace,
is charged with pelletised concentrates and fluxes. The heat needed is supplied by natural gas
or oil. The slag flows out continuously opposite the charging end and the matte is tapped
periodically from the bottom of the furnace for further processing. Two Noranda furnaces are
currently being used in Canada and in Australia [67]. The El Teniente converter technology
for autogeneous smelting of copper concentrates uses the heat produced from the oxidation of
the green charge for melting. Technical oxygen is used to produce a high grade matte, an off-
gas with a high sulphur dioxide content and a slag with 6 - 8 % copper. Both wet and dried
concentrates can be processed in the El Teniente converter. However, when charging wet
concentrate, seed matte, produced in a separate smelting unit, i.e. a reverberatory furnace,
needs to be added. The advantages of this technology are low capital investment and operating
costs and low energy consumption [56]. Teniente furnaces are in operation in Chile, Peru and
Samba and one is under construction in Thailand [67]. In the Vanjukov process the oxidising
gas is not injected into the matte layer, but directly into the foaming slag. The process was
commercialised in Russia in 1977; in 1992 five furnaces were producing about 400,000 tons
of copper per year [56]. In the Bayin process the smelting and roasting processes are
combined in a fixed rectangular furnace. The melting bath is divided into two parts into a
smelting and a settling zone separated by a wall. The oxidising gas is injected through blast
tuyères into the matte. It is operated at Lanzhau and has a capacity of 400 t of copper per day
[56]. In Table 2-2, Langner [49] has summarised technical data for some of the described
smelting processes.
Table 2-2: Technical data for different copper smelting processes

Reverberatory Outokumpu Inco Mitsubishi
furnace flash smelting (continuous)
(green batch)
Energy consumption [GJ/t Cu] 25.6 16.4 14.2 17.2
Copper content in the matte [wt.-%] 35 62 54 65
Oxygen feed rate [kg/t Cu] 0 480 790 390
Supplementary fuel [GJ/t Cu] 20.7 6.9 3.3 9.7
Off-gas rate [m³/t Cu] 17,700 5,300 3,800 5,100
*)
SO2 concentration [%] 3.8 13 20 14
*)
More recent operating results indicate the following off-gas compositions, depending also on the percentage
of ingress air: Outokumpu up to about 30 %, Inco up to about 80 %, Mitsubishi up to about 20 % SO2.
To compare the overall energy consumption for the production of primary copper with
different production processes, values on energy consumption according to [44] are shown in
Table 2-3. The given values include the drying of the concentrate, the smelting using the
different processes, the converting, the fire refining, the electrolytic refining and the
production of sulphuric acid.
Table 2-3: Energy consumption of the primary copper production by use of different
production processes
Reverberatory Outokumpu Inco Mitsubishi
furnace flash smelting (continuous)
(green batch)
Energy consumption [GJ/t Cu] 40.9 23.4*) 24.7 23.1
*)
Converter slag is recycled to the flash smelter
The Isasmelt process is a rather new process technology using a top-entry lance submerging
into the matte. Moist concentrate pellets, coal and fluxes are charged continuously into the
furnace, whereas oxygen enriched air is injected through a lance which submerges into the
slag. Both matte and slag are tapped simultaneously through a single hole into a settling
furnace where they are separated. The main characteristics of the Isasmelt process are a high
sulphur dioxide concentration in the off-gas, high specific smelting rates and a reduced fuel
consumption. Four Isamelt furnaces are in operation in Australia, Europe, India and the USA.
The Contop process is a new furnace concept which uses two furnaces, a flash cyclone
smelter for producing copper matte and a continuous converter and refining furnace for
producing anode copper. The inputs are injected tangentially into the cyclone and the reacting
mixture falls into a settling chamber underneath where the different phases separate. Slag
cleaning is carried out with oxygen and propane or methane as reductants. The matte flows
into the converting and refining vessel which is separated into three chambers for converting,
oxidation and reduction. This process is not in use, only in El Paso, USA, is a reverberatory
furnace equipped with a cyclone burner and an injection system for natural gas. Table 2-4
shows the technologies currently used for copper smelting.
Table 2-4: Current copper smelting processes

Conventional Flash smelting Bath smelting New/emerging technologies
technologies
Oxy-fuel reverberatory Outokumpu Mitsubishi Isasmelt
furnace Inco Noranda Contop
Electric furnace El Teniente
Vanjukov
Bayin
Source: Osparcom [56]
The converting of copper matte to blister copper is performed in a two-stage batch process. In
the first step the remaining iron sulphide is oxidised by blowing in compressed air into the
molten matte and then separated from the matte by forming a converter slag. In the second
step the copper matte is partly converted into copper oxide, which then reacts to metallic
copper (blister copper: copper content 96 - 99.5 %) with the remaining copper sulphide.
Typical temperatures of the copper phase are between 1,150 and 1,250 °C. The resulting slag
is skimmed off from the surface of the melt. The copper rich slag from the first converting
step is removed before the second step and is returned to the smelting process to recover the
copper content. The sulphur is oxidised to sulphur dioxide by the additional introduction of
compressed air, iron, lead, zinc, nickel, arsenic, antimony and bismuth are removed by
slagging or by volatilisation. The oxidation supplies enough heat to maintain the required
temperature for the converting process, in order that no additional fuel is required. The typical
composition of slags from copper smelting devices are shown in Table 2-5.
Table 2-5: Typical composition of copper smelting slags
Component Reverberatory Flash furnace Noranda reactor Pierce-Smith
[wt.-%] furnace converter
Copper 0.4 - 0.6 1 - 1.5 8 - 10 3-5
Iron (total) 35 40 35 50
Silica 38 30 21 25
Magnetite 7 - 12 13 25 - 29 25
Source: following Fabian [25]
Mainly converters of the Pierce-Smith type (Figure 2-2) are used for this process. At this type,
air or oxygen enriched air is blown into the copper matte through submerged tuyères.
Off-gas Gas cleaning

plant
Housing/
extraction hood
Input materials
Air with
addition of O2
Converter
Slag
Converter copper
Figure 2-2: Pierce-Smith converter

Source: VDI-Richtlinie 2102 [75]
The off-gas is collected by a steel hood, led through a cooler, and then to an electrostatic
precipitator and (usually) a sulphuric acid plant [8]. The Hoboken or siphon converter is
another converter type with a different gas collection system, which is in use in only very few
smelters. According to [56], it delivers an off-gas which is richer and more uniform than the
off-gas from the Pierce-Smith converter. The Kennecott-Outokumpu flash converter treats
ground, dried and high-grade granulate matte. It is a continuous working process which
delivers a constant SO2-concentration. Due to the constant concentration of SO2 the off-gas
can be handled easier in a sulphuric acid plant. One converter of this type went into operation
in 1995 [67].
For sulphur recovery, dedusted off-gases can be treated in the sulphuric acid plant, shown as
an example in Figure 2-3.
Tail gas
IV.
a III. h i
II.
d
Air
I.
SO2
b e f g
H2O H2O
H2SO4
a) Drying tower f) Superheater
b) Heat exchanger 4 g) Intermediate absorber
c) Heat excahnger 3 h) Heat exchanger
d) Heat exchanger 2 i) Final absorber
e) Converter
Figure 2-3: Double absorption contact plant

Source: Rentz [58]
Fire refining is a further purification process carried out in two steps. In the first step
selective oxidation of the remaining sulphur and other impurities is achieved by blowing air
through the molten metal. Thereby small amounts of a copper oxide containing slag are
formed, where the oxidised impurities concentrate. They can be recirculated into the smelting
furnace or the converter to recover the copper contained. The metals which are not oxidised
(e.g. precious metals) remain in the copper phase and have to be removed by electrolytic
refining. In the second step of the fire refining the oxygen content of the copper phase has to
be reduced to the required final level. This deoxidisation step is achieved by blowing
reductants in, such as natural gas, propane, naphta, reforming gas or ammonia through the
molten phase or by addition of wood piles. The fire refined copper with a copper content of 99
% and above is cast into anodes. Most copper anodes are cast on a casting wheel in open
anode-shaped impressions on the top of flat copper moulds. In 1994, continuous casting of
anodes on a Hazlett casting machine was applied by 6 smelters and refineries [8]. The copper
is thereby poured into the gap of two moving water-cooled steel belts and has to be cut out by
a shear or a plasma torch.
Fire refining is carried out in rotary refining furnaces or in hearth furnaces (fixed or tiltable
type (c.f. Figure 2-4)). Rotary furnaces dominate the fire refining in primary copper
production, whereas for secondary copper production hearth refining furnaces are used, as
they are better suited for the melting of solid scrap [8]. The Contimelt process, a continuous
two-stage process, from which the copper can be directly casted into anodes on a casting
wheel, is another technology used for fire refining of converter copper. Detailed information is
given in chapter 2.2.2.1.
Off-gas
Furnace off-gas Gas cleaning
Cooler
plant
Input materials
Slag
Natural gas
Fuel for poling
Copper
Mother copper
to anode production
Figure 2-4: Reverberatory furnace plant for anode production (example for a plant
having a tiltable furnace)
Source: VDI-Richtlinie 2102 [75]
To reach the desired high copper quality, further removing of impurities and the extraction of
chemical elements, such as noble metals, nickel, selenium and tellurium takes place at the
electrolytic refining. The electrolytic process provides a copper which has the required
properties due to a degree of purity of more than 99.99 %.
Thereby the copper anodes are dissolved in an electrolyte using electric current and the copper
is deposited on the cathode as pure metal. The main processes involved are the following
electrochemical reactions:
Anode: Cuo → Cu2+dissolved + 2e- Eo = +0.34 V

Cathode: Cu2+ + 2e- → Cuo Eo = -0.34 V
The electrolyte consists of dilute sulphuric acid containing dissolved copper and small
additions of organic substances (1 - 5 g of organic materials such as glue, thiourea, gelatine
and sulphite lye, per ton of copper [49]) in order to optimise the deposition characteristics.
Modern electrolytic plants using the ISA process employ permanent cathodes made of
stainless steel, on which the copper is deposited and removed mechanically in the form of
sheets. This technique avoids the expensive manufacturing of starter sheets and since this
technique allows mechanisation and automatisation, the production capacity can be increased.
The noble accompanying elements present in the copper anode, such as Ag and Au, and also
lead are collected in the anode slime from which they are extracted in downstream process
steps. The base elements, such as nickel (Ni), accumulate in the electrolyte, some of which is
continuously drawn off for the purpose of extracting metals, including the nickel in the form
of nickel sulphate, and then returned to the electrolysis plant.
The electrolyte is continuously circulated, in order, among other things, to establish uniform
temperature conditions between 60 and 65 °C in the tanks and to continuously replenish
additives. To keep the copper content constant, regulator tanks are included in the circulation
system. The anodes used in these tanks are lead sheets on which fine bubbles of oxygen are
formed by the following reaction.
Anode: H2O → ½ O2 + 2H+ + 2e-

Cathode: Cu2+dissolved + 2e- → Cuo
This oxygen produces an electrolytic spray above the surface of the tank and, because of the
associated health risk in the case of inhalation, the tanks should be covered (oil, polyurethane
beads, etc.) or provided with ventilation. In the case of vented tanks, a scrubber is provided
downstream, if necessary, to purify the ventilation air.
For structural reasons, the floor area underneath the electrolytic tanks has to be protected from
sulphuric acid attack by a suitable coating, thereby ensuring that the soil and ground water
underneath the building are protected at the same time.
Waste water is not produced in copper electrolysis. Any leakage from the plant is collected
and fed back to the electrolyte along with rinsing water to compensate for evaporation losses.
The same applies to the scrubbing water if the decopperising tanks are operated with an
extraction system. The anode scrap (approx. 12 - 16 % of the cast copper [64]) is recycled e.g.
by charging them back into the converter or the anode furnace after washing off the anode
slime.
2.2.1.2 Main outputs and environmental concerns of primary copper producing plants
The potential sources of stack and fugitive emissions into the air from primary copper
production processes and the arising contaminants are summarised in Table 2-6.
Table 2-6: Potential sources of stack and fugitive emissions from primary copper
producing plants
Process unit Operation/source Emission/main f s
contaminants
Raw materials storage Handling, storage, transport Particulate matter x x
Dryer Drying of flash smelting Particulate matter, gas x
furnace-Feed
(Roasting) Smelting (incl. Leaks, cleaning operations Gas, particulate matter, x
gas cleaning) inorganic volatiles
Converting (incl. gas Leaks Gas, particulate matter x
cleaning)
Sulphuric acid plant Off-gas from acid plant Mist, gas x
Electric slag cleaning Leaks Particulate matter x x
furnace
Off-gas Gas, particulate matter x
Anode furnace Off-gas Gas, particulate matter x
Leaks Particulate matter x x
Electrolytic refining Electrolysis Mist x
cells/tanks/washing chambers
Continuous casting, wire Material handling, off-gas Particulate matter, fumes x
rod plant from furnaces
f: fugitive emissions; s: stack emissions
The potential sources of water pollution are summarised in Table 2-7.

Table 2-7: Potential sources of water pollution from primary copper production
Process unit Operation/Potential source Use/treatment options
General Rain water from roads, yards, Waste water treatment plant
roofs, wet cleaning of roads
(Roasting) Smelting furnace Bleed of cooling water Waste water treatment plant
(incl.gas cleaning)
Converter Bleed of cooling water Waste water treatment plant
Electric slag cleaning Bleed of cooling water Waste water treatment plant
furnace
Cooling water for slag granulation Waste water treatment plant
Anode furnace (incl. casting Bleed of cooling water Waste water treatment plant
wheel)
Sulphuric acid plant Wet cleaning of roast gases Waste water treatment plant
Water treatment plant Effluent treatment Discharge, reuse as cooling water
(waste water/storm water)
The main solid outputs generated in primary copper production are summarised in Table 2-8.
Table 2-8: Outputs from primary copper producing plants
Process unit Outputs Use/treatment options
(Roasting) Smelting Slags Internal use or external use as construction material or
furnace (incl. gas abrasive manufacturing
cleaning)
Dust Internal use or bleed for external metal recovery
Converter (incl. gas Slags Internal use or external use as construction material or
cleaning) abrasive manufacturing
Electric slag cleaning Slags External use as construction material or abrasive
furnace (incl. gas manufacturing
cleaning)
Sulphuric acid plant Sulphuric acid By-product for sale
Fire refining (incl. gas Slags Internal use
cleaning)
Electrolytic refining Anode slime Internal precious metal recovery or sold for external
(incl. gas cleaning) treatment
Anode scrap Internal use
Electrolyte bleed Further processing for acid recovery and reuse as well as
nickel sulphate to be sold
Scrubber bleed Recycled to the electrolyte
Waste water treatment Sludges/residues Internal recovery of metal content, waste disposal, sale
plant product
2.2.2 Secondary copper production

Depending on the metal content and the type of feed, the smelting step to produce copper
metal from secondary materials may comprise several stages, like reduction,
oxidation/slagging and volatilisation, for upgrading the metal content and separating other
components from copper. The subsequent fire and electrolytic refining is analogue to the
primary copper production9. Depending on the purity and composition of the copper
containing materials, they are added at different stages of the process. In the following
sections, first a general process description of the secondary copper production is given (c.f.
2.2.2.1). Typical outputs to the different environmental media are then described in the section
2.2.2.2.
9
Process steps following the electrolytic refining such as founding, alloying, casting, etc., will not be
described in this report.
2.2.2.1 General process description

In Figure 2-5, a schematic flowsheet for the secondary copper production is given. In the
following sections the main input materials, the different production steps and process units of
secondary copper production are described in detail. The underlined terms refer to Figure 2-5.
Residues,
sludges,
electronic scrap,
slag, dust
Blast furnace Flue dust

or
Electric furnace Slag
Black copper
(70 - 80 % Cu)
Slag
Bronze, Converter Flue dust

gunmetal,
brass
Converter copper
Flue dust (83 - 98 % Cu)
Anode furnace
Slag or
Anode shaft furnace
Copper scrap
Copper anodes
(about 99 % Cu)
Electrolytic Electrolyte
refining
Anode slime
Wire rod production Cathodes

- cathode shaft furnace
- continuous casting
- wire rod plant
Wire rod
Figure 2-5: Flowsheet for secondary copper production

Source: following VDI-Richtlinie 2102 [75]
Inputs for secondary copper production

Inputs for secondary copper production are divided into:
- mainly metallic, oxidic and sulphidic raw materials,10

- fluxes and additives, and
- reductants (e.g. coal, coke, fuel oil, natural gas).
The most common raw materials for secondary copper production are metallic raw materials
(different scraps from copper and copper alloys) and oxidic materials (copper-rich slags,
ashes, drosses, dust and sludges).
Metallic materials
Pure copper scrap from manufacturing (fabrication scrap, wire scrap) or used product
recycling can be remelted directly at the semi-finished products plant just as alloy scrap
consisting of pure alloys (e.g. brass, bronze and nickel-silver). If not, the copper scrap is
processed in a converter to remove zinc, tin and lead by oxidation and volatilisation. The
converter copper is thereafter refined in an anode furnace and by electrolysis. Copper scrap
can be contaminated with plastic and organic materials such as grease or with other metals
such as lead and tin from soldered or brazed joints. Typical scraps are e.g. copper piping,
sheets or iron-bearing electrical scrap (electric motors) or heating appliances (immersion
heaters of washing machines). Another type of copper scrap is copper-iron scrap such as
electric motors, plated scrap, circuit elements and switchboard units, telephone scrap,
transformers, shredder materials. The processing depends on the composition and can take
place in an anode furnace or in a converter followed by electrical refining. A variety of special
materials such as cable scrap, electronic scrap etc. require special processing routes. When
cables are sheathed with lead, the sheath has to be removed manually [49] and/or by
segregation melting [67] before shredding. Depending on their chemical composition, the
different scrap fractions can be added into the process at different stages.
Oxidic materials
Oxidic materials are of a low grade with a copper content from 10 - 60 %. These raw
materials have to be reduced to a metallic intermediate product which then can be refined in a
converter. Some typical oxidic raw materials are listed in the following.
Drosses result from the melting of copper and its alloys when molten material comes into
contact with oxygen. A metal oxide is then formed on the surface and is skimmed off
periodically. Droplets of metals become trapped in the dross. Filter dust containing copper
10
Sulphur containing raw materials are only processed if a sulphuric acid plant is installed for off-gas
cleaning.
oxide are collected from the off-gas cleaning system. Other raw materials are catalysts from
copper based catalysts. They contain carbon which forms a deposit on the surface during the
use of the catalysts. Electroplating sludge and waste water sludges can also be recycled in
secondary copper production. Table 2-9 shows some typical external recycling material for
secondary copper production with the respective copper content and source.
Table 2-9: Major copper-containing external recycling materials
Type of material Cu-content Sources
[wt-%]
Mixed copper sludges 3 - 10 Electroplating
Computer scrap 15 - 20 Electronics industry
Copper mono-sludges 10 - 30 Electroplating
Copper-iron material (lumpy or comminuted) from 10 - 20 Electrical industry
armatures, stators, rotors etc.
Brass drosses, copper-containing ashes and slags 20 - 25 Foundries, semi-finished product plants
Red brass drosses, copper-containing and slags 20 - 25 Foundries, semi-finished product plants
Shredder material 60 - 65 Shredder plants
Copper-brass radiators 60 - 65 Cars
Mixed red brass scrap 75 - 85 Water meters, gear wheels, valves, taps,
machine components, bearing boxes,
propellers, fittings
Light copper scrap 88 - 92 Copper sheets, eaves, gutters, water
boilers, heaters
Heavy copper scrap 90 - 96 Sheets, copper punchings, slide rails,
wires, pipes
Mixed copper scrap 90 - 95 Light and heavy copper scrap
Copper granules 90 - 98 From cable comminution
Pure No. 1 scrap 99 Semi-finished products, wire, cuttings,
strip
Source: Stelter [64]
Production units in secondary copper producing plants11

The standard technology for smelting secondary raw materials is the blast furnace process as
shown schematically in Figure 2-6. It has a high flexibility in regard to raw material
processing. The copper blast furnace is a shaft-type counter-current reactor in which the
feedstock sinks downward from the top. The hot reaction gases flow upward from the bottom
and heat the column of material. The shaft is sealed at the bottom by a crucible (a vessel lined
with refractory material). The off-gas is extracted from the upper part of the shaft. In the case
of furnaces having a closed throat at the top, the feedstock material is fed into the shaft via a
transfer lock, while in the case of designs with an open throat, the feedstock material provides
11
The main parts of the process descriptions in this chapter are based on the current German VDI-Richtlinie
2102 [75].
a top seal itself. The furnace shell is either water-cooled over its entire height or in the lower
part.
Input Feed-
material water
Off-gas
Blast Afterburning Waste-heat Bag
Cooler
Blast furnace chamber boiler house
air
Black copper Steam
Blast furnace
oxide
Flue
dust
Figure 2-6: Treatment of blast furnace off-gas (secondary copper production)
The feedstock for blast furnaces includes secondary raw materials containing copper and noble
metals originating from copper smelting and refining, copper foundries, the metal processing
industry or mechanical concentrating plants for copper-containing materials (e.g. electronic
scrap). The processed raw materials are, for example, copper-rich slags, copper drosses, filter
or cyclone dusts, different sludges copper scrap, copper-iron scrap and copper-alloy scrap.
Iron, lime and silica carriers are added to form the slag and coke is added as a fuel and for the
purpose of reduction. As an example, the feedstock can be metered using a hopper system.
Charging can be carried out in batches using buckets, or continuously at the head of the
furnace. The transportation and charging systems are enclosed in order to prevent dust
dispersal.
The blast furnace is operated using blast air (pre-heated and/or oxygen-enriched air). The
molten phases of metal and slag collecting in the crucible are tapped off separately or together
as a mixture. In the case of a combined run-off, the slag and metal are separated in a
forehearth. The slag is granulated or poured into conical pots and mainly finds application as
synthetic iron-silicate brick in the building industry or as a blasting material.
Some of the impurities present in the feedstock, such as zinc, lead and tin, are reduced,
vaporised and oxidised by atmospheric oxygen above the stock column or in the subsequent
exhaust gas passage and discharged with the furnace off-gases. After passing a controlled
afterburning system12, the reaction gases are fed to a gas cleaning plant via a waste-heat
utilisation system. In a bag house, blast furnace oxide is precipitated. It is an important
intermediate for metal extraction in other smelting plants or is sold directly as a product.
12
To remove the furnace off-gases safely and in an environmentally acceptable manner in the case of blast
furnaces with an "unfired throat", it is necessary to fit an afterburning chamber in the downstream off-gas
system, in which the afterburning of carbon monoxide and organic constituents (or compounds) is
essentially carried out.
Emissions at the run-off of the blast furnace are collected by extraction hoods and fed to the
gas cleaning plant.
By using a rotary converter instead of a blast furnace, the movements and the mass transfer,
which are rather low in a blast furnace, can be increased. The rotary converter (TBRC) is
operated batchwise. The heat for reduction is produced with the help of a flame from a water-
cooled lance. Gas, heavy fuel and even powdery fuel can be used for the production of heat
and as a reductant.
A rather new technology is the electric furnace, which has the advantage that it produces
smaller amounts of off-gas. Compared to the blast furnace, the raw material generally has to
be pretreated as the electric furnace allows only a particle size of up to 100 mm and limited
humidity. It is used in three different ways, depending on the raw material processed:
- Raw material with a low copper content as well as raw material consisting of oxides and
sulphides are processed to copper matte, which is further processed in the converter to blister
copper,
- raw material with a low copper content as well as raw material consisting of lead and
sulphides is processed to copper-lead-matte, which is likewise processed in the converter to
blister copper. The lead is removed with the slag which is used for lead recovery and
- raw material with a low copper content as well as raw material consisting of oxides is
reduced to black copper,
For processing the latter, coke is likewise used as a reducing agent, but the melting heat is
generated by electrical energy introduced by electrodes immersed in the molten slag, which
provides electrical resistance. So the material usage per ton of black copper produced is less
for an electric furnace than for a blast furnace and it emits correspondingly low amounts of
off-gas. Since the electric furnace can be operated with a small amount of return slag, it is a
comparatively small and well enclosed unit. Fugitive emissions occur during tapping and in
the launders and these are extracted via off-takes ("subsidiary off-takes") and then fed to a gas
cleaning plant. The separate purification of the subsidiary off-take waste air makes it possible,
in the case of sulphur-containing feedstock, to purify the SO2-containing furnace off-gas in the
contact plant in which the SO2 is converted into sulphuric acid.
The charge is prepared with a composition to suit the particular smelting program and fed into
the furnace via an enclosed charging system. The molten product is tapped off via various
tapping holes into buckets or ladles.
As in the blast furnace, zinc, tin and lead are essentially volatilised during the reducing
smelting, discharged as oxides with the off-gas and precipitated in the gas cleaning plant. For
the purpose of further purification, the off-gas may be fed to a contact plant after additional
scrubbing. The precipitated flue dusts are processed further.
Besides the processing of the sulphidic phase (copper matte) in converters (c.f. 3.1.1.3), in
secondary smelters a converter is used for further copper enrichment of the metal phase (black
copper). This device is very flexible and can be used either for reduction as described above or
for volatilisation, depending on the fuel air ratio.
The converter is operated in a batchwise manner, the feedstock consisting of alloy scrap (for
example, bronze, red brass, brass, aluminium bronze, German silver, Tombac, tin alloys and
various special alloys), suitable Cu-Fe scrap (copper content higher than 75 %) and also black
copper and bronze from the in-house production, the latter being introduced partly in liquid
state. Copper-rich return slags from the furnace for anode production and converter sectors
can also be used, if possible in one heat, i.e. liquid.
Coke and iron-rich materials are used as fuel and as a reducing agent. The feedstock is
introduced using so-called "boats" (for solid materials) and ladles (for molten materials), the
latter also being used to collect the products, i.e. raw copper and slag. The boats and ladles for
charging are transported by means of a crane. In some cases, cold material may be fed into the
converter via a side charging hole during blowing.
Air, possibly enriched with oxygen, is blown into the bath from the rear through tuyéres.
Because of their greater affinity for oxygen, the base metals (for example Fe, Al, Zn, Sn, Pb)
largely undergo oxidation. Iron and aluminium are completely adsorbed by the slag, while
zinc, tin and lead are only partly adsorbed by the slag as oxides and partly volatilised and
discharged into the gas cleaning plant with the off-gases. The copper-containing slag is mainly
recirculated to the blast or electric furnace. The off-gases are fed to a gas cleaning plant. The
precipitated converter oxide can be used as an important intermediate for extracting the
quantities of lead, zinc and tin contained in the feedstock or it can be sold directly as a
product.
To collect or reduce the emissions occurring during charging and pouring, converters are
enclosed or provided with extraction hoods. The waste air extracted from the housing or
hoods is expediently used to convey the oxides, i.e. primary and secondary off-gases are
removed together.
For refining the converter metal (further removal of accompanying elements), reverberatory
(anode) furnaces (hearth type) are used, as they are better suited for the melting of solid
scrap than rotary furnaces. This is an advantage since, in contrast to the primary copper
production industry, in the secondary copper production industry copper scrap is used for the
anode production on a large scale. The fixed or tiltable hearth-type furnaces are heated with
fuel oil, gas and pulverised coal either individually or in combination. The combustion air is
blown in cold or pre-heated and can, if necessary, be enriched with oxygen. The feedstock
consists of converter copper (solid or molten), used copper material, in-house returns such as
anode scrap from electrolysis and blister copper from primary smelting, if available.
Solid feedstock is introduced by means of charging machines, while liquid feedstock is poured
in via launders. Reverberatory anode furnaces are operated batchwise, one charge involving
loading, melting, refining and pouring.
After the feedstock has been melted completely, the melt is refined, i.e. the impurities are
oxidised using air. In this process, traces of sulphur present in the raw copper are
simultaneously oxidised to SO2 and are then discharged with the off-gas. In the case of fixed
furnaces, the air is blown onto the bath, while in the case of tiltable furnaces it is blown into
the bath. The slag formed in this process is drained off, then the melt is heated to
approximately 1,250°C and rendered pourable, i.e. the oxygen content (mainly present as
Cu2O) is reduced to about 0.1 %, under reducing conditions established by immersing wooden
poles in the bath or blowing in reducing gases. The copper is cast in anode formats on a rotary
casting machine.
The firing, and the amount and composition of the off-gases and also their dust content varies
with the furnace phase. The off-gases are first fed to a heat exchanger (waste-heat boiler and
tubular cooler) and then to a gas cleaning plant. To counteract corrosion due to SO2 and off-
gas humidity, lime (white lime hydrate) is blown into the off-gas. The precipitated dusts and
the drained off slags are reused, generally in a blast furnace.
The Contimelt process, developed by Norddeutsche Affinerie and Union Minière, is an

energy-saving process for continuously melting and refining raw and used copper and also for
casting refined copper as anodes. The plant consists of three units:
- hearth furnace equipped with a shaft for charging and pre-heating and for the oxidation of
the molten copper,
- poling furnace for continuous reduction of the molten copper from the Contimelt furnace,
and
- a casting plant for anode casting.
Natural gas is used as fuel and poling gas. The feedstock is transported by means of a skip into
the shaft of the furnace and is pre-heated in the latter by the hot furnace off-gas. During the
refining in the hearth of the furnace, a slag is produced which is drawn off and processed
further. The refined, molten copper flows continuously via a launder into the poling and
casting furnace and, after being poled with natural gas in the latter, it is fed via a launder to
the casting plant.
The off-gas plant consists of a waste-heat boiler for generating steam, a heat exchanger for
pre-heating the burner air, a cooler and a gas cleaning plant. Carbon containing lime, for
example, may be introduced via a metering system for conditioning agents into the off-gas to
adsorb organic constituents. Tapping holes and launders are provided with extraction hoods,
via which diffuse emissions are likewise fed into the gas cleaning plant. The precipitated filter
dust is recycled.
The remaining minor elements such as lead, nickel and precious metals are removed in the
subsequent electrolytic refining as already described in section 2.2.1.1.
2.2.2.2 Main outputs and environmental concerns of secondary copper producing

plants
The potential sources of stack and fugitive emissions into the atmosphere from secondary
copper production processes and arising contaminants are summarised in Table 2-10.
Table 2-10: Potential sources of stack and fugitive emissions from German secondary
copper producing plants
Process unit Operation/source Emission/main contaminants f s
Raw materials Handling, storage, transport Particulate matter x x
storage
Blast furnace (incl. Smelting/off-gas Gas, particulate matter x x
Gas cleaning)
Electric furnace Smelting/off-gas Gas, particulate matter x x
(incl. Gas cleaning)
Converter (incl. Converting/off-gas Gas, particulate matter x x
Gas cleaning)
Contimelt furnace Smelting/refining Gas, particulate matter x x
Electrolytic refining Electrolysis cells/tanks/washing Mist x
chambers
Continuous casting, Material handling, off-gas from Particulate matter, fumes x
wire rod plant furnaces
f: fugitive emissions; s: stack emissions
In the processing of secondary raw material, mostly the same liquid effluents occur as for
primary copper production (c.f. 2.2.1.2), nevertheless the potential sources of water pollution
are summarised in Table 2-11.
Table 2-11: Potential sources of water pollution from secondary copper production
Process unit Operation/ Potential source Use/treatment options
General Rain water from roads, yards, roofs, Waste water treatment plant
wet cleaning of roads
Blast furnace Bleed of cooling water Waste water treatment plant
Electric furnace Bleed of cooling water Waste water treatment plant
Converter Bleed of cooling water Waste water treatment plant
Contimelt furnace Bleed of cooling water Waste water treatment plant
Anode furnace Casting wheel Waste water treatment plant
Water treatment plant Effluent treatment Discharge/ reuse as cooling water
(waste water/storm water)
The main outputs generated in secondary copper production are summarised in Table 2-12.
Table 2-12: Outputs from secondary copper producing plants
Blast furnace Blast furnace oxide (flue dust) Internal recycling or sale for metal
recovery
Slags External use as construction material
or abrasive manufacturing
Electric furnace Slags External use as construction material
Lead bullion Further processing (refining)
Gas cleaning (furnace off-gas) Dust Recycling
Converter Slags Internal use or external reuse
Gas cleaning (converter off-gas) Converter dust Recycling
Contimelt furnace Dust Recycling
Slags Internal use or external reuse
Electrolytic refining Bleed electrolyte Further processing for acid recovery
and reuse as well as nickel sulphate to
be sold
Anode slime Internal recovery of precious metal or
sold for external treatment
Electrolyte bleed Further processing for acid recovery
and reuse as well as nickel sulphate to
be sold
Gas cleaning (gas from refining) Scrubber bleed Recycled to the electrolyte
Tin-lead alloy plant Tin lead alloy Sale product
Slags Recycling or waste disposal
Dust Sale product (ZnO)
Waste water treatment plant Sludges/residues Internal recovery of metal content,
waste disposal, sale product
2.2.3 Further processing of copper cathodes

Copper cathodes must be remelted and cast into shapes, because the structure of copper
formed by the electrolytic refining is not suitable for working to semi-finished products.
Cathodes are remelted in several types of special furnaces that perform the tasks of melting,
post-refining (if necessary), holding and casting. In the following continuous processes to
fabricate wire rod and processes for the fabrication of semi-finished products from copper and
copper alloys are described.
2.2.3.1 Fabrication of wire rod

The most common continuous rod casting processes are further developments of the wheel-
belt casting principle. Copper cathodes and recycling copper are melted in a shaft furnace. The
molten copper is fed continuously via a launder to the grooved periphery of the casting wheel.
After being shaved, the cast bar is fed to a rolling mill. The rolled rod is treated in a pickler
with isopropanol, dilute sulphuric acid, water or steam rinsing to remove the oxidised surface
and then coated with wax (c.f. Figure 2-7).
Off-gas
Shaft Rolling mill Wire

Caster Pickler
Cathodes, furnace train rod
recycling copper
Figure 2-7: Wire rod plant

Another process to produce wire rod is the CONTIROD process. There, the copper is melted
in a furnace and caste in a Hazellet-Caster. The caster is followed by a hot-rolling mill to
produce wire rod which is sent to a coiler after being treated in a pickler. The basic concept of
this process is shown in Figure 2-8.
Copper cathodes from

electrolytic plant
Shaft
furnace
Holding
furnace
Metering
vessel
Caster
Mill Pickler Coiler
Figure 2-8: Basic concept of the CONTIROD process
Wire rod can also be produced by dip forming. With this process, a copper core wire (mother
rod) is drawn through a molten bath of oxygen-free copper. Thereby additional copper
solidifies on the surface to form a new rod. The rod produced is reduced in diameter in a mill
under inert gas, so the copper wire is oxygen-free. About one third of the rolled wire is
returned to form the core material.
2.2.3.2 Fabrication of semi-finished products from copper and copper alloys13

The following description represents a compilation of the most common processes and
techniques for the fabrication of semi-finished products from copper and copper alloys
including the applied abatement techniques.
Feed materials for the manufacture of semi-finished copper and copper alloy products are
mainly: Copper cathodes, high grade copper scrap, fire-refined copper, copper alloy scrap,
alloy metals, master alloys, etc. The main process steps for the fabrication of semis are
illustrated as summary in Figure 2-9. The production steps for the different products are
normally:
- Raw material processing,

- melting and casting,
- rolling mills for strips and sheets,
- extrusion and fabrication of tubes, rod and sections using different methods for working
down,
13
Based on „Fabrication of Semi-Finished Products From Copper and Copper Alloys“, EUROMETAUX Copper
Industry [66]
- annealing and pickling (this step is often integrated in other process steps), and
- degreasing (this step is often integrated in other process steps).
Copper Cathodes
High grade copper scrap
Fire-refined copper
Alloy metals; Master alloys
Internal scrap Alloy scrap
Gas
Gas cleaning
Melting
Slag to Dust to
smelters smelters
Casting of shapes
Billets, cakes
Hot & cold working

(Extrusion and drawing or rolling)
Semi-Finished Products
Figure 2-9: General flowsheet of semi-finished product fabrication

Source: [67]
Before charging into the melting furnace, raw materials like wires, punchings, cuttings, tubes
etc. are pressed into blocks. Oil contaminated scraps are decreased or the off-gases of the
furnace have to be treated in an afterburning chamber.
For melting, there are different kinds of furnaces in use: Batchwise operated electric furnaces
are mainly used for copper alloy melting and to a lesser extend for unalloyed copper. Natural
gas or fuel fired crucible, drum or hearth/reverberatory type furnaces are used for the
discontinuous fire refining of the input materials. As in the fire refining step of the copper
production, minor accompanying elements are reduced by an oxidation step and the oxygen
content is reduced in the following reduction step by means of wood poles. If continuous
operation and/or high capacity is necessary, shaft furnaces like the ASARCO furnace are in
use. The ASARCO furnace is an energy saving melting facility, because the combustion gases
of the natural gas fired burner are used to pre-heat the charge. Fire-refining and alloying are
not possible in this furnace. The off-gases of the furnaces are collected and cleaned in a
cyclone and a baghouse.
The molten copper is either directed directly to the casting units or to a holding furnace, where
some alloying can take place. Then the materials are casted into billets or cakes/slabs in
continuous or discontinuous casters. Discontinuous casting is always carried out in the vertical
mode, continuous casting can be either in the vertical or horizontal mode. The basic principle
is shown in Figure 2-10.
Stopper Rod
Holding and Casting Furnace

Surface covered by carbon
Out
Primary cooling Casting Mould
water
In
Secondary (spray) cooling
Cast Shape (Billet or Cake/Slab)
Stripping Roller
Start Head
Figure 2-10: Principle of continuous or discontinuous casting
The casted slabs/cakes are used for the fabrication of sheets and strips by a rolling mill, billets
are used for the fabrication of copper and copper alloy tubes, rods and sections by extrusion
presses or rolling mills. The fabrication processes are described in detail in section 3.1.5.2.
2.2.3.3 Main outputs and environmental concerns of the further processing of copper
The main outputs generated in the casting and wire rod plants are summarised in Table 2-13.
Table 2-13: Outputs from the further processing of copper
Melting/holding furnace Dust Internal or external reuse
Caster Cooling water Waste water treatment plant, if necessary
Rolling mill train, pickler Pickling acid Recovery of copper content by electrowinning
(electrical extraction), internal reuse
Rolling emulsion Treatment
Cooling water Waste water treatment plant, if necessary
2.2.4 Plants for copper production and further processing of copper cathodes
In Germany, one flash smelting process is in use for primary copper production, for secondary
copper production, two plants use blast furnaces and one an electric furnace. Table 2-14 gives
detailed information on German copper production plants.
Table 2-14: Copper production and recycling plants in Germany
Norddeutsche Affinerie Hüttenwerke Mansfelder Kupfer
Aktiengesellschaft, Kayser AG, Lünen und Messing GmbH,
Hamburg Hettstedt
Primary smelter Flash smelting furnace - -
Electric furnace for slag
purification
Copper converters
Anode furnace
Secondary smelter Electric furnace Blast furnaces Blast furnaces
Copper converters Scrap converters Scrap converters
Contimelt plant Rev. anode furnaces Anode hearth shaft
Scrap converter/TLA plant Tin-lead alloy plant furnaces
Rotary anode plant
Electrolysis ISA technology ISA technology Conventional
technology
Further processing Continuous casting - Cathode shaft furnace
Wire rod plant Continuous casting
Wire rod plant
Feed consumption 1,2 Mio 250,000 n. a.
[t/a]/composition (primary and secondary raw (secondary raw materials)
materials)
Cu-cathode 380,000 170,000 n. a.
production
capacity [t/a]
Wire production (60+40) - n. a.
capacity [t/h]
Casting (30+30) - n.a.
Main by- Sulphuric acid Zinc-oxide n. a.
products Slag Tin-lead alloy
Precious metals Anode slime
Lead Copper sulphate
Nickel sulphate
Slag
Certificates ISO 9002 ISO 9002 n. a.
ISO 14001
EMAS
Dealt with in 3.1 3.2 3.3
section
In Table 2-15 information about the products and capacity of main plants for further copper
processing in Germany is given. German cable manufacturing plants are not mentioned in this
Table.
Table 2-15 : Main plants for the further processing of copper

Company Site Production Production line Employment
[t/a] (1996)
Deutsche Gießdraht GmbH Emmerich 225,000 (1997) Wire rod -
Friedrich Kemper GmbH & Co KG, Duisburg - Bar, section and rod, -
Kupfer und Drahtwerke strip/sections, wire rod,
wire
MKM Mansfelder Kupfer und Messing Hettstedt 170,000 Sheet, plate, bar, section 1,100
GmbH, Hettstedt and rod, strip, foil, tube,
wires
Norddeutsche Affinerie Aktiengesellschaft Hamburg 350,000 Wire rod, billets, bar, 2,100
section
Wieland Werke AG Ulm, 307,000 Sheets, strip, tubes, rods, 3,800
Vöhringen bars, wires, sections,
finned tubes
KM Europa Metal AG Osnabrück 225,000 Tubes, strips, sheets, 2,380
specials
Berlin 63,000 Brass products (tubes, 420
wires, sections)
Schwermetall GmbH Stolberg 261,000 Sheets 318
Prym Stolberg 58,000 Strips, sheets, wires 417
Sundwinger Messingwerk Hemer 12,000 Strips, sheets 450
Lacroix & Kress GmbH Bramsche - Wire rod, wires -
The locations of German copper production and main further processing plants are shown in
Figure 2-11.
Hamburg
Bramsche Berlin
Osnabrück
Emmerich Hettstedt
Lünen
Duisburg Menden
Hemer
Stolberg
Ulm
Primary and secondary copper production

Further processing of copper cathodes (examples)
Figure 2-11: Locations of copper producing plants in Germany

3 Process technology, abatement techniques and present

consumption/emission levels in German copper production
In the following, the copper producing plants operated in Germany are presented in detail.
Based on the general description given in chapter 2, the process technology and abatement
techniques applied are described. The present consumption and emission levels for each plant
are given, if available.
3.1 Copper production at Norddeutsche Affinerie Aktiengesellschaft

Norddeutsche Affinerie Aktiengesellschaft (NA) was founded in Hamburg in 1866 and is
today the largest copper producing plant in Western Europe with an annual output of at
present 405,000 t/a of copper. NA is the only primary copper plant in Germany. It had a
turnover of 2.15 billion DM and more than 2000 employees in 1996. Both primary copper
(220,000 t/a) from copper concentrates (700,000 t of copper concentrates with an average
copper concentration of about 31 % are processed yearly) as well as secondary copper
(150,000 t/a) from different internal and external recycling materials are produced. An
additional 35,000 t/a of external copper cathodes are purchased. Various by-products of
copper production such as slags (at present 400,000 t/a), miscellaneous chemicals (e.g.
sulphuric acid: 656,000 t/a) and precious metals (gold: 7.8 t/a, silver: 200 t/a) are obtained. In
Figure 3-1 an overview of the copper production pathways at NA is given and in Table 3-1 the
main input materials and products are listed.
In the following sections, detailed descriptions of the main process units of the NA plant are
given, divided into:
- primary smelting plant,

- secondary smelting plant,
- electrolysis of primary and secondary copper,
- Southwire copper wire rod plant, and
- continuous casting of billets and slabs/cakes.
Finally, data on emissions and environmental concerns are summarised in section 3.1.7.
External Copper alloy Internal and external Copper scrap Copper
raw lead scrap intermediate products electronic scrap concentrates
Pelletizing
Briquetting
Slag
Slag SO2 containing

Pb-dross gases
Electric Flash smelting
furnace Copper furnace
Slag (sec. plant) matte
Lead bullion Copper Electric

matte furnace
Copper-lead
matte Copper
Slag matte Slag
Scrap
Lead converter Copper scrap
Converter Copper SO2 containing gases
refinery blister copper
(sec. plant) converter
Lead-tin-
zink- Raw copper Raw copper Raw copper SO2 containing gases
flue dust
TLA Anode Anode Slag

plant shaft furnace furnace
Drosses
Poling and Copper scrap
casting furnace
Copper scrap
blister copper
Anodes
Doré spent
Cupellation metal Electric Anode slime electrolyte Chemical Chemical
Chemical Electrolysis
plant furnace plant plants plants
Zinc
Crude silver Selen tin
solution lead
Cathodes
Precious Selenium Continuous Rod Powder Sulphuric acid

metal plant casting plant plant plant plant
plant
Copper
Refined Antimony tin Au Ag Pt Pd Selenium Zinc Tin lead Copper Casting Rolling Nickel oxychloride Building
Metal powder sulphate Sulphuric acid
lead compounds oxide alloy cathodes products wire Copper material
abrasives
hydroxide
Copper
oxidule
Figure 3-1: Copper production at Norddeutsche Affinerie Aktiengesellschaft

Source: Company information by NA [55]
272 Process Technology, Abatement Techniques And Present Consumption/Emission Levels
Table 3-1: Input/output data from NA (1996)

Input materials Quantity [t/a] Products Quantity [t/a]
Copper concentrates 690,000 Electrolytic copper 370,000
Copper scrap 95,000 Copper salts 6,500
Shredded material 1,200 Nickel sulphate 1,800
from electronic scraps
External intermediate 86,000 Precious metals 150
products
Refined lead 9,000
Sulphuric acid 660,000
Slags 410,000
Source: Company information NA, 1998
3.1.1 Primary smelting plant
3.1.1.1 Outokumpu flash smelting furnace

NA uses an Outokumpu flash smelting furnace for the processing of copper concentrates. The
furnace was commissioned in 1972 and now has a permitted concentrate capacity of
950,000 t/a. The concentrates, which have a copper content between 30 and 34 %, are fed via
a concentrate burner into the flash smelting furnace. The particle size is about 50 µm for the
concentrate and 2 mm or less for the fluxes. 2,400 t/d of input material are fed into the furnace
including 200 t/d of silica flux and recycled flash smelting furnace dust as well as 200 t/d of
liquid converter slag from the Pierce-Smith converter (c.f. Figure 3-1). The use of oxygen
enriched air amounts to 500 Nm³/min. Table 3-2 shows some process data for the Outokumpu
flash smelter used at NA.
Table 3-2: Process parameter of the Outokumpu flash smelting furnace at NA
Blast details:
Temperature [°C] 400 - 420
Oxygen enrichment [vol.-%] > 45
Flow rate [m³/min] 420
Copper matte:
Cu content [wt-%] 60 – 65
Temperature [°C] 1,200
Slag:
Cu content [wt-%] 1-3
Fe content [wt-%] 37 - 42
SiO2 content [wt-%] 30 - 32
Source: Biswas/Davenport [8], Langner [49]; company information NA, 1998
Process Technology, Abatement Techniques And Present Consumption/Emission Levels 273
About 1,400 t/d of copper matte with an average copper content of about 65 % and an output
temperature of about 1,200 °C are transferred to the Pierce-Smith converter for further
processing. The flash smelting furnace slag (1,200 t/d) with a relatively high copper content of
1 - 3 % is processed in the electric furnace to reduce the copper content.
The off-gases from the Outokumpu furnace (40,000 - 60,000 Nm3/h) leave the furnace at a
temperature of 1,200 - 1,300 °C and a sulphur dioxide concentration of about 25 – 30 vol.-%.
The off-gas is cooled in a waste-heat boiler and with recycled gas, which has a temperature of
about 260 °C. With an off-gas temperature below 400 °C, the formation of sticky dusts is
prevented. Part of the flue dust is thereby precipitated in the waste-heat boiler. The gas is then
cleaned in a hot-gas electrostatic precipitator. After pre-heating the process air and the feed
water for the waste heat boiler in a heat exchanger, the gas enters the sulphuric acid plant,
where it is treated together with the dedusted off-gases from the converting operations. Figure
3-2 shows a diagram of the off-gas treatment applied for off-gases with a high content of
sulphur dioxide at NA.
Off-gas from flash

smelting furnace
Scrubbing and
Hot-gas ESP Wet electrostatic Mercury removal
cooling unit
precipitator (absorption)
(multistage)
Off-gas from Pierce-Smith
converter (primary plant)
Gas cleaning
Drying tower
(Absorption in conc. Catalysis Absorption Cleaned off-gas
sulphuric acid)
Sulphuric acid plant
Sulphuric acid
Figure 3-2: Treatment of Outokumpu flash smelting furnace and Pierce-Smith converter
off-gas at NA
3.1.1.2 Electric furnace for slag cleaning (primary plant)

The slag produced in the flash smelting furnace contains about 1-3 % copper and is
channelled to an electric furnace with a requirement of electrical energy of 50 kWh/t liquid
slag for decopperising. During the slag cleaning process a C-bearing agent is added to the
molten slag. The copper is collected at the bottom as a sulphide phase (matte) which is tapped
and further treated in the converter process. 420 t/d of copper matte are recovered and sent for
further processing to the converter. Depending on the market requirements, the 1,200 t/d of
slag with a copper content of less than 0.8 % are either granulated (abrasives) or cast in slag
pots, slowly cooled down and broken into lumps. The lumpy slag is used as a construction
material. The dust arising during the slag cleaning (2 t/d) is sold for further processing.
The off-gas from the electric slag cleaning furnace (40,000 Nm3/h) is afterburned, cleaned in a
fabric filter and further cleaned together with the ventilation gases from secondary hoods
above the furnace roof, the tapholes, launders and slag ladles as well as the doghouse for the
matte ladle in a central baghouse.
The water used for granulation is operated in a closed circuit and cooled by cooling towers.
Water from surface run-off is added if necessary, to make-up the required volume.
3.1.1.3 Pierce-Smith converter (primary plant)

The matte from the flash smelting furnace and the electric slag cleaning furnace is transferred
in ladles by crane to the Pierce-Smith converters for conversion into blister copper by blowing
with oxygen enriched air.
At Norddeutsche Affinerie’s primary smelter, 3 converters are installed with a capacity of

250 t each. Two converters are in operation while one is under repair.
The produced converter copper (230 t/charge) with a copper content of 98 - 99 % is further
processed in the anode furnace. The slag formed during the slag blowing phase (200,000 t/a)
is recycled in the flash furnace via a launder. When pouring slag the launder is enclosed by a
removable hood and the gases are vented and dedusted in the central secondary gas handling
system.
The heat generated during matte blowing is used for melting internal reverts like ladle skulls,
etc., and copper scrap and/or tankhouse anode scrap. Scrap and flux are charged through the
hood to the converter during blowing. In this way, the rolling of the converters in or out of the
stack can be avoided, thus reducing uncontrolled gas releases into the surrounding air.
The SO2 containing furnace process gases (95,000 Nm3/h) are collected in water cooled
primary hoods and have a temperature of about 1,250 °C. After being dedusted in an
electrostatic precipitator, the heat content is used for the pre-heating of boiler feed water. Then
it is conveyed to the sulphuric acid plant for further treatment. Depending on the chemical
composition, the dust collected is recycled to the flash smelting furnace or - when e.g. rich in
lead - transferred to the secondary smelter for treatment.
A secondary hood system at each converter ensures that the secondary gases arising during
converter charging, skimming or metal pouring are collected. The secondary gases are cleaned
in the central baghouse.
3.1.1.4 Anode furnace (primary plant)

NA uses two rotary anode furnaces with natural gas as a reductant for the pyrometallurgical
refining of copper. The tap-to-tap cycle duration is 6 hours; 220 t of anodes with a copper
content of 98.5 - 99.6 % can be produced per cycle. Oxidation lasts half an hour with an air
flow rate of 10 Nm³/min; reduction (poling) takes 3 hours and the flow rate of the reducing
gas is thereby 10 Nm³/min [8]. The 15 t of slag produced during the processing of one charge
are recycled to the converter.
Anode casting is done by mould on a wheel at a rate of 80 tons per hour, the anodes have a
mass of about 420 kg, which is controlled by automatic weighing [8].
For the prevention of fugitive emissions, a secondary hood system is installed. The captured
gases are cleaned in a central fabric filter. The furnace off-gases (75,000 Nm3/h) are
afterburned during poling in a post-combustion chamber and are cleaned in a fabric filter after
being cooled in an air to gas cooler to protect the filter media. The concentration of the main
constituents in the cleaned furnace off-gas (measured as well as authorised values) are given
in Table 3-3.
Table 3-3: Concentrations of main constituents in the cleaned off-gases from the anode
furnace (primary plant)
Substance Unit Measured Value Authorised value
SOx (as SO2) mg/m³ 80 - 380 500
(Mean value of whole refining
cycle)
mg/m³ 2 - 700 1000
(hourly mean value)
NOx (as NO2) mg/m³ 30 - 60 200
-
Cl (as HCl) mg/m³ < 2 - 20 30
Ctotal mg/m³ 6 - 23 50
(if cold input material is used)
Particulate matter*) mg/m³ <1-8 20
*)
The main constituents of the particulate matter are given in Table 3-12
Source: Emission values which are accessible to the authority
The measured values represent the typical range. However, the results of single measurements
can be higher than the given range and reach the authorised values depending on different
operation conditions (charging, pouring, poling etc.), different input materials and changes of
the operating mode.
3.1.1.5 Sulphuric acid plant

The dedusted and combined off-gases from the smelter furnace, the Pierce-Smith converters
of the primary smelter and the electric furnace in the secondary smelter enter a multi-stage
scrubbing and cooling plant to remove any remaining particles and volatile compounds such
as arsenic and halogens. These off-gases are combined with the scrubbed and cooled off-gases
of the secondary plant converters (Pierce-Smith type), and are subsequently channelled to the
mercury removal plant. After absorption of the moisture in concentrated sulphuric acid (the
sulphur dioxide concentration in the off-gas amounts to between 6 - 8.4 vol.-% at this stage)
and the catalytic conversion of sulphur dioxide to sulphur trioxide in the double contact plant,
the gas is processed to sulphuric acid of different concentrations (94, 96, 98, 20 % SO3,
oleum). The production rate of the sulphuric acid amounts to about 2,000 t/d (100 %)
sulphuric acid, the conversion rate for SO2 to SO3 is more than 99.6 % and the off-gas volume
is up to about 290,000 Nm3/h. The main constituents in these off-gases released into the
surrounding air (measured values as well as authorised values) are given in Table 3-4.
Table 3-4: Concentrations of main constituents in the cleaned gas from the sulphuric
acid plant
Substance Unit Measured value Authorised value
SOx (as SO2) mg/m³ 100 - 1100 1250
SO3 mg/m³ 20 - 40 120
NOx (as NO2) mg/m³ 20 - 45 50
-
Cl (as HCl) mg/m³ 2-7 10
-
F (as HF) mg/m³ 1-4 4.5
Class I (TA-Luft)
Cd mg/m³ < 0.001 - 0.02
Hg mg/m³ < 0.001 - 0.07 0.1 (daily average)
TI mg/m³ < 0.001 - 0.02
Sum class I (TA-Luft) mg/m³ 0.001 - 0.11 0.2
Class II (TA-Luft)
As mg/m³ < 0.01 - 0.1
Se mg/m³ < 0.01 - 0.02
Sum class II (TA-Luft) mg/m³ < 0.01 - 0.12 0.5
Class III (TA-Luft)
Sb mg/m³ < 0.01 - 0.03 1
Pb mg/m³ < 0.01 - 0.15 1
Cu mg/m³ < 0.01 - 0.09 1
Sum class III (TA-Luft) mg/m³ < 0.01 - 0.027 1
PCDD/PCDF ng ITE/m³ 0.001 - 0.01 < 0.02
If substances of several classes are present, the mass concentration in the emitted gas should
not exceed a total of 1 mg/m3 for coinciding class I and II substances as well as a total of 5
mg/m3 for coinciding class I and III or class II and III substances. The emissions of substances
class I - III have to be determined as a sum of the particulate matter, the vapour and the gas
share of the respective element and its compounds (according to TA Luft [1]). More
information about the German regulations can be found in section 6.1.2.
operation conditions and changes of the operating mode.
3.1.2 Secondary smelting plant
3.1.2.1 Electric furnace (secondary plant)

Since 1991, NA has been using the electric furnace technology for the processing of smelter
intermediates as well as external recycling materials. This resistance type furnace with a
nominal capacity of 8 MVA replaced four blast furnaces operated up to then. The electric
furnace with a height of 3.3 m and a diameter of 7.4 m reaches a melting capacity of 8 - 25 t/h
[40] and 25 - 60 kg coke are required per ton of burden. As the electric furnace puts higher
demands on the physical properties of the charge than the blast furnace, the input material is
limited to a size of 100 mm and a humidity of < 3 %. A pretreatment of the raw materials can
therefore be necessary (e.g. pelletising). Up to 10 t of copper matte with a copper content of
55 - 63 % are produced per hour which are further processed in the converter. The 13 t of slag
arising during one hour have a low copper content of about 0.7 % and can be sold as
construction material. The off-gas, with a volume of 15,000 Nm3/h and a temperature of about
1,200 °C, enters the off-gas system, which is composed of a cooling device and a fabric filter.
Additional treatment is necessary when the concentration of sulphur dioxide exceeds 800
mg/Nm3. In this case, e.g. during the melting stage, the off-gas is led to the sulphuric acid
plant. The flue dust, which contains high concentrations of zinc and lead, is marketed or
recycled. Secondary hoods are installed to capture fugitive emissions, which can occur during
charging and transfer operations. The secondary off-gas has a volume up to 150,000 Nm³/h
[72].
The electric furnace is cooled with conditioned river water, which is recirculated in a closed
cooling circuit. The water is cooled down in cooling towers, whereby a circuit water bleed of
about 10 m³/h is necessary. In Table 3-5 the formerly used blast furnaces (i.e. two blast
furnaces which together have the same capacity as one electric furnace) are compared to the
newly installed electric furnace.
Table 3-5: Data for the formerly used blast furnaces and the new electric furnace
Blast furnace Electric furnace

Yield of metal Lower High, due to better reduction
Requirement for recycling slags Yes No
Quality of raw materials High flexibility Lower flexibility
Process control system Undemanding Demanding
2 blast furnaces 1 electric furnace
Off-gas (melting stage) [m³/h] 100,000 15,000
Secondary hoods (melting stage) [m³/h] 125,000 150,000
Cooling water [m³/h] 350 10
Emissions (estimation from measurements)
CO [t/a] 20,000 10
SO2 [t/a] 1,300 20
Particulate matter [t/a] 14.5 1.5
Pb [t/a] 1.7 0.4
As [t/a] 0.8 0.04
Source: Velten [72]
3.1.2.2 Pierce-Smith converter (secondary plant)

The copper matte and the copper lead-matte from the electric furnace are further processed in
the Pierce-Smith converter of the secondary smelter with a capacity of 35 t Cu/charge (c.f.
Figure 3-1). 30 - 60 t per charge of converter copper with a copper content of 97 % is
produced and further processed in the anode shaft furnace, the 20 - 40 t per charge of slag as
well as the 0.5 - 2.5 t per charge of dust are re-fed to the electric furnace. The off-gas volume
of 30,000 Nm3/h is used for steam generation in a waste heat boiler, dedusted in an ESP and
led to the sulphuric acid plant.
3.1.2.3 Scrap converter (Pierce-Smith type)

NA operates three scrap converters of the Pierce-Smith type using the so called Knudsen
process. Raw material, such as alloy scraps and shredder material with a copper content
between 60 and 90 %, is charged into the converter as well as black copper from the electric
furnace. The converters have a capacity of approximately 15 t each and about six batches are
processed per day. The converter metal with a copper content of approximately 97 % (7 - 10 t
per charge) is further processed in the Contimelt process as well as in the matte converter at
the primary smelter. The 2 - 4 t per charge of converter slag, containing approximately 30 %
of copper, are returned to the electric furnace for recycling. The off-gas volume of 50,000 -
80,000 Nm3/h is cleaned in a fabric filter. Since zinc, lead and tin are volatilised during the
process, the collected flue dust (2 - 3 t per charge) has a high content of these metals and is
therefore processed in the tin-lead alloy plant.
The particulate matter content and its main constituents in the raw furnace off-gas are shown
in Table 3-6, the concentrations of the main constituents in the cleaned off-gases can be seen
in Table 3-7.
Table 3-6: Particulate matter content and its main constituents in the raw off-gases from
the scrap converter (secondary plant)
Particulate matter
Total [mg/m3] 10,000 - 30,000
Pb [wt.-%] 5 - 30
Zn [wt.-%] 25 - 70
Sn [wt.-%] 1 - 20
Table 3-7: Concentrations of main constituents in the cleaned off-gases from the scrap
converter (secondary plant)
SOx (as SO2) mg/m³ 200 - 500 800
NOx (as NO2) mg/m³ 20 - 30 500
PCDD/PCDF ng/ m³ < 0.1 < 0.5
*)
Particulate matter mg/m³ <1 - 10 20
*)
The main constituents of the particulate matter are given in Table 3-12.
operation conditions (charging, blowing, pouring, etc.), different input materials and changes
of the operating mode.
3.1.2.4 Tin-lead alloy plant

In the tin-lead alloy plant, technical zinc oxide and tin-lead alloy are produced from oxides
arising during the smelting and converting processes. The converter flue dust and, if the tin
content is high enough, also the electric furnace flue dust are mixed with fluxes (sodium
carbonate) and reductants (anthracite coal) and are fed to a Dörschel furnace (25 t dust per
charge). The heat is supplied by an oil burner with a fuel consumption of 200 l/h. The
collected flue dust has a high content of zinc oxide, since the zinc content of the input
materials is transferred to the flue dust as zinc oxide. The remaining metal phase of 10 t per
charge consists mainly of tin (20 - 50 %) and lead (50 - 80 %) which is refined and cast into
ingots and then sold. 8 t of slag, consisting mainly of caustic soda and zinc, is processed in the
flash furnace.
The furnace is equipped with secondary hoods to avoid fugitive emissions. The arising
ventilation gases of these hoods with a volume of 15,000 - 36,000 Nm3/h are cleaned in the
central system. The furnace off-gas (25,000 - 35,000 Nm3/h) is cleaned in a fabric filter. The
concentration of the main constituents in the cleaned furnace off-gas can be seen in the
following Table.
Table 3-8: Concentration of the main constituents in the cleaned furnace off-gas from
the tin-lead alloy plant
SOx (as SO2) mg/m³ n.d. 800
NOx (as NO2) mg/m³ 40 - 100 500
Particulate matter mg/m³ 2-8 20
*)
operation conditions (charging, pouring, etc.), different input materials and changes in the
operating mode.
3.1.2.5 Contimelt process

NA uses the Contimelt process for the fire refining of the converter copper from the electric
furnace path and from the scrap converter. Pure scrap including anode scrap and blister copper
are fed at this stage and melted in the furnace as well. Figure 3-3 shows a schematic view of
the Contimelt process.
Off-gas
Cooler Filter
Anode
Poling Furnace furnace
Copper
Charging
Figure 3-3: The Contimelt process for fire refining of secondary copper
The two-stage process comprises a shaft, which is placed on a hearth furnace, and a
continuously processed poling furnace, from which the copper is cast into anodes on a casting
wheel. The production capacity of the Contimelt plant is about 80 t/h of anode copper with a
copper content of 98 - 99 %. 30 Nm3/t of natural gas are needed for the heat supply and 8
Nm3/t as a reducing agent. The slag from the Contimelt process with a copper content of 55 -
70 % is recycled to the converter of the primary smelter (c.f. Figure 3-1).
An integrated concept for the utilisation of heat has been implemented in the Contimelt plant.
The hot off-gas from the hearth furnace travels in counterflow to the feedstock materials so
that its energy content is utilised to pre-heat the latter and save fuel. After the anode shaft
furnace off-gas has been combined with the hot off-gas from the downstream poling and
casting furnace, the residual heat content is used for heat steam generation in a waste heat
boiler and to pre-heat the process air. Then carbon containing lime is injected into the off-gas
(140,000 Nm3/h) to adsorb organic constituents before it is cleaned by a fabric filter. In Figure
3-4 the energy flows of the Contimelt process are presented in the form of a Sankey diagram.
Poling Furnace Anode Shaft Furnace

0,06 Gcal/t 0,27 Gcal/t
19 % 79 %
Heat of formation
slag oxides
2%
100 %
Poling furnace Shaft furnace
Superheat copper Copper
2%
53 %
Radiation and
convection 4,5 %
Air
1% preheater
Slag
5%
Radiation, convection
and cooling water 5%
Waste heat boiler
Steam
Air
preheater 15 %
Stack losses
19 %
Figure 3-4: Energy flows in the Contimelt process

Source: Company information NA, 1998 [55]
Since the secondary hood system installed to prevent fugitive emissions is part of a central
system, these emissions are shown in Table 3-11.The values of the main constituents in the
cleaned furnace off-gases can be seen in Table 3-9.
Table 3-9: Concentrations of the main constituents in the cleaned furnace off-gases from
the Contimelt process (secondary plant)
SOx (as SO2) mg/m³ 50 - 520 570
NOx (as NO2) mg/m³ 50 - 960 1000
(mean value of daily operation period
referring to 2 shift operation)
mg/m³ 800
(mean value of daily operation period)
kg/d 1700
(referring to 2 shift operation)
CO mg/m³ < 500 500 (mean value of daily operation
period referring to 2 shift operation)
700 kg/h (if post-combustion breaks
down)
PCDD/PCDF ng ITE/m³ < 0.1 - 0.4 0.1
(value for orientation)
Particulate matter mg/m³ <1-8 20
*)
3.1.3 Electrolysis plant for primary and secondary copper

NA uses the ISA technology for the electrolytic refining of anode copper with a production
capacity of about 380,000 t/a of cathode copper. This process is operated with about
60,000 stainless steel plate cathodes and 1080 electrolytic cells. The current density is
between 300 and 330 A/m² and a current efficiency of 95 - 98 % is reached. A low cell
voltage (< 300 mV) is achieved by monitoring the glue content in the electrolyte and a short
anode-anode distance of 95 mm. The cell current amounts to 35,000 A. The power
consumption of the tankhouse amounts to 300 - 350 kWh/t copper. The anodes, which have a
copper concentration of 98.5 - 99.6 %, have a weight of about 420 kg and a lifetime of 21
days. The anode scrap (about 11 % of the anode mass) is recycled. The cathodes have a
plating time of 7 days. The electrolyte has a concentration of about 150 - 200 g/l of sulphuric
acid and about 40 - 50 g/l of copper. The concentration of glue is automatically controlled by
the Collamat® glue control system. 70 - 100 kg of steam per hour are needed to keep the
temperature of the electrolyte between 55 and 65 °C. In Table 3-10 the distribution of
accompanying metals in the anodes and cathodes is shown for the ISA technology used at NA.
Table 3-10: Accompanying metals in anodes and cathodes at NA

Element Anode Cathode
[g/t] [g/t]
Ag 720 9
Se 510 < 0.5
Te 130 < 0.5
As 760 <1
Sb 330 <1
Bi 60 < 0.5
Pb 990 <1
Ni 1,080 <3
5 - 10 kg of anode slime is obtained per ton of anode processed, which is further treated to
recover the precious metals (c.f. Figure 3-1).
3.1.3.1 Secondary hood system

As in the plant descriptions above, some of the furnaces of the primary as well as the
secondary copper production line are equipped with secondary hoods in order to prevent
fugitive emissions. The suction is provided directly at the source to optimise the reduction of
fugitive emissions. Alternatively, the air could be suctioned at the ridge, but therefore, a large
volume of air has to be handled which cannot be cleaned effectively in a fabric filter. Other
disadvantages are likewise high energy consumption, high investment, more waste (used filter
media) and especially the worse conditions at individual working places. In addition, the
applied system reduces the heat input in the aisle. So the lift of the air in the aisle is reduced,
which reduces the emission through the ridge.
Depending on the SO2 content in the suctioned air from the primary smelter, dry sorption
(injection of Ca(OH)2) is applied before the gas stream is cleaned in fabric filters. The calcium
hydroxide is re-circulated to improve its conversion and so to minimise the amount of solid
material arising during the gas-cleaning. The air flow rate is controlled via a closed-cycle
control system by reducing dampers and ventilators with speed control in order to minimise
the energy consumption. 580,000 Nm3/h of secondary gases are captured and cleaned in fabric
filters. Thereby 13.6 GWh/a of electrical energy are consumed and 700 kg of dust are
collected per hour.
S e c o n d a r yhoods
Secondary h o o dofs Cleaned
o f f l a s h s m e l li n g Dust and used filter media
flash smelting furnace
f u r n a c e ( c . f . .. . . . ) recycled to flash smelting furnace off-gas
S e c o n d a rhoods
Secondary y h o o of ds Off-gas conditioning
o f f l a s h s m e l li n g and fabric filter
electric furnace
f u r n a c e ( c . f . .. . . . )
S e c o n d a r hoods
Secondary y h o o of ds Ca(OH)2
o f f la s h s m e llin g Cleaned
converters
fu r n a c e ( c . f . .. . . . ) off-gas
Dust and used filter media
recycled to flash smelting furnace
Off-gas and secondary Fabric filter

hoods of anode furnace
Dust and used filter media

SHoods
e c o n dfor
a r auxiliary
y hoods recycled to flash smelting furnace
odevices
f f la s h e.g.
s m loading
e llin g
station
fu r n a c e ( c . f . .. . . . )
Fabric filter
S e c o n d a rhoods
Secondary y h o o of
ds
o f f la s h s m e llin g
flash smelting furnace
fu r n a c e ( c . f . .. . . . )
Figure 3-5: Secondary hood system of the primary smelter
All solid materials arising during the gas-cleaning are recycled to the flash smelting furnace.
The concentrations of the main constituents in the cleaned gas stream are shown in Table 3-
11.
Table 3-11: Concentrations of the main constituents in the cleaned gas from the central
fabric filter
*)
SOx (as SO2) mg/m³ 20 - 600 500
kg/h 111 (1996) 155
(annually mean value)
Particulate matter**) mg/m³ <1-7 10
*)
Continuously measured value (c.f. section 4.1.1)
**)
operation conditions (charging, pouring, etc.), different input materials and changes in the
operating mode.
3.1.4 Characteristics of fabrics filters at NA

In the following Table, the measured and authorised values of the constituents in the
particulate matter content in off-gases released into the ambient after being cleaned in a fabric
filter are given.
Table 3-12: The main constituents in the dust content of the off-gas after treatment in a
fabric filter
Class I (TA-Luft)
Cd mg/m³ < 0.01 - 0.1 0.2
Hg mg/m³ < 0.01 - 0.2 0.2
Tl mg/m³ < 0.01 0.2
Sum class I (TA-Luft) mg/m³ < 0.03 - 0.2 0.2
Class II (TA-Luft)
As mg/m³ < 0.01 - 0.8 1
Ni mg/m³ < 0.01 - 0.3 1
Co mg/m³ < 0.01 - 0.1 1
Se mg/m³ < 0.01 - 0.9 1
Te mg/m³ < 0.01 - 0.1 1
Sum class II (TA-Luft) mg/m³ < 0.05 - 1 1
Class III (TA-Luft)
Sb mg/m³ < 0.01 - 0.5 5
Pb mg/m³ 0.1 - 2 5
Cr mg/m³ < 0.01 - 0.1 5
Cu mg/m³ 0.02 - 2 5
Sn mg/m³ < 0.01 - 1 5
Sum class III (TA-Luft) mg/m³ < 0.15 - 5 5
operation conditions (charging, blowing, pouring, poling etc.), different input materials and
changes in the operating mode.
3.1.5 Further processing of copper at NA
3.1.5.1 Southwire copper wire rod plant

Cathodes from NA’s copper electrolysis are the main input of a continuously operating shaft
furnace. The other feed materials are recycled, i.e. off-specification or damaged wire rod and
bar from cropping operations during the start up and shut down of the process
(c.f. Figure 3-6).
Cathodes from tankhouse

Shaft
furnace
Holding furnace
Burner
Pickling, cooling
Stand1 Stand 2-5 Stand 6-13
and waxing line
Cooling water Mill

Caster Coiler
Steel strip
Stand
Caster
Roughing Oval Circular Oval Circular Oval Circular Etc.
(Wheel type)
pass flat
Figure 3-6: Southwire copper wire rod plant at NA

Source: company information NA, 1998
Bundles of cathodes are loaded into a bucket elevator as well as scrap bar, scrap wire, copper
ingots (pigs) and copper shavings, produced when the edges of the cast bar are trimmed prior
to rolling. Coils of reject rod are also charged via a cutter. The buckets are raised by an
overhead crane and hoisted above the opening of the furnace and then emptied.
The feed materials are melted by natural gas fired burners arranged in rows around the furnace
shell. It is essential that oxygen is not introduced into the copper during the melting operation.
Consequently, the fuel is burnt under closely controlled combustion conditions to maintain a
slightly reducing atmosphere. Thus, the off-gases from the furnace contain small quantities of
carbon monoxide (less than 0.5 vol-%). Independent control of the fuel/air ratio is provided
for each burner. The off-gas of the shaft furnace is cleaned in a bag house and the separated
dust is processed in the flash smelter furnace.
The holding furnace, which is fired with natural gas, serves as a reservoir to provide a
constant flow of metal to the casting process and, if required, can be used to superheat the
metal. The molten copper flows from the holding furnace via a gas-fired launder to a pot with
a pouring spout, which feeds the grooved periphery of the casting wheel. A water cooled steel
band encloses half of the circumference of the wheel, forming the casting cavity in which the
molten copper solidifies to form a trapezoidal bar. Acetylene, burnt with air, produces a soot
dressing for the casting wheel and steel band.
After being bevelled and shaved, the cast bar is fed by pinch rolls to a rolling mill consisting
of a roughing section and one finishing section, which reduces the bar to its final diameter. A
special emulsion in water is used as a rolling fluid; the fluid is re-circulated and continuously
filtered to remove copper fines and oxide scale.
Subsequently the wire rod is pickled with a solution of isopropanol and later followed by acid
pickling with diluted sulphuric acid. Then the residual acid is washed off the rod surface by
water spray and cooled. In the next stages the rod is dried by compressed air, coated with wax
and coiled on pallets. These coils are weighed automatically and then taken to an automatic
packing unit, where they are strapped and covered with the heat-shrunk polyethylene film. The
copper contained in the pickling acid is recovered in a small electrowinning facility, and then
decopperised acid is channelled back to the pickling equipment.
Cooling water is required for the caster and for different temperature control purposes of the
mill process, i.e. pickle lubrication or rolling emulsion. Direct cooling is applied at the caster
and indirect cooling at the mill. River water is used in an open circuit concept. The discharge
of cooling water back to the river depends on the volume of fresh water needed to control the
temperature. With this concept biocides are not required. The water used amounts to
approximately 25 m3/t.
3.1.5.2 Continuous casting of Copper Billets and Slabs/Cakes

The production of copper billets and cakes/slabs is another important production line of
Norddeutsche Affinerie. The cakes are used for sheet and strip rolling while the billets are
applied for extrusion and fabrication of tubes and sections.
Billets and cakes are produced in different copper qualities depending on the final application.
Typical qualities are: ETP copper - oxygen containing copper - has a high conductivity in line
with low impurity levels; phosphorised copper with improved properties related to brazing,
welding and corrosion resistance; low oxygen or oxygen free copper; low alloyed copper -
mostly silver alloyed. In Table 3-13, some data of the continuous casting plant are given.
Table 3-13: Continuous casting plant data
Melting furnaces:
Number 2
Type Cathode shaft furnace, gas fired
Melting rate 30 t/h max, each
Off-gas cleaning Baghouse
Casting/holding furnace
Number 3
Type Induction furnace
Caster
Number 3
Type Continuous caster, multi-strand for billet
casting
Casting rate 5 - 30 t/h, depending on shape, copper quality,
number of strands
Normally both shaft furnaces, each serving one caster, are in operation continuously for 24
hours per day. Cathodes and other high purity copper casting scrap and chips from cutting
cakes and billets to length are charged by skip hoist to the shaft furnaces. The molten copper
is transferred by launder from the shaft to the holding and casting furnace. Alloying elements
or phosphorus (as copper alloy) are dosed to the launders and evenly distributed in the molten
copper within the holding furnace. From the holding furnace the copper is dosed into the
casting moulds of the vertical casters.
The solidified copper, leaving the casting mould, forms a continuous, cake or billet strands
which are cut to length by a flying saw as the cast strands come down. The product castings
are inspected on roller conveyors and then transported to the open storage area for shipment.
Products normally are shipped by truck and railway, occasionally also by ship.
The cast strand is cooled by river water from the Elbe. The water is partly recirculated; the
bleed is discharged after settling and separation of solids.
3.1.6 Waste water treatment plant

All waste waters arising at NA are treated in a central waste water treatment plant. The plant
with an energy consumption of 9 - 13 kWh/m3 waste water is mainly designed to minimise the
arsenic content in the waste water and process water, precipitation water and direct cooling
water are treated and discharged separately. 15 - 25 kg sludge per m3 waste water arise
(mainly depending on the arsenic content in the waste water) with an arsenic content of 5 - 15
% and an iron content of 20 - 35 %. In Table 3-14 the concentrations of the main constituents
in the raw waste waters are given. Since the waste waters discharged from the central waste
water treatment plant arise in the primary and secondary plant and therefore have to be seen as
overall emissions into the water from NA, the concentration of pollutants are shown in the
next section.
Table 3-14: Concentrations of the main constituents in the untreated waste water at NA
Main components before treatment [mg/l]
Cu Pb As Ni Cd Zn
Process water 2,000 500 10,000 1,000 500 1,000
*)
Precipitation water 15 - 30 <5 <2 <2 < 0.5 <2
Direct cooling water <3 < 0.5 < 0.1 < 0.1 < 0.05 < 0.5
*)
Calculated back from the analysis of the precipitated sludge
3.1.7 Summarised data on outputs and environmental concerns at NA
Emissions into the air

Table 3-15 shows the emissions at Norddeutsche Affinerie Aktiengesellschaft. The given
concentrations include all captured emissions, the given loads are calculated values and
include all captured emissions (from stacks and exhaust pipes) and fugitive emissions from
baghouses, cooling towers, ridges, storage and loading places as well as from traffic areas.
The calculations are based partly on measured values and partly on emission factors.
Table 3-15: Total emissions from copper production at NA (primary and secondary
plant), 1996
Main components Particulate SO2 Cu Pb As
matter
Loads 168 5.55⋅103 29 7 2.5
[g/t]
Concentration 2 - 10 0 - 1250 0.01 - 5*) 0.01 - 5*) 0.01 - 1**)
[mg/Nm3]
*)
In total with several substances of the same class TA Luft (Sb, Pb, Cr, Cn, F, Cu, Mn, Pt, Pd, Rh, V, Sn)
**)
In total with several substances of the same class TA Luft (As, Co, Ni, Se, Te)
operation conditions, different input materials and changes in the operating mode (e.g. start-up
and shut-down operations). More information about measurements, to ensure that the
emissions specified are representative, mutually comparable and clearly describe the relevant
operating state of the plant, can be found in section 4.1.1.
Waste water
In Table 3-16 measured values and in Table 3-18 authorised values on the annual use of water
and the pollutants in the three separately captured, treated and discharged waterstreams in
1996 are given. The concentrations of the various substances are determined by qualified
composite samples. The samples are taken and analysed according to the German regulations.
(c.f.6.1.2.2)
Table 3-16: Pollutants in the three separately discharged waterstreams at NA (primary
and secondary plant) based on measured values from 1996
Flow Main components [mg/l]
[m³/a) Cu Pb As Ni Cd Zn
Process water 72,000 0.01-0.2 0.001-0.04 0.01-0.1 0.004-0.15 0.0001-0.1 0.01-0.2
Precipitation water 322,000 0.01-0.4 0.005-0.2 0.003-0.07 0.002-0.4 0.0002-0.1 0.03-0.4
Direct cooling water 11,300,000 0.01-0.25 0.001-0.1 0.001-0.1 0.002-0.06 0.0001-0.003 0.02-0.5
Cooling water 82,000,000
(total)
Table 3-17: Authorised pollutant concentrations in the three separately discharged

waterstreams at NA (primary and secondary plant), 1996
Flow Main components [mg/l]
[m³/a) Cu Pb As Ni Cd Zn
Process water 100,000 0.3 0.2 0.1 0.5 0.1 1
Precipitation water - 0.5 0.5 0.1 0.5 0.2 1
Direct cooling water 16,000,000 0.1 – 0.5 0.1 - 0.3 0.1 0.1 0.005 1
In Table 3-18 the measured overall pollutant rate of waste water discharged from NA in 1996
is given.
Table 3-18: Overall pollutant rate of waste water discharges from NA based on
measured values from 1996
Main components Cu Pb As Ni Cd Zn
Overall pollutant rate 2.3 0.3 0.23 0.1 0.05 0.8
[g/t]
Main intermediates, by-products and residues

In Table 3-19 an overview of the main intermediates, by-products and residues is given.
Table 3-19: The main intermediates, by-products and residues from copper production
at NA
Process unit By-product/residue Amount Use/treatment option
[t/a]
Primary plant:
Flash smelting Dust 100,000 Internal use at the flash smelting furnace
furnace
Slag 400,000 Further processing in the electric furnace
Electric furnace Dust 400 External use for Zn/Pb production
Slag 400,000 External use as construction material
Copper converter Dust 4,000 Internal recycling to the flash smelter or electric
furnace (sec. plant)
Slag 150,000 Internal use at the flash smelting furnace
Anode furnace Dust 200 Internal use at the flash smelting furnace
Slag 20,000 Internal use at the copper converter
Sulphuric acid plant Sulphuric acid 656,000 By-product for sale
Secondary plant:
Electric furnace Dust 10,000 By-product for sale
Slag 40,000 External use as construction material
Converter Dust 400 Internal use at electric furnace
Slag 10,000 Internal use at electric furnace
Contimelt process Dust 1,000 Internal use at the flash smelter/electric furnace
Slag 2,000 Internal use at copper converter
Scrap converter/TLA Dust 1,000 Further processing in TLA plant
plant
Slag 2,000 Internal use at the electric furnace
Others:
Electrolysis Anode slime 3,000 Internal use at the chemical plant for the recovery
of precious metals and Se, Te, Pb
Final liquor 35,000 m3 Internal use at the chemical plant for the
production of nickel sulphate, As2O3
Process waste water Sludge 1,500 Dumping as hazardous waste
treatment plant
General Household refuse 400
Source: Company information NA, 1998
3.2 Secondary copper production at Hüttenwerke Kayser AG

Hüttenwerke Kayser AG (HK), located in Lünen, was founded in 1861 and is today the largest
secondary copper producing plant in the world with a turnover of 1 billion DM and about 700
employees. In 1997 250,000 t of raw materials such as copper scrap, residues, slags, etc. were
processed to 176,000 t of Grade A cathodes, which accounts for more than eight percent of the
world-wide secondary copper production. By-products from secondary copper production are
slags, zinc oxide, tin-lead alloy, copper and nickel sulphate and anode slime containing
precious metals. In Figure 3-7 a scheme of the pathways for secondary copper production at
HK is given and in Table 3-20 the main input materials and products are specified.
Secondary raw materials,

e.g. slags, ashes,
drosses, dusts, sludges, Lump slag
cooper-iron material Granulated slag
Blast furnaces
SiO2- and CaO-additives Zinc oxide
Spent linings Sn-Pb-oxides
Black copper und -residues
Cu-alloy scrap
Tin-lead alloy
Converters TLA plant
Dust Slag
Slag
Converter copper
Electrolysis
Copper cathodes
(Tankhouse)
Slag,
Dust
Copper scrap
Blister copper Anode furnaces Copper anodes
Anode slime
Electrolyte
Cu-Ni-salts purification Copper sulphate
and -solutions Nickel sulphate
Figure 3-7: Copper recycling at Hüttenwerke Kayser AG
Source: Meyer-Wulf/Nolte [52]

Table 3-20: Input/output data from Hüttenwerke Kayser AG (1997)

*)
Copper scrap 130,000 Copper cathodes 176,000
Blister copper 20,000 Copper sulphate 2,200
*)
Copper alloy scrap 35,000 Nickel sulphate 2,400
External intermediate 40,000 Zinc oxides 9,000
materials (e.g. slags,
dusts, ashes, sludges,
sweepings, etc.)
Copper-iron material 25,000 Lead-tin alloys 3,700
Limestone 13,000 Anode slime 1,000
Silica 11,000 Slag 80,000
Coke 25,000
Coal 15,000
Fuel (oil) 11,000
*)
including electronic scrap
Source: Nolte[54] and company information HK
The main input material is copper scrap in the form of plates, tubes, wire, etc. and copper
alloy scrap (bronze, brass). Another group consists of external intermediate materials (e.g.
slags, dusts, ashes, sludges, sweepings, etc.). Blister copper from primary smelters is added at
a level of 10% of the feed. 13 % of the materials treated at HK in 1995 originated from
electronic scrap processing [54]. The main share consists of relais scrap, scrap from electronic
scrap processing of household appliances and granulates from cable disassembly. The
processed raw materials have to be free from PCB and mercury. Organics as well as harmful
constituents such as arsenic, antimony and cadmium are limited. The copper content varies
within a range between 94 % (granulate from cable assembly) and 1.5 % (shredded iron from
household appliances, electronic scrap).
3.2.1 Blast furnaces

Various oxidic materials such as ashes, drosses, dusts and sludges, different copper-iron
containing materials with an average copper content of 20 - 30 % as well as internal recycling
slag from converter and anode furnace are processed in three blast furnaces using coke as fuel
and reductant. Silica and limestone and iron are added for slag formation. Black copper and a
slag which is poor in copper are produced. 150 - 180 tons of feed material are charged per
furnace and day of operation. The raw materials are commuted or compacted if necessary. In
1996, the blast furnaces had a throughput of 148,000 t, of which 67,000 t was from secondary
material. A schematic view of the blast furnace operation is given in Figure 3-8.
Blast Furnace Settling Tower Boiler
O2
Oxide
to filter plant
Inputs
Water jackets
Blowing air pipe

with tuyers
Return slags Dusts from boiler
Black copper Slag
Figure 3-8: Schematic view of a blast furnace at HK

Source: Nolte [54]
The black copper fraction with a copper content of 70 - 80 % is tapped into a holding furnace
and then led to the converter for further processing. The blast furnace slag, which has a rather
low copper content and a high density, is marketed in granulated form (15,000 t/a) or as lump
slag (50,000 t/a) for construction purposes or as blasting media. In order to maintain the
required mechanical properties of the slag, the chemical composition must be kept in a fixed
range. Table 3-21 shows the typical chemical composition of blast furnace slag produced at
HK.
Table 3-21: Chemical composition of blast furnace slag from HK
Substance FeO SiO2 CaO Al2O3 MgO Na2O Zn

Share 32 - 38 20 - 25 14 - 17 10 3 2 4-8
[wt.-%]
Substance Cu Sn Pb Ni As Cd
Share 0.7 - 1.2 0.5 - 1.0 0.2 - 0.4 0.1 < 0.1 < 0.1
[wt.-%]
Source: Meyer-Wulf/Nolte [52]
The heavy metals, which are still present in significant quantities, are hardly leachable under
normal conditions, so that this slag can be used in similar ways to primary copper slag in
many fields of application.
A further product from the blast furnace is zinc oxide with a zinc content of 60 - 70 %. Zinc
evaporates at the existing temperatures in the blast furnace (about 1,250 °C in the lower part
of the shaft) and a part of it is carried out with the furnace process gas where it is converted to
zinc oxide. Lead and tin are found in the flue dust as well. Depending on the tin content, the
flue dust collected in the baghouse is further processed in the tin-lead alloy plant or, in the
case of a low tin content, sold as raw material for external processing. Some further process
parameters of the blast furnace are shown in Table 3-22.
Table 3-22: Process parameters of the blast furnace
Process data Typical value or range
Burden throughput [t/h] 5 - 20
Requirement of coke [kg/t burden] 100 - 120
Requirement of process air [Nm3/t burden] 5,000 - 12,000
Requirement of natural gas for support of post-combustion*) [Nm3/t burden] 3 - 10
Intermediates and by-products
Black copper (further processed in converter [kg/t burden] 200 - 400
Slag (sold as construction material or for abrasive manufacturing) [kg/t burden] 400 - 600
Dust (processed in TLA plant) or directly sold as zinc oxide) [kg/t burden] 20 - 50
*)
Natural gas necessary to support the throat gas afterburning in the case of a "cold feed".
To support the volatilisation and oxidation of the accompanying metals such as zinc, tin and
lead, the furnaces are operated with top gas temperatures of about 1,000 °C and more. Figure
3-9 shows the off-gas treatment operated at HK for the three blast furnaces.
The air, which is needed for the oxidation of fugitive metals and furnace process gases (e.g.
carbon monoxide, low temperature carbonisation gases and the volatilised metals), is
suctioned through the charging door. The off-gases pass a settling chamber which also serves
as a post-combustion chamber. The heat content of the furnace process gas is used for
producing steam in a boiler. The temperature of the off-gases is then about 300 - 400 °C.
Before the gases with a volume of 50,000 - 100,000 Nm3/h are dedusted by filtration, further
cooling is necessary. This is achieved by leading the gases through a tubular cooler and by
subsequent mixing with cold off-gas from the secondary hoods in a mixing chamber. The off-
gases, which now have a temperature of about 120 °C, are dedusted in a bag house.
Stack
Ventilators
Filters
Mixing chamber
Cooler
Convective part
Radiation part
Waste heat boiler
Smoke flue
Settling chamber
Secondary Secondary
3 hoods hoods
2 1
Hoods Hoods
Blast furnaces
Figure 3-9: Off-gas treatment from blast furnaces at HK

Source: Meyer -Wulf [51]
In the past, the top gas temperature varied between 800 and 1,100 °C, and PCDD/PCDF
emissions were between 2 and 30 ng/Nm3 [14]. Since 1990 additional oxygen has been
injected into the top area of the blast furnace which led to a higher level of temperatures and a
considerable reduction of PCDD/PCDF emissions because of the improved post-
combustion14. Values lower than 0.5 ng/Nm³ have been achieved. The particulate matter
content as well as its main constituents in the raw off-gases can be found in Table 3-23.
Measured and authorised emission values of the cleaned off-gases are given in
Table 3-24.
Table 3-23: Particulate matter content and its main constituents in the raw off-gases
from the blast furnace
Particulate matter
Total [mg/m3] 20,000 - 30,000
Pb [wt.-%] 10 - 40
Zn [wt.-%] 30 - 60
Sn [wt.-%] 1-5
14
A detailed description regarding the decrease of PCDD/PCDF emissions by oxygen injection can be found
in Meyer-Wulf [51] and Bußmann [14].
Table 3-24: Concentrations of main constituents in the cleaned off-gases from the blast
furnace
SOx (as SO2) mg/m³ 50 - 150 800
NOx (as NO2) mg/m³ 30 - 100 500
PCDD/PCDF ng/ m³ < 0.5 < 0.5
*)
Particulate matter mg/m³ <1-8 20
*)
in the operating mode.
3.2.2 Scrap converters (Pierce-Smith type)

HK operates two converters of the Pierce-Smith type using the Knudsen process. Black
copper from the blast furnaces as well as further raw material such as alloy scraps and
shredder material with a copper content between 60 and 80 % is charged into the converter.
The converters have a capacity of approx. 35 t each and four to six batches are processed per
day and converter. 8 - 25 t per charge of converter metal with a copper content of approx.
95 % are further processed in the anode furnace. The converter slag, containing approx. 30 %
of copper, is returned to the blast furnace. Zinc, lead and tin are volatilised and oxidised by the
process air. The flue dusts collected in the baghouse are processed in the tin-lead alloy plant.
The particulate matter content in the raw off-gas ( 80,000 - 150,000 Nm3/h ) and its main
constituents are shown in Table 3-25. Measured and authorised emission values of the cleaned
scrap converter off-gas are given in Table 3-26.
from the scrap converter
Particulate matter
Total [mg/m3] 10,000 - 30,000
Pb [wt.-%] 5 - 30
Zn [wt.-%] 25 - 70
Sn [wt.-%] 1 - 20
Table 3-26: Concentrations of the main constituents in the cleaned off-gases from the
scrap converter
**)
SOx (as SO2) mg/m³ 200 - 500 800
NOx (as NO2) mg/m³ 20 - 30 500
PCDD/PCDF ng/ m³ < 0.1 < 0.1
*)
Particulate matter mg/m³ < 1 - 10 20
*)
**)
Typical mean value of a charge
3.2.3 Reverberatory anode furnaces

Scrap with an average copper content of 90 to 95 % together with the metal phase from the
converter is fed into the anode furnace and refined by oxidation. For this purpose HK operates
two reverberatory furnaces: a stationary furnace, where the oxidation is accomplished by top
blowing, which has a capacity of 300 t/d of anode copper and a new tilting furnace (since
1995) where the air is injected by nozzles and which produces 400 t/d. The two-component
burners are fired with oil and lignite. For deoxidisation, wood is used in the stationary furnace
and in the tiltable furnace natural gas is blown into the molten phase. The refined copper is
cast into anodes on two casting wheels and is further refined in the electrolysis plant.
Further products resulting from fire refining are a slag with a copper content of about 30 %,
which is re-fed into the blast furnaces, and filter dust with a copper content of 15 to 25 %,
which is recycled in the blast furnace.
A secondary hood system is installed to prevent fugitive emissions. The heat of the furnace
off-gas is used to generate steam in a waste heat boiler before the off-gas is cleaned by a fabric
filter. The particulate matter content in the raw furnace off-gas and its main constituents are
shown in Table 3-27. Measured and authorised emission values of the cleaned off-gas are
given in Table 3-28.
from the reverberatory anode furnace
Particulate matter
Total [mg/m3] 1,000
*)
CaO [wt.-%] 30 - 50
Pb [wt.-%] 2-6
Zn [wt.-%] 5 - 15
Cu [wt.-%] 15 - 25
As [wt.-%] 0.5 - 5**)
*)
from off-gas conditioning
**)
depending on type of raw materials
Table 3-28: Concentrations of main constituents in the cleaned off-gases from the
reverberatory anode furnace
**)
SOx (as SO2) mg/m³ 150 - 500 800
NOx (as NO2) mg/m³ 100 - 500 500
PCDD/PCDF ng/ m³ < 0.1 < 0.1
*)
Particulate matter mg/m³ 1 - 10 20
*)
**)
Typical mean value of a charge
operation conditions (charging, pouring, poling etc.), different input materials and changes in
the operating mode.
3.2.4 Electrolysis plant

In 1994 an electrolysis plant according to the ISA technology was installed to replace the old
conventional one. The capacity is about 170,000 t/a of cathode copper with a current density
of approx. 310 A/m² [22]. In Table 3-29 the accompanying metals contained in anode copper
and the copper cathode from the electrolysis plant at HK are shown.
Table 3-29: Accompanying metals in anodes and cathodes at HK

Element Anode Cathode
[wt.-%] [g/t]
Ag 0.06 10
Se 0.005 0.1
Te 0.002 < 0.1
As 0.07 0.7
Sb 0.07 <1
Pb 0.2-0.4 <1
Sn 0.08 <1
Ni 0.3-0.5 1
O2 0.15-0.22 -
Source: Dobner [22], Dobner/Schwill [23]
In comparison with Table 3-10 it can be seen, that anodes from secondary smelting are
different from the primary ones, but cathodes are very similar and so they have the same
quality.
The anode slime, which results from the precipitation of lead sulphate and insoluble precious
metals, has a content of 5 - 10 % of precious metals. It is further processed in subsequent
processes to recover the precious metals such as silver, gold, platinum and palladium. 1,000 t
of anode slime were obtained in 1997 [52]. The sludge is pretreated (elimination of copper
and zinc, partial dewatering) before it is marketed.
3.2.5 Electrolyte purification15

Nickel is dissolved during electrolysis and has to be removed from the electrolyte (tankhouse
bleed) in a special auxiliary plant. To maintain a nickel concentration of approximately 20 g/l,
120 - 130 m³ of electrolyte are withdrawn per day and purified. In the case of 203,000 t/a
anode feed and a nickel content of approximately 0.5 %, and considering an anode scrap
return of 13 %, about 880 t/a of nickel have to be withdrawn from the system via anode slimes
and bleed. With an extraction rate of 85 % in the electrolyte purification plant, 110 m³/d of
bleed and 35 m³/d of liquor from anode slime leaching have to be treated.
The main stages in the purification of the electrolyte are copper sulphate recovery via
evaporation process, further decopperisation in liberator cells and nickel sulphate recovery via
evaporation processes. There are three sales products which can be gained from electrolyte
purification:
- fine copper sulphate (CuSO4 ⋅ 5H2O)
15
A detailed description of the electrolyte purification can be found in Dobner [22].
- crude nickel sulphate (NiSO4 ⋅ 2H2O)

- fine nickel sulphate (NiSO4 ⋅ 6H2O).
About 2,000 t/a of nickel sulphate and 2,000 t/a of copper sulphate are recovered from the
electrolyte. Elutriation from condensing and cooling has to be treated by the precipitation of
arsenic.
3.2.6 Tin-lead alloy plant

In the tin-lead alloy plant, technical zinc oxide and tin-lead alloy are produced from oxides
arising during the smelting and converting processes. The converter flue dust and, if the tin
content is high enough, also the blast furnace flue dust are mixed with fluxes (soda) and
reductants (anthracite coal or petrol coke) and are fed to two hearth furnaces. The heat is
supplied by oil burners. Zinc is transferred to the flue dust as zinc oxide and is collected in
bag filters. The remaining metal phase consists mainly of tin and lead which is refined and
cast into ingots. 3,500 t of tin-lead alloy with a composition of 30 % tin and 70 % lead were
produced in 1997 and sold for the production of soft solder. The slag, consisting mainly of
caustic soda, zinc and sulphur, has to be dumped [27]. Other residuals such as drosses and
skimmings are recycled in the copper recovery process steps.
The off-gases from the TLA plant are cleaned by a fabric filter before being released into the
surrounding atmosphere. Measured and authorised emission values of the cleaned gas are
given in Table 3-30.
Table 3-30: Concentrations of main constituents in the cleaned off-gases from the TLA
plant
SOx (as SO2) mg/m³ n.d. 400
NOx (as NO2) mg/m³ 30 - 50 200
PCDD/PCDF ng ITE/m³ < 0.1 < 0.1
Particulate matter mg/m³ 5 - 20 20
*)
operation conditions (charging, pouring, poling etc.), different input materials and changes in
the operating mode.
3.2.7 Characteristics of fabric filters at HK

All off-gases arising at processes at HK are cleaned in a fabric filter before being released into
the surrounding atmosphere. The measured and authorised values of the constituents in the
particulate matter content in these off-gases are shown in Table 3-31.
Table 3-31: Main constituents in the dust content of the off-gas after treatment in a
fabric filter
Class I (TA-Luft)
Cd mg/m³ < 0.01 - 0.1 0.2
Hg mg/m³ < 0.01 - 0.2 0.2
Tl mg/m³ < 0.01 0.2
Class II (TA-Luft)
As mg/m³ < 0.01 - 0.8 1
Ni mg/m³ < 0.01 - 0.3 1
Co mg/m³ < 0.01 - 0.1 1
Se mg/m³ < 0.01 - 0.9 1
Te mg/m³ < 0.01 - 0.1 1
Class III (TA-Luft)
Sb mg/m³ < 0.01 - 0.5 5
Pb mg/m³ 0.1 - 2 5
Cr mg/m³ < 0.01 - 0.1 5
Cu mg/m³ 0.02 - 2 5
Sn mg/m³ < 0.01 - 1 5
3.2.8 Waste water treatment

The present waste water situation at HK is characterised by collecting process water,
precipitation water and cooling water in a mixed water drain and by fed them through the
municipal sewage system to a communal waste water treatment plant. Parts of the waste water
stream are pretreated at HK before the final treatment is carried out at the communal waste
water treatment plant. Currently, the waste water system at HK is modified in order to fulfil
the requirements of the 39th annex of the Abwasserverordnung (AbwV) [84]; especially the
multiple use of waters will be intensified.
Since the waste waters discharged from the communal waste water treatment plant arise at all
processes carried out HK, the concentration of pollutants are shown in the next section.
3.2.9 Summarised data on outputs and environmental concerns at HK

Table 3-32 shows the main stack emissions from the different process units at Hüttenwerke
Kayser AG. The given values are the mean values of a charge.
Table 3-32: Stack emissions from secondary copper production at HK, measured values
Clean gas
Flow Particulate SO2 NOx CO PCDD/PCDF
Process unit matter
[m³/h] [mg/m³] [mg/m³] [mg/m³] [mg/m³] [ng/m³]
3 blast furnaces (incl. 200,000 - 250,000 1 - 20 50 - 150 30 - 100 20 - 100 < 0.5
secondary hoods) (500)*)
2 scrap converters 150,000 - 300,000 1 - 10 200 - 500 20 - 30 30 - 80 < 0.1
(1,600)*) (300)*)
2 rev. Anode furnaces 100,000 - 150,000 1 - 10 150 - 500 100 - 500 20 - 80 < 0.1
(1,600)*)
Tin-lead alloy plant 30,000 - 40,000 1 - 20 n.d. 10 - 100 10 - 30 < 0.1
*)
peak value
In Table 3-33 the calculated overall values of both, stack and fugitive emissions, can be seen.
The calculations are based partly on measured values and partly on emission factors.
Table 3-33: Total emission from copper production at HK, calculated values
Particulate SO2 NOx CO Pb As Cu Zn
Main components matter
[kg/t] [kg/t] [kg/t] [kg/t] [g/t] [g/t] [g/t] [g/t]
Overall loads 0.47 3 1 2 50 1 50 100
and shut-down operations). More information about measurements to ensure that the
operating state of the plant can be found in section 4.1.1.
Waste water
In Table 3-34 data on the waste water from HK after treatment in a communal waste water
treatment plant is given.
Table 3-34: Pollutants (based on measurements) from HK
Main components Cu Pb As Ni Cd Zn
Overall pollutant rate 1.0 0.5 0.1 0.3 < 0.01. 0.2
[g/t]

Table 3-35: Main intermediates, by-products and residues from copper production at HK
Process unit By- Amount Use/treatment option
product/residue [t/a]
Blast furnace Zinc oxide 7,500 Partly internal use at the TLA plant,
partly external use for the production of
zinc metal and chemicals
Slag 80,000 External use as construction material or
abrasive manufacturing
Scrap converters Zinc oxide 8,500 Internal use at the TLA plant
Slag 20,000 Internal use at the blast furnace
Rev. Anode furnaces Dust 1,000 Internal use at the blast furnace
Slag 20,000 Internal use at the blast furnace
Electrolysis Anode slime 1,000 External use for the recovery of precious
metals and Se, Te, Pb
Nickel sulphate 2,400 By-product for sale
Copper sulphate 2,200 By-product for sale
TLA plant Tin-lead alloy 3,700 By-product for sale
Zinc oxide 5,000 External use for the production of zinc
metal and chemicals
Caustic slag 3,000 Dumping
General Household refuse 200
Source: company information Hüttenwerke Kayser AG, 1998
3.3 Copper production at Mansfelder Kupfer und Messing GmbH, Hettstedt

At Hettstedt copper has been processed for centuries. The mining of copper schist in the area
of Hettstedt goes back to the end of the 12th century. Already at the end of the middle ages,
Hettstedt was one of the most important metallurgical plants of its region. The processing of
copper schist from this area was carried out until 1990. The production of secondary copper at
the present site of Mansfelder Kupfer und Messing GmbH Hettstedt (MKM) started in the
seventies.
In 1996, 105,000 tons of copper containing raw materials such as copper containing scrap,
copper containing residues (drosses, slags, sludges, dusts), brass scrap, copper containing iron
scrap and copper granulates were processed to 60,000 tons of copper cathodes. The produced
copper is further processed in a wire rod plant and a continuous casting plant as well as in a
newly installed wire rod and strip plant. In Figure 3-10 a scheme of the pathways for the
secondary copper production at MKM is given and in Table 3-36 the main input materials and
products are specified.
Raw materials,
20 - 30 % Cu Blast furnace oxide
(Filter oxide)
Blast furnace
Slag
Converter slag
Black copper (75 - 85 % Cu)
Raw materials
65 - 80 % Cu Converter oxide
Scrap converter
Anodes flue dust
(Filter oxide)
Slag
Converter copper (83 - 98 % Cu)
Raw materials
90 - 95 % Cu
Anode hearth shaft
furnace
Anodes residues
Rotary anode furnace
Copper anodes (≈ 99 % Cu)
Cathodes (99,98 % Cu)
Electrolytic plant Anode slime
Electrolyte
Figure 3-10: Copper Production at MKM GmbH, Hettstedt

Table 3-36: Input/output data from Mansfeld Kupfer und Messing GmbH (1996)
Drosses/slags 40,000 Copper cathodes 60,000
Copper-iron 7,000 Nickel sulphate 800
containing scrap
Brass scrap 20,000 Slags 35,000
Refining scrap 40,000 Flue dust 5,000
Granulated copper 1,000
Coke 10,000
Limestone 4,500
Natural gas n.a.
Silica 2,000
Wood 900
Source: Company information MKM, 1996
3.3.1 Blast furnace

Since 1995, MKM has been operating a new blast furnace with a maximum melting capacity
of 8.45 t/h (referring to the input material). There, copper containing secondary raw materials
are processed together with limestone and coke to 2.5 - 3 t/h of black copper. The input
materials of the blast furnace are specified in Table 3-37.
Table 3-37: Input materials for blast furnace
Input materials Amount [t/a]
Drosses, slags 40,000
Copper-iron containing scrap 7,000
Filter oxide from afterburning chamber and 1,200
cooler
Filter oxide from anodes shaft furnace 150
Coke 7,000
Limestone 4,200
The produced black copper with a copper content of 75 - 85 % is further processed together
with additional metal in the converter. The blast furnace slag is used for construction
purposes. Table 3-38 shows the typical chemical composition of the blast furnace slag
produced at MKM. In 1996, about 15,200 t of black copper and 30,000 t of slag were
produced.
Table 3-38: Chemical composition of blast furnace slag from MKM

Substance FeO SiO2 CaO MgO Cu Ni Pb Zn
Share 25 -30 22 -32 8 -12 0,5 -3 1 -4 0,1 -1 0,5 -2 5 -15
[wt.-%]
The furnace off-gas (Gichtgas) is afterburned with additional oxygen and natural gas in a post-
combustion chamber which also serves as a settling chamber at about 1,000 °C. The heat of
the off-gas is used for steam production in a waste heat boiler, before the off-gas is cooled
with air in a tubular cooler and then sent to a purification plant. There, adsorption is used to
deposit dioxines and furanes (PCDD/PCDF), after the off-gas is dedusted in a fabric filter.
The released clean gas (32,000 m³/h) has a temperature of about 90 °C and an oxygen content
of 14.9 vol.-%. In Table 3-39 the measured and authorised emission values of the clean gas
are given.
The off-gas of the settler is dedusted in an extra filter and is released into the surrounding
atmosphere via a separate stack. The concentration of particulate matter in the clean gas is 2
mg/m3 as a yearly average (emission declaration 1996). Figure 3-11 shows a schematic view
of the blast furnace process.
Blast furnace Afterburning Waste-heat Cooler Filter Filter

chamber boiler
Lime/coke
Input materials Burner air Water Steam
Hood offgas
Offgas Natural
gas
Oxide of Flue dust

blast furnace (input to blast
furnace)
Air
(Input to blast furnace)
Ventilation
Stack
Slag
Metal (70 - 80 % Cu)
Figure 3-11: Blast furnace process

Table 3-39: Concentrations of main constituents in the cleaned off-gas from the blast
furnace
SOx (as SO2) mg/m³ 50 800
NOx (as NO2) mg/m³ 47 500
CO mg/m³ 19 50
C total mg/m³ 3 50
PCDD/PCDF ng (ITE)/m³ < 0.5 < 0.5**)
Particulate matter*) mg/m³ 3 10
*)
**)
Value to be achieved: 0.1 ng (ITE)/m³
The dust arising in the post-combustion chamber as well as the dust arising in the waste heat
boiler and the tubular cooler is recycled to the blast furnace. In 1996, the following amounts
of dust were collected and recycled to the blast furnace:
- 550 t from the post-combustion chamber,

- 100 t from the waste heat boiler, and
- 100 t from the tubular cooler.
The filter dust (1,300 t in 1996) with a high content of zinc and lead is sold for hydro- and
pyro-metallurgical processing. The metallic components of this filter dust are given in Table
3-40.
Table 3-40: Metallic components of filter-oxide from blast furnace
Substance Zn Pb Cu Sn Ni
Share 20 - 50 5 - 20 2 - 12 0.2 - 4 0.1 - 1
[wt.-%]
Source: Company information MKM
The lower part of the blast furnace is cooled by cooling water. Thereby 400 m3 per year of so-
called changing water has to be discharged.
3.3.2 Converter
The converter plant in operation since 1972 consists of two drum type converters (capacity:
20 t of input material) with a post-combustion chamber, ducted cooling, a gas cleaning plant
as well as auxiliary plants such as a cooling water supply, an air supply and an electrical load
center. One converter is in operation while one is on stand-by or is being relined. In Figure 3-
12 a schematic view of a converter is shown.
Post-combustion
Cooler Filter
chamber
Stack
A1
A2
A3
Housing/
extracting hood
Input
materials
Oxygen
enriched air
A1 : Oxide of post-combustion chamber
Slag
A2 : Oxide of cooler
Converter A3 : Filter oxide

Converter
copper
Figure 3-12: Schematic view of converter process
The black copper of the blast furnace is used as flush material and is processed together with
brass scrap, copper containing drosses, refining scrap and coke as well as other fluxes. The
input materials are blown to converter copper by use of a special mixture of oxygen and
nitrogen. The input materials for the converter are specified in Table 3-41. In 1996 about
21,000 t of converter copper were produced.
Table 3-41: Input materials for converter
Input materials Amount
[t/a]
Black copper 15.200
Brass scrap 20.000
Anodes scrap 250
Coke 3.000
Silica 1.700
Between 12 t and 13 t of converter copper with a copper content of 92 - 98 % are produced

per batch and are sent to the anode furnace for further refining. The converter slag produced
(about 18,500 t in 1996) is mainly recycled to the blast furnace to recover its copper content.
The accompanying metals in the converter slag are shown in Table 3-42.
Table 3-42: Accompanying metals in the converter slag
Substance Cu Ni Pb Zn
Share 15 - 35 1 - 30 1-5 5 - 15
[wt.-%]
The off-gas arising during blowing is captured by hoods and sent to a post-combustion
chamber together with secondary air with the aim of oxidising the volatile metal components
in the off-gas, whereby, temperatures of 800 - 1,300 °C are reached. This off-gas with a
volume of 100,300 m³/h is divided into partial currents and cooled with air before being
combined and directed to a baghouse. The dedusted gas is released into the surrounding
atmosphere at a temperature of 65 °C. The measured and authorised emission values of the
clean off-gas are given in Table 3-43.
Table 3-43: Emissions in clean gas of the converter
SO2 mg/m³ 300 800
NOx mg/m³ 27 500
CO mg/m³ 173 -
PCDD/PCDF ng (ITE)/m³ n.a. 0.5
*)
Particulate matter mg/m³ 6 20
*)
The dust collected at the post-combustion chamber as well as the dust settled in the coolers is
recycled to the blast furnace. The filter dust from the baghouse (3,650 t in 1996) can be sold
as so-called filter oxide due to its high zinc content and it is used as a raw material in the
secondary zinc production industry. The metallic accompanying metals in the filter oxide are
shown in Table 3-44.
Table 3-44: Metallic accompanying metals in filter-oxide of the converter

Substance Cu Ni Pb Zn Sn
Share 2 - 10 0.1 - 1 5 - 20 45 - 65 0.2 - 4
[wt.-%]
The cooling water for the hoods of the converters and the charging chutes is operated in a
closed circuit. A necessary bleed of 215 m3 per year has to be discharged as waste water.
3.3.3 Anode plant

The converter copper produced in the converter is fire refined in the anode furnace together
with additional raw copper material. Until now, this process step was carried out by 3 fixed-
head reverberatory furnaces. Currently a new anode plant with an authorised capacity of
99,500 t/a anode copper is in test operation. The anode copper should have a copper content
of about 99 %. A principal flow sheet of the new anode plant can be seen in Figure 3-13.
Anode hearth shaft

furnace
Cooler Stack
Filter
Oxygen
enriched air
NVK Flue dust
Natural gas
Water
Liquid black copper
Input materials Lime/coke
Air
Slag Copper
Poling furnace
Stack
Natural gas
NVK = After burning chamber
Anode casting plant
Figure 3-13: Flow sheet of the new anode plant

Besides the gas cleaning facilities, the plant consists of 3 units:
- the melting furnace,

- the refining furnace, and
- the anode casting machine.
The melting furnace with a melting capacity of 30 t/h is an open-hearth furnace with a shaft
stacked up. The furnace is charged with solid material (about 240 t /d) via the shaft. A natural
gas/air burner is installed in the lower part of the shaft to melt the input material. Oxygen
enrichment of the burner air is possible. The molten copper accumulates in the hearth of the
melting furnace (capacity: about 80 t). There, the liquid converter copper is poured in directly
(70 - 80 t per day). In Table 3-45 the maximum input materials according to the operation
permit of the competent authority are given.
Table 3-45: Input materials of anode hearth shaft furnace
Input materials max. amount
[t/a]
Refined copper 58,000
Brass scrap 1,500
Blister (black copper) 10,000
Granulated copper 4,000
Converter copper 24,000
Anode residues from electrolysis plant 11,000
Casting residues 310
Anode copper 600
Silica 7,000
Charcoal 50
Source: Company information MKM
The slag produced in the melting furnace is recycled to the blast furnace after mechanical
preparation. 4,000 t of slag with a copper content of 15 - 32 % are expected.
The superheated melt is transferred from the melting furnace to the refining furnace via a
skimmer tap. The refining furnace is a rotary or drum furnace with a capacity of 300 t and is
also equipped with a natural gas/air burner. After the oxidation of the copper with air, the
reduction (poling) is applied by blowing in natural gas. The slag arising during the oxidation
as well as the reduction step (expected amount: 7,500 t) is recycled to the shaft furnace.
The refined copper is directed to the continuous casting machine (capacity: 50 t/h) via a
launder and a metering vessel. The continuous bar is hydraulically cut into anodes, which are
cooled in a cooling tunnel by water spray before being sent to the electrolytic plant. The water
vapour arising during the cooling of the casting machine is captured by hoods and directed to
a wet separation plant.
The off-gases of the melting furnace and the refining furnace are afterburned in post-
combustion chambers at a temperature of at most 900 °C. The off-gas of the refining furnace
is then used to pre-heat the burner air up to approximately 400 °C, before the off-gases of both
furnaces are cooled in a quench cooler. Afterwards, they are treated in a gas cleaning plant
that consists mainly of an adsorption filter plant and a fabric filter. In the adsorption filter
plant, a mixture of dust from lignite coke and lime hydrate is injected into the off-gas mainly
to reduce the emission of dioxines and furanes (PCDD/PCDF). The emission values in the
clean gas with an expected volume of 97,000 m3/h shown in Table 3-46 are authorised.
Table 3-46: Emission values in the clean gas of anode furnace and poling furnace
Substance Unit Authorised value
Cd, Hg, Tl mg/m³ 0.2
As, Co, Ni, Se mg/m³ 1
Sb, Pb, Cr, Cu, Mn, Sn, V mg/m³ 5
NOx g/m³ 0.5
HCl mg/m³ 30
HF mg/m³ 5
C total mg/m³ 50
PCDD/PCDF ng (ITE)/m³ < 0.5
*)
Particulate matter mg/m³ 10
*)
To avoid fugitive emissions, all holes at the smelting furnace and the refining furnace as well
as the metering vessel are equipped with hoods or enclosures. The captured ventilation gases
are directed to the gas cleaning system.
Cooling water is necessary to cool both furnaces, to quench the hot furnace off-gases and also
to cool the casting machine, the anode cutting facility and the cast and cut anodes. The
different cooling waters are operated in a closed circuit and are conditioned depending on
their application. The arising waste water is used to operate the quench cooler, so the
discharge of waste water is not necessary. The copper containing residues arising both, at the
cooling tunnel to cool the cast anodes and during operation of the quench cooler, can be
recycled to the blast furnace.
3.3.4 Electrolytic plant

The electrolytic refining of the copper anodes is carried out by a conventional electrolytic
plant. The produced copper cathodes have a copper content of 99.98 %. Currently, this plant
has a production capacity of 60,000 t/h copper cathodes. As by-products, anode slime and raw
nickel sulphate are produced.
3.3.5 Characteristics of fabric filters at MKM

All off-gases arising from processes at MKM are cleaned in a fabric filter before being
released into the surrounding atmosphere. The measured and authorised values of the
constituents in the particulate matter content in these off-gases are shown in Table 3-47.
Table 3-47: Main constituents in the dust content of the off-gas after treatment in a
fabric filter
Class I (TA-Luft)
Cd mg/m³ < 0.01 - 0.1 0.2
Hg mg/m³ < 0.01 - 0.2 0.2
Tl mg/m³ < 0.01 0.2
Class II (TA-Luft)
As mg/m³ < 0.01 - 0.8 1
Ni mg/m³ < 0.01 - 0.3 1
Co mg/m³ < 0.01 - 0.1 1
Se mg/m³ < 0.01 - 0.9 1
Te mg/m³ < 0.01 - 0.1 1
Class III (TA-Luft)
Sb mg/m³ < 0.01 - 0.5 5
Pb mg/m³ 0.1 - 2 5
Cr mg/m³ < 0.01 - 0.1 5
Cu mg/m³ 0.02 - 2 5
Sn mg/m³ < 0.01 - 1 5
3.3.6 Further processing of copper at MKM

No information is available about further processing of copper at MKM.
3.3.7 Summarised data on outputs and environmental concerns at MKM

Table 3-48 shows the main emissions from the different process units at MKM.
Table 3-48: Stack emissions (max. measured values) from secondary copper production
at MKM
Process unit Flow Particulate SO2 CO NOx PCDD/PCDF
matter
[m3/h] [mg/m3] [mg/m3] [mg/m3] [mg/m3] ng (I-TE)/m3
1 blast furnace 32,000 3 50 20 50 < 0.5
1 converter 100,000 6 300 175 30 n.a.
*)
Anode furnace 11.000 - 15.000 3-6 20 - 200 10 - 80 10 - 160 n.a.
*)
Emissions are given for the 3 reverberatory furnaces (old anode plant)
In Table 3-49 the specific stack emission can be seen. Thereby the annual emission load is
related to the annually produced amount of shaft furnace copper (shaft furnace), black copper
(converter) or anode copper (anode plant). Fugitive emissions are not included in these values.
Table 3-49: Specific stack emissions of different process units at MKM
Component Particulate SO2 NOx CO Pb As Zn Cu Cd Ni Sn
matter
[kg/t] [kg/t] [kg/t] [kg/t] [g/t] [g/t] [g/t] [g/t] [g/t] [g/t] [g/t]
Blast furnace 0.15 0.08 0.7 0.3 18 0.1 5 25 0.2 3 6
Converter 0.26 11.8 1.0 6.8 31 0.1 13 17 1 1 15
*)
Anode furnace 0.08 0.26 0.8 0.2 14 2 4 26 0.3 2 4
*)
Emissions are given for the 3 fixed-hearth reverberatory furnaces (old anode plant)
and shut-down operations). More information about measurements to ensure that the
operating state of the plant can be found in section 4.1.1.
Waste water
From the cooling circuits of the shaft furnace and the converters, 615 m3 are directed to the
draining ditch. The cooling water from the anode hearth shaft furnace, the refining furnace
and the casting machine is operated in a closed circuit. The necessary bleed is partly used in
the quench cooler.

Table 3-50:Main intermediates, by-products and residues from copper production at
MKM
Process unit By-product/residue Amount Use/treatment option
[t/a]
Blast furnace Slag 30,000 - 35,000 Sold as construction material
Oxide from 700 - 800 Internal use at the blast furnace
afterburning
chamber, boiler and
cooler
Filter oxide 1,000 - 1,300 External use
Converters Slag 17,000 - 19,000 Internal use at the blast furnace
Oxide from 250 - 300 Internal use at the blast furnace
afterburning
chamber
Oxide from cooler 100 Internal use at the blast furnace
Residues 300 Internal use at the blast furnace
Filter oxide 3,500 - 3,700 External use
*)
Anode furnace Anode copper 7,000 - 8,000 Internal use at the blast furnace
residues
Filter oxide 150 Internal use at the blast furnace
Residues from 200 Internal use at the blast furnace
furnace
Electrolysis Anode slime 360 External use
Nickel sulphate 700 External use
General Household refuse n.a.
*)
By-products and residues are given for the 3 fixed-hearth reverberatory furnaces (old anode plant)
3.4 Fabrication of wire rod at Friedrich Kemper GmbH & Co KG, Duisburg and
Lacroix & Kress GmbH, Bramsche
At Friedrich Kemper GmbH & Co KG, Duisburg and Lacroix & Kress GmbH, Bramsche, the
dip forming wire rod process is used for the further processing of copper. In this process, a
copper core wire of 9 - 12.5 mm diameter (mother rod) is drawn through a molten bath of
oxygen-free copper. Thereby additional copper solidifies at the surface to form a new rod of
about 20 mm diameter. A special induction furnace is used for this process.
The rod produced in the furnace is reduced in diameter in a mill under inert gas, so the copper
wire is oxygen-free. About one third of this wire is returned to form the core material. The
basic concept of the process is shown in Figure 3-14.
Copper cathode and Emissions to

recycled rod atmosphere
Fume
Natural Preheating
handling
gas furnace
equipment
Melting
furnace
Copper wire
Rolling Coiler rod
Holding Crucible
furnace
Mother rod
Figure 3-14: Basic concept of the dip forming copper wire rod plant
The main input material to the process is cathode copper as well as recycled scrap; both are
charged automatically into a gas fired rotating drying furnace. There, the charge is conditioned
and pre-heated up to 800 °C. This pre-heated feed material is discharged into a channel
induction melting furnace with a capacity of 5 - 10 t/h providing copper at about 1,100 °C to
the holding furnace and crucible. To ensure there is a constant level of molten metal in the
crucible, it is attached to the holding furnace. Mother rod is drawn through an inlet die at the
base of the crucible, increasing the diameter by drawing the core wire through the metal pool.
The final diameter of the cast rod produced is controlled through the upper die, e.g. at < 20
mm dia before being directed via dancers to a three stand rolling mill. There, 8.0 mm and 12.5
mm rod is produced and coiled to 3,5 t palletised coils.
16
3.5 Fabrication of semi-finished products from copper and copper alloys
There are numerous German fabricators of copper and copper alloyed semi-finished products.
Size of the companies and the product range differ significantly so that not all fabrication
facilities can be described. The following description represents a compilation of the most
common processes and techniques for the fabrication of semi-finished products from copper
and copper alloys including the applied abatement techniques. Not all German fabricators will
be dealt with in this section. The descriptions and explanations will be restricted to plants
which have melting and casting shops integrated with extrusion and/or mills. The general
concept of the semi-finished product fabrication is shown in Figure 3-15.
Copper Cathodes
High grade copper scrap
Fire-refined copper
Alloy metals; Master alloys
Internal scrap Alloy scrap
Gas
Gas cleaning
Melting
Slag to Dust to
smelters smelters
Casting of shapes
Billets, cakes
Hot & cold working

(Extrusion and drawing or rolling)
Semi-Finished Products
Figure 3-15: General flowsheet of semi-finished product fabrication
As raw material only metallic components are used. Some materials may be slightly
contaminated with oil, paper and/or dirt. The following list shows the metallic components
typically used as feed in meltshops of a semis fabrication plant :
- Cathodes,
- wire bars,
- ingots (copper and alloys),
16
Based on Traulsen, H.: „Fabrication of Semi-Finished Products From Copper and Copper Alloys“,
EUROMETAUX Copper Industry [66]
- anodes (only for fire refining),

- swarf (usually returned from customers), and
- scraps from own factory, customers, other factories or from other sources.
The scraps are classified in technical and commercial (e.g. customs) specifications. The
incoming raw material is controlled by scanners for radioactivity and by visual control for the
compliance with the specification. This is true for a increasing number of factories.
The storage of raw material is done outdoors and indoors; outdoors storage areas are protected
by a hard surface, in most cases concrete slabs. The rainwater is collected and treated by
settling before discharge. Swarf, oil contaminated scrap and fines are stored indoors to avoid
rainwater contamination.
Raw materials like wires, punchings, cuttings, tubes, etc are pressed to blocks. Oil
contaminated scraps are processed for decreasing before melting. This can be done by
washing with detergents and drying or heating in a rotary kiln. The distilling oil can be used as
a fuel substitute or it is burned in an afterburner. Swarf is not pre-treated but charged directly
3.5.1 Melting
The input materials are handled by cranes or fork lifters for transport to the smelter. Different
scrap types and alloy metals are selected with the objective to compose the correct feed for the
specific charge to be processed. The melting furnaces may be distinguished by the energy
sources applied: Electrically heated and (natural) gas- or fuel-fired units to melt the metallic
feed. Furthermore, the melting and casting rate may determine the type of furnace and casting
equipment selected: High production rates may lead to the use of a continuously melting shaft
furnace and continuous casting equipment; batchwise melting and discontinuous casting may
be preferred for copper alloys or special copper shape casting.
When using electric power for melting induction furnaces are applied. Both, coreless or
channel type induction furnaces, are in use. Capacities of electric furnaces may range between
0.5 and 15 t of metal. Electric furnaces are mainly used for copper alloy melting and to a
lesser extend for unalloyed copper. Typical data of a slab fabrication plant are compiled in
Table 3-51 as an example.
Table 3-51: Typical data of an Electric furnace based discontinuous casting plant
Product
Alloy Brass
Shape Slab
Dimensions 720 mm W x 130 mm H x 6500 mm L
Melting unit
Type of furnace Coreless induction furnace
Number of furnaces 2
Capacity 12 t metal
Power rating 2.8 MW each
Power consumption 165 – 184 kWh/t
Holding furnace
Type of furnace Channel type
Capacity 8t
Caster
Type Discontinuous
o
N strands cast parallel 3
Primary cooling /mould Indirectly water cooled copper mould
Secondary cooling Direct spray cooling
Cooling water system Primary: Once-through concept
Secondary: Returned to water treatment plant
Off-gas handling
Volume Approx. 50,000 Nm³/h
Cleaning by Cyclone followed by baghouse
The melting furnace operation is discontinuous: Normally the total amount of the feed
materials is charged to the furnace and melted down. As the furnace charge is carefully pre-
adjusted, only slight corrections of the alloys are necessary before casting. When the material
is completely molten and the composition correctly adjusted the melt is ready for casting.
Frequently the melt is not directly cast from the melting unit but transferred to a holding and
casting furnace and then casted. Such furnaces have less electric power installed so that
energy is saved. The main purpose of this concept is to make the melting unit rapidly available
for melting the next charge. So casting can be carried out while the melting furnace melts
down the next charge. Depending on the type of alloy and the furnace capacity a batch may
last between 0.5 and 2.5 hours.
The electric furnaces are lined with silicate or phosphate based brickwork, but also alumina or
silicate castable refractory masses or refractory concrete are in use. The gases and fumes from
the electric furnaces are capture by adequate hooding systems and dedusted in bag houses. The
dust is sold to secondary smelters for metal recovery.
Natural gas- or fuel-fired crucible, drum or hearth/reverberatory type furnaces are also applied
in the different semi’s operations. These types of furnaces are used for melting and fire-
refining of copper and not for alloying. The furnaces are also operating batchwise. The
material of a complete charge is added in portions during melting. Drum type furnaces in use
have capacities of 5-20 t.
The fire-refining practice applied covers an oxidation phase to remove minor elements and an
reduction phase to adjust the oxygen content in the metal. The oxidised copper is reduced by
means of wood poles which are inserted into the molten bath and held in position by crane.
The refined copper is tapped into ladles and transferred to holding furnaces for casting. The
off-gases are collected in adequate gas handling systems and cleaned in baghouses. The dust
and the slag formed during the refining process are shipped to third parties for treatment and
metal recovery.
The refining furnace is bricklined with magnesite based bricks. The campaign of a furnace
may have a lifetime of more than 2 years (e.g. up to 5 years) before it needs to be relined.
Used brickwork bricks are separated into a contaminated part, which is shipped with the slag
for recovery, and a less contaminated portion which can be used as building material on
deposit sites.
For continuous operation and/or high production rates mostly shaft furnaces, like the
ASARCO furnace, are selected. These furnaces are equipped in the lower (crucible) part with
one to three rows of air/gas burners. The shaft furnace is charged from the top. The
combustion gases, raising in the shaft, are pre-heating the charge which finally melts in the
crucible area; the molten copper flows out through an open tapping slot.
The ASARCO furnace is a continuous smelting unit for copper and not suitable for refining or
alloying. Therefore, the charge composition requires close control to maintain the metal
quality. As fuel for the ASARCO furnace mostly natural gas is used. The combustion air may
be enriched with oxygen to improve the melting capacity. Reducing conditions are maintained
within the furnace in order to control the oxygen content in the metal at low levels. The
melting rate of such units is between 5 and 25 t/h. The furnace is lined with silicon carbide
refractory. The molten copper is normally transferred by ladle to the casting units. It will be
either tapped directly into the ladles or to a holding furnace, where some alloying can take
place.
Compared to other melting facilities, the ASARCO furnace is an energy saving process, since
the combustion gases are utilised to pre-heat the charge. If the charge is contaminated by oil,
an afterburning chamber is necessary for off-gas cleaning, since the organic compounds are
thermally cracked and vaporised. One shaft furnaces is used for example at KME located in
Osnabrück. Typical data of an ARSACO shaft furnace based plant are given in Table 3-52.
Table 3-52: Typical data of an ASARCO shaft furnace based plant

Shaft furnace
Melting rate 20 to 25 t/h
Input Cathodes, internal fabrication scrap
Mode of operation Continuous melting
Fuel Natural gas
Consumption 930 Nm³/h
Holding furnace
Number 2
Capacity 80 t each
Heated by Natural gas, 600 Nm³/h, each
Caster
Type Vertical, continuous
Mould Indirectly water cooled mould
Production rate 20 t/h
Cooling water system Closed cooling water circuit with cooling tower;
solid separation by settling, de-watering by means
of a mobile filter press; recirculation of the solids
Off-gas handling
Volume 12,000 Nm³/h
Afterburning Applied, 220 Nm³/h gas
Gas Cooling Indirectly by pre-heating combustion air
Cleaning Baghouse
Controlled handling of the off-gases from the furnaces is common practice in the casting
shops. The gases are collected in specifically designed gas handling systems and cleaned in
bagfilters which are combined with cyclones as a first dedusting step. The collected dust is
recycled to other operations for pyro- or hydrometallurgical treatment and metal. Frequently
the gas handling systems of shaft furnaces are equipped with an afterburning system for the
elimination of hydrocarbons and for conversion of carbon monoxide in carbon dioxide. Then
the off-gas handling system includes a heat recovery system before the off-gas is cleaned in
bagfilters. For heat recovery combustion air pre-heaters or boilers are used.
Electric furnaces of the channel type are mainly used to melt larger charges. Coreless type
induction furnaces are in application for alloy melting/casting or as casting furnaces in
combination with separate melting units and casting machines. The metal produced and cast
covers the full range of industrially applied copper alloys, low alloyed copper e.g. with silver
or tin, and the different copper qualities, like oxygen-free, phosphorous desoxidised, ETP
copper. Special alloys are CuNi, CuZnPb, CuNiZn, CuCoBe, and similar. During processing
(melting, grinding) of these alloys special care is required to control fume and dust
development. For the production of oxygen-free copper induction furnaces are used. The
induction furnace is normally combined with a semi-continuous caster for billets or cakes.
Emissions during all melting operations can be reduced by removing as much of non-metallic
material as practicable, e.g. centrifuging and thermal de-oiling of swarf in a rotary kiln.
Techniques for thermal swarf handling are: Melting with slow feed and afterburning of the
off-gases, de-oiling using indirectly heated dryers with separate afterburners holding the
combustion gases at 850 °C for minimum 2 seconds.
3.5.2 Casting
Conventional casting processes

The conventional way for semi-finished product fabrication is via casting of billets and
cakes/slabs which are then further processed. The most widely spread methods in use for
production of shapes like cakes/slabs and billets at higher rates are discontinuous casting and
continuous casting.
Discontinuous casting is carried out in the vertical mode. Continuous casting can be either in
the vertical or horizontal mode. In most cases the casting unit is not directly fed from the
melting furnace. Depending on the type of operation and the production rate, holding/casting
furnaces and/or heated tundishes are installed in-between melting unit and caster.
The normal shapes produced are billets for the production of tubes, rods and section and
cakes/slabs for the production of sheets and strips. The cast strand on vertical or horizontal
casting units is cut using the flying saw technique.
In a discontinuous casting unit the format length is determined by the depth of the casting pit.
After reaching the maximum format length, casting is interrupted and the cast shapes is
extracted by crane or elevator. Then the moulds are prepared and the next casting cycle starts.
All casting operations need direct cooling water for final solidification and cooling down of
the cast strand down to temperatures allowing further handling. The cooling water normally is
recycled after sedimentation and separation of particulates (casting scales). The scales are
recirculated to a smelter for processing if not directly reused in the casting shop. Most of the
equipment components are movable by hydraulic systems.
Special Processes
A special ASARCO casting process, using graphite casting dies, is occasional applied for
direct casting of tubes, rods and sections from high alloyed copper. With this process, very
narrow tolerances as close as possible to the final dimensions can be casted. Typical
constituents in the copper alloys cast by this process are lead, tin, silicon and nickel.
Copper Cathode
Clean Recycles
Fume Handling
Equipment
Electric
Melting Furnace
Cooling Water
System
El. Holding Furnace

Cooling Water
System
Up-Casting Process
Pinch Rollers
Coiler Coiled Product
Figure 3-16: Simplified flow diagram of an upcast process
An upward casting method is used at Wieland-Werke AG for the fabrication of wires made
from copper alloys. The diameter of the wires ranges from 16 up to 24 mm. The principle of
the method is explained in Figure 3-16. After melting in an electric furnace, the liquid alloy is
transferred to the holding furnace. The casting direction is vertically upwards. The metal is
continuously drawn through a vertical die; the lower end of the die reaches into the melt,
while the upper end is surrounded by a water-cooled jacket. The solidified wires are moved
upwards through the pinch rolls of the withdrawal machine. The output of one cooler unit is
limited by its cooling efficiency. As one single strand is not sufficient to meet capacity
requirements, a multi-strand unit is in use.
3.5.3 Fabrication of Sheet and Strip

Cakes from the cast shop are in most cases the starting material for the fabrication of sheets
and strips. The key elements of the fabrication process for flat products are the hot and
subsequent cold rolling operations. In detail the fabrication process comprises the following
steps, which are also illustrated in some detail in Figure 3-17.
- Pre-heating,
- hot rolling and milling,
- intermediate annealing,
- cold rolling,
- pickling, washing and drying,

- re-rolling and strand annealing,
- Finishing, and
- for sheets: Cutting to length,
- for strips: Cutting to width.
Slabs/Cakes
Preheating Hot Rolling Milling
Intermed. Washing
Preheating Pickling
Annealing Drying
Cutting to Sheets
Length Copper & Alloy
Strand
Rerolling Finishing
Annealing
Cutting to Strips
Width Copper & Alloy
Cooling Protection
Lubricant Pickling
Water Gas
Systems Systems
Systems Supply
Neutalisation
Effluent Treatment Spent Sludge
Lubricant Sulfates (Cu, Ni, Zn, etc)
Figure 3-17: Fabrication of sheets and strips of copper and copper alloys
Normally the slabs/cakes are pre-heated prior to hot rolling in gas- or oil-fired furnaces. In
some plants the off-gas is used for heat recovery.
The hot rolling is usually done with a dual rolling mill equipped with benches up to 200 m
and a final coiling device. The width of the rolled product is up to 1,400 mm, the thickness of
the slabs is reduced from approximately 250 mm down to approximately 10 mm. The cooling
water for the rolls has small amounts of lubricant added for improving the attachment to the
steel rolls. The vapour generated is vented and the vent gas is demisted prior to release to
atmosphere.
The hot rolling of the cast slabs takes only a short time per slab and is determined by the slab
weight. There is no loss of metal during hot rolling so slab and coils weight are identical. The
hot rolling mill does not require protection gas. The noise development during rolling is
controlled by protective measures. The surface and side milling units installed after hot rolling
are equipped with ventilation and dust filtration systems. The loss of material is around 5 %,
the chips are recycled for metal recovery. The surface milling requires protective measures
against noise emissions.
Further cold rolling operations result in a hardened metal. In most cases the coil is annealed
prior to cold rolling. Annealing is done under reducing conditions to avoid oxidation. As
protection gas exogas or nitrogen/hydrogen mixtures are in use. Exogas is produced at site
from natural gas in a special reactor which is indirectly fired. N2 and H2 are purchased and
stored at site in special tanks. The N2/H2 protection gas mixtures are produced from the
storage tanks by mixing the components in the ration required. For annealing before cold
rolling usually bell type furnaces are used with electric heating or indirectly fired by natural
gas or fuel oil. Tower type furnaces are applied for intermediate annealing of pre-rolled coils.
They are heated by natural gas and are operated with protection gas. Strand annealing furnaces
are in use for final and also for intermediate annealing. This method is a so-called touchless
annealing process, surface oxidation is avoided by applying protection gas. In some cases,
heat content of the off-gases is utilised to pre-heat combustion air or to generate steam. Prior
to annealing the material will be degreased after the coiling by washing with water which
contains detergents. The used solutions are cleaned by ultra-filtration.
After annealing the material is normally pickled in line in order to remove residual surface
contaminants and oxides. For pickling purposes systems of sulphuric acid as well as mixtures
from sulphuric and nitric acid are in use. The burden generated during usage of nitric acid is
treated in a gas cleaning system (scrubbing with caustic soda). The pickling is done in
continuous lines or in automatic processing, the acid is changed from time to time, the criteria
is the pickling result. The spent acid is given to recovery. The pickling is vented for workers
protection. Connected with the pickling bath a rinsing system is attached working with
rotating brushes, water and at last with deionised water to get a clean and acid free surface.
The rinsing water is given to the waste water treatment plant. Sludges are separated from the
pickling media and disposed of or recycled. After washing the handling steps following are
drying and coiling.
The sheet thickness is further reduced by stepwise cold rolling operations on different
reversing mills. For cold rolling different types of mills called Duo, Quarto, Sexto, Sendzimir
(12 rolls) are in use. Rolling mill designs as single-stand which are combined to an in-line
multi-stand rolling mill are also applied. It depends on the thickness of the sheet on the coils
and on the finishing status the coil has already been reached which combination of the
different types is applied.
During cold rolling an emulsion or oil is used for roll protection. Therefore, the roll stands are
vented and the ventilation gases are cleaned by mechanical filters, wet electrostatic
precipitators or scrubbing. The emulsion and the oil is cleaned from metal and cracked oil
particles by paper or textile band filters. Alternatively, the rolling mill coolant liquid is mixed
with inert adsorbing agents and filtered. The duration of use for the original emulsion or oil
may reach several years before it has to be replaced.
Also after cold rolling the surface of the rolled products is degreased by water containing
washing agents. The washing solution is cleaned by ultra-filtration and reused. The oil
separated from the washing water is given to authorised external companies for further
treatment.
For strip fabrication special cutting units are available to cut the rolled and finished sheet coils
into strips of the defined width. Table 3-53 compiles some typical data for the fabrication of
brass strips by hot and cold rolling.
Table 3-53: Typical data of a facility to roll brass strips

Hot rolling
Type of mill Mainly Duo
Dimensions start 250 - 130 mm thickness,
450 - 1.000 mm width
Final dimensions 15 - 12 mm thickness,
450 - 1.000 mm width
Temperature 750 - 800 °C
Rolling force Abt. 10 - 12 kN/mm sheet width
Surface milling 0,3 - 0,7 mm cutting of both surfaces
st
1 Cold rolling
Type of mill Mainly Quarto
Rolling force Abt. 15 - 20 kN/mm sheet width
Dimension reduction and Reduction 15 mm to 4 mm thickness in multiple
rolling speed passes, speed 100-200 m/min
Conversion ratio 70 - 80 %
*)
Annealing (recrystallisation)
Temperature 550 - 600 °C
nd
2 and final rolling
Type of mill Mainly Quarto, alternatively, depending on sheet
thickness, Sexto or stands with 20 rolls are used
Rolling force Abt. 2 - 1o kN/mm sheet width, depending of type of
mill used
Rolling speed Reduction 4 to 1 mm: 300 - 500 m/min, multiple
passes
Reduction 1 to 0,1 mm: 500 - 1000 m/min, multiple
passes
Cutting of sheets to strips
Type of equipment Longitudinal strip cutting machine
*)
Annealing required after every conversion ratio of more than 70-80 %.
Annealing temperatures selected depending of material properties to be achieved.
The described concept for sheet and strip fabrication, based on hot and cold rolling
corresponds to the conventional concept and is also suitable for high production rates.
However, there are concepts industrially applied or under development for direct casting of
sheets or strips followed by cold rolling. Such concepts bypass the hot rolling operation. One
method is the horizontal casting used for copper alloy strip production. These concepts are
also applied for rod and profile casting. Furthermore, different other systems have been
proposed for continuous strip and sheet casting and some are under development.
3.5.4 Fabrication of Copper and Copper Alloy Tubes, Rods and Sections
The fabrication process lines can be subdivided into two product groups, with each product
group following the same process steps. The groups are copper tubes in straight length and
coils and copper alloy tubes as well as copper and copper alloy rod and sections. In both cases
the start material for the fabrication process are copper and/or copper alloy billets. The
production concept of copper tubes (c.f. Figure 3-18) is somewhat different from the
production concept required for the fabrication of copper alloy tubes, rods and sections (c.f.
Figure 3-19).
Copper Billets
Breakdown
Preheating Drawing Annealing
Rolling
Section
Extruding Drawing
Rolling
Copper
Tubes
Sawing to
Drawing Straighten
Length
Copper
Annealing Coiling
Tube Coils
Cooling Protection
Lubricant
Water Gas
Systems
Systems Supply
Effluent Treatment
Spent
Lubricant
Figure 3-18: Fabrication of copper tubes
Billets
Preheating Extruding De-Scaling
Tubes
Copper & Alloy
Sawing to
Pickling Drawing Annealing Pickling Rods
Length
Copper
Copper & Alloy
Sections
Pickling Drawing Annealing Pickling Straighten Copper
Copper & Alloy
Cooling Protection
Lubricant Pickling
Water Gas
Systems Systems
Systems Supply
Neutralisation
Effluent Treatment Spent Sludge
Lubricant CuSO4, NiSo4
Figure 3-19: Fabrication of copper alloy tubes and rod/sections from copper and copper
alloys
The billets in a first stage are electrically or indirectly pre-heated by gas-fired units. Starting
from pre-heated billets, hydraulically operated extrusion presses are used for pressing
unfinished tubes from copper and copper alloy as well as for the production of copper alloy
rods and sections. For the fabrication of copper tubes different processes are industrially
applied:
- Tube extrusion followed by multi-step drawing to size,

- tube extrusion followed by breakdown rolling followed by several steps of drawing to size,
and
- hot piercing mill followed by breakdown rolling and drawing to size.
The process concept applied depends of the type of product to be fabricated. For billets, which
are extruded or rolled to tubes with thick walls, breakdown rolling has normally the
preference as first size reduction step. For tubes extruded to thin walls, tube drawing machines
are applied. For the fabrication of copper alloy rods and sections material extruding in coils or
straight length, cleaning and pickling, drawing to size using drawbenches or continuous
drawing machines, heat treatment for certain alloys and straightening and sawing are normally
the sequences of the fabrication process.
The whole process, started by the extrusion press or the hot piercing mill, is a sequence of
(mostly) reducing steps changing shape and size. During these processing steps the tools of
the equipment for size and shape changing are cooled and protected by adequate media, using
emulsions for the breakdown rolling and lubricants for the drawing units. The emulsions for
the breakdown rolling are cleaned up by filtration, thus increasing the life time and reducing
the amount of lubricant to be disposed for treatment. However, the lubricants used for the
drawing steps are completely lost with the product and no oily materials have to be rejected
from the drawing processes.
Annealing may be required as intermediate operation during the stepwise size reduction
process in order to enable the fabrication of the different finished products of copper and
copper alloys. For annealing a reducing atmosphere has to be maintained exogas or N2/H2
mixtures using as protection gas. Exogas is produced in reactors at site, N2/H2 mixtures are
generated by mixing of pure gases which are purchased and stored at site in special tanks.
Annealing furnaces in use have inductive electrical or indirect gas-fired heating. Also pickling
or degreasing operations may be required as finishing procedure for the products. As pickling
solution, mainly sulphuric acid is used, for some special alloys mixtures of nitric and
sulphuric acid are applied.
For degreasing the tubes after the final working down step chlorine/hydrocarbons or aliphatic
hydrocarbons are in use. For some special products also alkaline solutions can be applied.
Chlorine hydrocarbons require gas capture and cleaning. Special chemicals are in use to
obtain special high standard surfaces of specific products. The chlorine/hydrocarbons

containing vent gases from degreasing of the tubes after the final processing stage are treated
in a reactor by passing through active carbon or resin. Loaded carbon is re-generated by
treatment with steam, resin by treatment with hot air.
The fabrication scrap produced during the different size reduction steps is reused in the
melting and casting shop. Cooling water is required for extrusion and for different other
purposes. The cooling water for direct or indirect cooling is provided in once-trough systems
or from circuits with re-cooling in cooling towers. Blowdowns are treated; solids as scale and
oxides are separated and recycled.
3.5.5 Waste water treatment

The effluent treatment concepts in use are depending of the type and range of contamination
of the waste water. In general oil separation is applied prior to discharge.. Process water like
rinse water from pickling, laboratory effluent waters, waters from polishing operations and
used galvanic waters from tool preparation are treated by chemical and physical operations in
a waste water treatment plant (neutralisation with lime and optional ironsulphate; additional
reduction of metals with sandfilter and ion exchanger). The arising sludges are de-watered on
filter presses or similar. The surface water is collected and solids and oil are removed in a
settler prior to discharge. Indirect cooling waters are not contaminated by metals, the
blowdown from the cooling towers are discharged to the sewer. If direct cooling is applied
with a closed system, the cooling water is completely recycled and only treatment sludge
occurs. If direct cooling water passes through after treatment without reuse or only partly
reuse, waste water as well as treatment sludge occur.
3.5.6 Summarised data on outputs and environmental concerns of the fabrication of

semi-finished products

Table 3-54 shows stack emissions into the air from the fabrication of semi-finished products
(annual average concentration).
Table 3-54: Emissions from the fabrication of semi-finished products (annual average
concentration)
Process unit Particulate CO TOC
matter
[mg/m3] [mg/m3] [mg/m3]
Melt shop: Electric furnace < 10 - < 20
Rotary furnace < 10 - < 50
*)
Shaft furnace (ASARCO type) < 10 < 100 < 20
Rolling mill: - - < 50
Milling: < 10 - -
*) With afterburner (afterburning depending on type of feed (oil/organic content))
The annual average concentrations represent the typical range. However, the results of single
measurements can be higher than the given range and reach the authorised values depending
on different operation conditions (charging, blowing, pouring, poling etc.), different input
materials and changes in the operating mode.
In Table 3-55 specific emissions from the fabrication of semi-finished products are given.
They include the emissions from all cleaned off-gases captured by hoods and from cleaned
ventilation gases (arising from venting the shed). Fugitive emissions are not included.
Table 3-55: Specific emissions from the fabrication of semi-finished products (annual
average loads)
Particulate CO TOC Oil mist PCDD/PCDF
matter
[g/t] [g/t] [g/t] [g/t] [µg/t TE]***)
Melt shop: Electric furnace < 70 - < 80 - <5
Rotary furnace < 50 - < 11 - < 10
Shaft furnace (ASARCO Type) < 12 - - < 10
without afterburner*) < 10,000
with afterburner*) < 45
Rolling mill: - < 100 < 30**)
Milling: < 20
*) Afterburning depending on type of feed (oil/organic content)
**) Usually included in value for TOC
***) Values according to Krüger [45]
In Table 3-56 the main constituents in the dust content of all furnace off-gases cleaned in
fabric filters are given.
Table 3-56: Main constituents in the dust content of off-gas cleaned in a fabric filter
Substance Unit Measured value Authorised
value
Electric Furnace Rotary Furnace Shaft furnace
Class I (TA Luft)
Cd mg/m³ < 0.006 < 0.1 < 0.1
Hg mg/m³
>Tl mg/m³
Sum Class I (TA Luft) mg/m³ < 0.2 < 0.2 < 0.2 0.2
Class II (TA Luft)
As mg/m³ < 0.025 < 0.005 < 0.005
Ni mg/m³ < 0.003 < 0.003 < 0.003
Co mg/m³
Se mg/m³
Te mg/m³
Sum Class II (TA Luft) mg/m³ <1 <1 <1 1
Class III (TA Luft)
Sb mg/m³
Pb mg/m³ < 0.1 < 0.05 < 0.05
Cr mg/m³ < 0.007
Cu mg/m³ < 0.5 < 0.6 < 0.6
Sn + Mn mg/m³ < 0.05
Sum Class III (TA Luft) mg/m³ <5 <5 <5 5
The specific emission values (annual average) of substances in the dust content of off-gases
cleaned in a fabric filter are given in Table 3-57.
Table 3-57: Specific emissions of the main constituents in the dust content of the off-gas
cleaned in a fabric filter (annual average loads)
Substance Unit Value (calculated)
Electric furnace Rotary furnace Shaft furnace
Cd g/t 0.05 0.5 0.2
As g/t 0.2 0.03 0.01
Ni g/t 0.03 0.02 0.005
Pb g/t 1 0.3 0.1
Cr g/t 0.05 - -
Cu g/t 3.5 3 1
Sn - Mn g/t 0.4 - -
Waste water
In Table 3-58 data on the concentration of contaminants in the waste water (process, cooling
and surface water) from the fabrication of semi-finished products is given (annual average).
Table 3-58: Pollutants in the different waste water streams from the fabrication of semi-
finished products (annual average)
Item Units Value
pH Units pH 6.5 – 9.5
Copper mg/l < 0.5
Cadmium mg/l < 0.2
Lead mg/l < 0.5
Mercury mg/l < 0.05
Nickel mg/l < 0.5
Tin mg/l <2
Chromium total mg/l < 0.5
Arsenic (As) mg/l < 0.3
Zinc mg/l <2
Suspended solids mg/l < 100
*)
COD (COD : TOC = 4 : 1) mg/l < 100
*)
COD only for discharge into waters, for discharge to sewer no limits are required
In Table 3-59 the amount of contaminants discharged per year with the process water of a
plant are given as an example. A volume of 35,000 m3/a process water are discharged at this
plant. The values are real figures and not calculated on the basis of statutory limits.
Table 3-59: Contaminants discharged per year with the process water of a semis
fabrication plant (example)
Substance Unit Value
Cu kg/a 11
Ni kg/a 3
Zn kg/a 25
Pb kg/a 1
Cr kg/a 1
As kg/a 0.01
Cd kg/a 0.01
Hg kg/a 0.01
Sn kg/a 1
In the amount of solids and oil in the surface water of the hardened water-proof storage place
are given as an example. At this plant, 60,000 m3 of surface water are discharged per year.
Table 3-60: Solids and oil discharged per year with the surface water of a semis
fabrication plant (example)
Substance Unit Value
Cu (solid) kg/a <6
HC (Hydrocarbon) kg/a < 10
Main residues
In Table 3-61 an overview of the main residues is given.
Table 3-61: Main residues from the fabrication of semi-finished products
Process unit Residue Use/treatment option
Melting/casting shop Dust Recycled to smelter for metal recovery.
Refractory Partly used for construction, balance dumped.
Slag Recycled to smelter for metal recovery.
Scale Recycled to smelter for metal recovery or internal
use.
Hot rolling mill Scale Recycled to smelter for metal recovery.
Milling chips Internal recycle.
Used emulsion/oil Given to authorised companies for treatment.
Cold rolling mill Used emulsion/oil Given to authorised companies for treatment.
Pickling Sludge Recycled for metal recovery.
De-greasing Sludge Given to authorised companies for treatment.
(CHC containing)
Used detergents Given to authorised companies for treatment.
Used oil Given to authorised companies for treatment.
Direct cooling water treatment Sludge Discarded
General Used packing materials Given to authorised companies for treatment.
340 German Candidates Best Available Techniques
4 German candidate best available techniques (BAT) for integrated

pollution prevention and control in the copper production
In this chapter, German best available techniques (BAT) will be described that serve as
possible candidates for the later determination of best available techniques on an EU level.
For the identification of the German BAT, the IPPC-Directive, that is to say the definition of
BAT in Art. 2.11 IPPC-D, serves as a basis:
"Best available techniques should mean the most effective and advanced stage in the
development of activities and their methods of operation which indicate the practical
suitability of particular techniques for providing in principle the basis for emission limit
values designed to prevent and, where that is not practicable, generally to reduce emissions
and the impact on the environment as a whole: Techniques should include both the technology
used and the way in which the installation is designed, built, maintained, operated and
decommissioned, available techniques should mean those developed on a scale which allows
implementation in the relevant industrial sector, under economically and technically viable
conditions, taking into consideration the costs and advantages, whether or not the techniques
are used or produced inside the Member State in question, as long as they are reasonably
accessible to the operator. Best should mean most-effective in achieving a high general level
of protection of the environment as a whole." According to the IPPC-Directive, in the
identification of BAT special consideration should be given to the following items listed in
Annex IV:
- "the use of low-waste technology",

- "the use of less hazardous substances",
- "the furthering of recovery and recycling of substances generated and used in the process and
of waste, where appropriate",
- "comparable processes, facilities or methods of operation which have been tried with success
on an industrial scale",
- "the nature, effects and volume of the emissions concerned",
- "the commissioning dates for new or existing installations",
- "the consumption and nature of raw materials (including water) used in the process and their
energy efficiency",
- "the need to prevent or reduce to a minimum the overall impact of the emissions on the
environment and the risk to it", and
- "the need to prevent accidents and to minimise the consequences for the environment".
On basis of the processes used in the German copper production industry described in
chapter 3, proposed emission guide values for BAT are given in this chapter. These values
can be reached with the process units in combination with abatement techniques. Since this
German Candidates Best Available Techniques 341
paper deals only with German techniques, only German BAT are described which work within
the proposed emission guide values. They should be seen as one possible combination of
process unit and abatement technique, other combinations of process and abatement
techniques in operation within Europe are not excluded.
4.1 General provisions and requirements for the prevention and control of
environmental pollution
In the following sections the monitoring of emissions and general measures, which can be
applied to prevent and control emissions into the air as well as discharges of waste water and
to prevent the formation of solid wastes are presented. In addition measures and general rules
for other areas of environmental concerns as noise, plant safety and energy aspects are
described. Only a short overview will be given; detailed technical information can be found
elsewhere e.g. in [56], [88].
4.1.1 Monitoring of emissions

The following section is intended to ensure that emissions are measured in such a way that the
results are representative, mutually comparable and clearly describe the relevant operating
state of the plant.
Measurement Planning
The objective and scope of measurements are governed by the requirements in the approval
decision or by particular events. In principle, the measurements serve to determine substances
in the clean gas. Measurement planning should take account of the mode of operation and the
operating state of off-gas purification plants, operating conditions in the plant (continuous,
discontinuous, start-up and shut-down operations, load change) and the effect of
thermodynamic interference factors. These data form the basis for determining the selection of
operating conditions at which the highest emissions will presumably be recorded, the number
and duration of the measurements, the method of measurement to be chosen, and the position
of the measurement locations and points.
In the case of continuous and batchwise operation, a sample collection time or measurement
time of half an hour (half-hour mean value) is, as a rule, necessary. If dust contents are low or
if PCDD/PCDF are to be determined, other measurement times and, consequently, other
reference times may be necessary because of the limitation of detection. In particular cases,
for example batch operation, the measurement time and, consequently, the averaging time
should be appropriately modified. For continuous operation and only slight fluctuations in the
emission characteristics, at least 3 individual measurements should be performed at the
highest emission level. If it is anticipated that the emission level will be very variable during
continuous operation, at least 6 measurements should be carried out, the sampling and
averaging time being limited to the emission phase.
Sampling Locations
The sampling points should meet the requirements of Guidelines VDI 2066 Part 1 [77]and
VDI 2448 Part 1 [80]. According to the latter, the sampling points
- should be clearly marked,

- should have, if possible, have a disturbance-free flow in the measurement section,
- should have measurement openings that can be closed,
- should have the required energy supplies,
- should have sufficiently large working platforms, and
- should ensure that the requirements for safety at work are met.
Measured Variables, Methods of Measurement and Instruments

Measurements of the components specified in Table 4-1, where the VDI guideline is quoted in
which the methods of measuring the components are described, should be carried out to
characterise the emission behaviour of a plant, where the off-gas is removed via a known
outlet:
Table 4-1: VDI guidlines on emission measurements
Component VDI Guideline or DIN Standard
Total dust VDI 2066 [77]
Dust constituents VDI 2066 [77]
Cd, Cr, Cu, Pb, Zn VDI 2268 [81]
As VDI 2066 [77]
VDI 2268 [81]
Total organic carbon VDI 3481 [78]
Sulphur dioxide VDI 2462 [79]
PCDD/PCDF DIN EN 1948 [21], [76]
The parameters sulphur oxides (mass flow > 50 kg/h) and total dust (mass flow > 2 kg/h)
should be continuously observed using an approved measurement apparatus, the suitability of
which has been tested and, as a rule, evaluated using an emission evaluation computer.
The reference quantities necessary for evaluating and assessing the continuous measurement
should also be continuously observed. The continuous measurement of these parameters may
be dispensed with, if experience shows they are subject to only small fluctuations. The
instruments should be calibrated after installation of a measurement location and then every 5
years, and should be checked once a year for serviceability.
Reference Quantities
To convert the emission concentrations obtained to standard conditions (po = 1013 hPa, To =
273 K, p(H2O) = 0 hPa), the volumetric off-gas flow (in order to calculate the emission mass
flow), the off-gas temperature, the water vapour content of the off-gas, the static pressure in
the off-gas duct and the atmospheric pressure should be determined as off-gas parameters.
Measurement Result Evaluation and Measurement Report

All the emission measurement results should be reported as masses, in mg/m3 or, for
PCDD/PCDF, in ng/m3 (ITE), of the emitted components, relative to the volume of the off-gas
in the standard state after subtracting the water vapour content. From the measured values of
instantaneous samples for gaseous components, the measurement result should be determined
as a half-hour mean value or as a computed half-hour mean value. From the measured values
of individual measurements of particulate emissions, the measurement result should be
reported as a half-hour mean value or, if the sampling time is longer, as a mean value for the
sampling time.
Continuously determined measurements should be evaluated as follows:

From the measured values, the half-hourly mean value should always be determined for each
consecutive half hour. The half-hourly mean values should, if necessary, be converted to the
respective reference quantities, assigned to at least 20 class intervals and stored as a frequency
distribution. A daily mean value for the daily operating time should be calculated from the
half-hourly mean values for each day of the year. The emission limits are deemed to be met if
none of the daily mean values do not exceed the specified concentration by mass, 97% of all
the half-hour mean values exceed 6/5 of the specified concentration by mass and none of the
half-hour mean values exceed twice the specified concentration by mass. Any measurement
report and measurement protocol drawn up should conform to Guideline VDI 2066 Part 1 [77]
and should in particular contain:
- the objective,
- general information on the measurements,
- a description of the plant, its state and operating data,
- operating conditions during the measurement,
- information on the measurement planning,
- sampling locations,
- methods of measurement,
- tabular presentation of the individual measurements,
- evaluation of the results,
- consideration of errors,
- presentation of the quality assurance measures, and
- an abstract.
Determination of specific emission values

If emissions are stated as specific emissions, it should be defined properly which emission
sources (stack emissions/fugitive emissions) are included. Often only stack emissions are base
of the calculation of specific emissions. This is not sufficient, since nowadays the stack
emissions of copper smelting plants are cleaned so efficient that the total released emissions in
Germany are determined mainly by fugitive emissions. If the calculation of specific emissions
are only based on stack emissions, all measures to minimise fugitive emissions by capturing
and cleaning them result in an increase of the specific emissions although the total emissions
released are reduced.
4.1.2 Techniques to prevent and control emissions into the atmosphere

In chapter 2 general information on the main emissions into the air from copper production
plants is given, whilst in chapter 3 detailed information is provided. In this section, general
measures and techniques to minimise emissions as well as end of pipe measures to reduce the
content of pollutants in off-gases from the copper production industry are summarised. Since
process integrated measures, that prevent the formation of contaminants during the production
process, are mainly process specific, they are dealt with in section 4.2.
The emissions are subdivided into stack and fugitive emissions. Stack emissions are captured
emissions, which can usually be treated with appropriate gas cleaning devices. Sources for
fugitive emissions are roofs and openings of production buildings as well as inadequate
enclosed transport system and leakages. They also can arise during open handling and storing
of materials.
4.1.2.1 Measures to prevent fugitive emissions

The contribution of fugitive emissions to the total emissions from a process site can be very
significant and, if appropriate cleaning of the captured gases is applied, in most cases exceed
the stack emissions. Several general measures are used to prevent fugitive emissions from
storage, handling and transfer operations of dusty materials, from production processes
(mainly furnaces) and from recycling operations. It should be mentioned, that, as a rule, these
measures are wide-spread, although their realisation depends strongly on the site-specific
constraints.
Storage, handling and transfer operations of dusty materials

During storing, handling and transport of materials consisting of fine particles such as ore
concentrates, drosses and filter dusts, emissions of particulate matter can occur. When these
dusty materials are stored, the following measures can help to reduce fugitive emissions:
- roofing and complete side coverage for the storage of bulk goods including secondary
facilities,
- capturing of exhaust air and adequate cleaning (c.f. 4.1.2.2),

- storage in closed containers (protection against wind-blown emissions),
- coverage of the surface, e.g. with mats,
- planting,
- establishing overgrown earth embankment, windbreak plantings or windbreak hedges, and
- continual maintenance of a sufficient moisture level on the surface, i.e. with sprinkler
devices.
For the handling of dusty materials, the following measures can be applied to reduce fugitive
emissions:
- installation of exhausters and dedusters at main emission relevant parts, i.e. stationary
reception, transfer and discharge points of dried ore concentrates, shovel loaders and
transport units, downspout of loading facilities,
- complete enclosure of the machinery, equipment and other facilities used for the treatment or
production of dusty goods, and
- dusts can be received wetted and/or in sealed containers or in enclosed vehicles.
When dusty materials are transported, fugitive emissions can be reduced by the following
measures:
- usage of adequate transport facilities, like covered conveyor belts or closed recycling
systems for filter dusts) and collection of remaining dust containing air,
- usage of underfed conveyors,
- reduction of vehicle contact with the stockpile,
- roads should be well constructed, well maintained, kerbed, cambered and equipped with
drains to obtain a maximum run-off and collection of water,
- regular cleaning of access roads with cleaning machines,
- keeping roads wet and cleaning when appropriate,
- reducing speed for vehicles at the plant site,
- careful on-site traffic management (e.g. minimisation of number of private vehicles passing,
restriction of vehicles to designated functions and areas), and
- careful cleaning of vehicles, especially their wheels, before leaving the concentrate storage
buildings.
Operation of production and recycling units

To prevent fugitive emissions during operation of production and recycling units, devices for
the extraction of process gases should be installed at emission sources such as furnaces,
launders, melting pots, crushers for recycling material, etc. The extraction volumes of these
devices should be sufficient to cope with abnormal operation conditions and overloads. The
captured off-gases have to be cleaned adequately(c.f. 4.1.2.2). Encapsulating measures can

include:
- lock chambers on charging systems,

- close hooding at tapping points,
- housing for ladles during tapping,
- enclosure of hot metal material handling, and
- arrestment devices for crushers.
To prevent emissions of particulate matter in the working area, high capacity vacuum cleaning
systems should be used.
4.1.2.2 Measures to prevent and control stack emissions

In order to control stack emissions, measures to clean the gas streams before being released
should be applied. Depending on their physical state, contaminants contained in the gas
streams can be classified in two groups:
- gases and vapours, and

- particulate matter.
For their removal from the gas streams (raw gas, exhaust air, process gas), different gas
cleaning devices are available as shown in the examples in Table 4-2. Normally dry off-gas
cleaning is applied. Only when gaseous compounds or vapours such as e.g. mercury vapour
have to be precipitated, a wet gas cleaning may be necessary.
Table 4-2: Selection of gas cleaning devices

Removal of ... Gas cleaning device Remark / example Reference
Particulate matter Settling chambers
Cyclones Used as pre-precipitator VDI 3676
device
Electrostatic precipitators - Dedusting of SO2-containing VDI 3678
- Dry off-gases (dry/wet ESP)
- Wet - off-gas from slag granulation
(wet ESP)
Scrubber (Venturi) Usage of water requires VDI 3679
- water treatment
- corrosion control
Fabric filter - selection of adequate filter VDI 3677
materials (elevated
temperatures)
Gaseous contaminants Absorption into a liquid Boliden/Norzink process for VDI 3675
and vapours using packed, plate or spray removal of mercury
towers
Adsorption on a solid in a Lead sulphide process for VDI 3674
fixed bed removal of mercury
Chemical conversion using VDI 3476
catalytic reactors
When choosing a gas cleaning device, the following criteria have to be considered in each
specific case:
- process and operation characteristics,

- raw gas characteristic: temperature, humidity, composition, flow, etc.,
- dust characteristic: mass flow, grain size distribution, etc.,
- space requirements,
- separation efficiency, clean dust content, and
- operation safety, capital expenditure and operation costs.
As an example, different gas cleaning techniques to remove certain gaseous contaminants and
vapours are shown in Table 4-3. Sulphuric acid plants are used in the copper production
industry with the primary function to remove sulphur dioxide from the off-gas.
Table 4-3: Techniques to remove gaseous contaminants

Substance to remove Process Remarks
Sulphur dioxide Recovery of sulphuric acid in - minimum concentration of
- Single contact plant SO2 necessary
- Double contact plant1) - steady off-gas conditions
- Wet catalysis necessary
- Processes based on NOx
Recovery as liquid sulphur dioxides by
- Condensation processes
- Absorption processes
Recovery as elemental sulphur
Dry sorption of SO2 by calcium oxide - SO2 concentration too low for
contact acid plant
- unsteady conditions
Mercury vapour Wet absorption processes: - subsequent sulphuric acid
- Selenium filter recovery
- Boliden/Norzink1)
- Outokumpu process Scrubbing with H2SO4
- Sodium thiocynate process
Dry adsorption processes
- Activated carbon filter
- Lead sulphide process
Carbon monoxide Afterburning chamber1)
1)
: These techniques are applied in the German copper production industry.
4.1.3 Water management

In chapter 2 general information on the main water discharges and their contaminants from
copper production plants is given, whilst chapter 3 provides detailed information. In this
section, general measures and techniques to prevent uncontrolled discharges, different cooling
water concepts, as well as end-of pipe treatment techniques to reduce the content of pollutants
in the effluent are summarised.
In general, measures in order to prevent accidents (c.f. 4.1.7) and devices to avoid
uncontrolled discharges due to leakages or accidents are necessary. These devices should
include facilities to contain process waters, site drainage waters, emergency fire water and
chemically contaminated waters. Bunding of storage tanks or double walls for tanks are
essential in many cases, where there is a risk to controlled waters, sewers and drains, and on-
site effluent treatment plants. Shared bunds are possible in cases where the materials stored
are not incompatible. Bund capacities should always have sufficient volume for the maximum
storage. High level alarms and trip switches on storage tanks should be designed to an
appropriate integrity. These devices as well as the bunds should be inspected on a regular
basis, especially where corrosive substances are involved.
The main liquid effluents arising in the copper production industry are from cooling water for
cooling furnaces and sulphuric acid plants, slag granulation and surface run-off. An additional
source of waste water are wet gas cleaning operations. So, to minimise the amount of waste
waters, this kind of gas cleaning should only be carried out if it is not possible to clean the gas
sufficiently with dry gas cleaning devices.
Cooling water concepts

The waste water situation in copper production plants is strongly determined by site specific
conditions [75]. The main location dependent factor is the availability of water, especially for
cooling purposes. If the smelting plant is situated alongside a river containing sufficient water,
the cooling of furnaces, runners, burners etc. is carried out in temperature-controlled, open
recirculating systems without re-cooling (once-through cooling). The heat is removed by
heating the cooling water. If water resources are in short supply, cooling is carried out in a
closed recirculating system, with recooling by means of cooling towers. The latter are
operated, as a rule, as spray towers and the heat is removed by evaporating the water. Cooling
water used in closed recirculating systems must, as a rule, be conditioned to prevent the
growth of algae, corrosion etc. In addition, elutriation of the recirculation water is necessary in
order to keep the salination within limits. The elutriation water contains agents and increased
concentrations of substances introduced into the recirculatory cooling system with the make-
up water.
Purification of indirect cooling water, i.e. cooling water not polluted by the product, in an
open recirculatory cooling system is not necessary. Polluted cooling water from the elutriation
of the recirculating systems or from casting plants may need treatment. The slag granulation
water is always recirculated without a conditioning agent and elutriation is often not
necessary.
End-of-pipe treatment of waste water

Contaminated water generated by the copper production industry is usually characterised by
the presence of elevated metal concentrations (for example lead, copper, tin, zinc, cadmium,
mercury, and nickel), elevated elements like arsenic as well as suspended solids. So the end-
of-pipe treatment techniques used in this industry are applied in order to minimise the
concentration of these pollutants in final effluent discharges to the aquatic environment.
Depending on the site specific conditions, the plant can be connected to an urban waste water
system where the end-of-pipe treatment is applied or the treatment is carried out in a central
waste water treatment plant at the plant site. Because of different pollutant loads, the
effectiveness of the end-of-pipe treatment can be improved by separating cooling water,
surface runoff water from roofs and roadways and stockyard as well as process water.
If the treatment is carried out at the plant site, the waste water from the different production
plants is usually brought together in a collecting tank. If necessary, surface water is collected
in a separate tank and is then usually supplied to the collecting tank to guarantee a more
constant flow. Only a few companies treat their surface water in an extra facility. The tank for
the surface water has to be dimensioned to handle worst-case rainfalls. In the collecting tank,
oil, grease and plastics are removed mechanically. The subsequent treatment is based on
chemical precipitation and neutralisation, sedimentation and filtration or centrifugation.
Devices for this treatment are described in Table 4-4 [24].
Table 4-4: Devices for waste water treatment
Process step Principle Device Remark
Precipitation Chemical precipitation: Precipitation reactor, To remove heavy metals,
and forming of insoluble tanks hydroxides and afterwards
neutralisation compounds by addition of sulphides are used as precipitants;
precipitants, ferric sulphate is used to eliminate
adjustment of pH the surplus sulphide
Solids Sedimentation: Clarifier, two Coagulants: polymers
separation Settling due to gravity, often compartment tank
use of additional flocculants
Polishing step Filtration Gravity filter with a
sand bed
Precipitate Filtration, Belt filter, vacuum Dewatered sludge is recycled to
dewatering centrifugation filter (rotary drum the metal production process or
filter), filter press, dumped
cyclone
Especially where large discharges of effluent with high or low pH are possible, consideration
should be given to a two or three stage pH control system. Dosing systems are unable to cope
with effluent with extreme pH; therefore, an intermediate facility capable of storing acidic or
alkaline effluent should be installed with an automatic control, if such effluents are likely.
In selecting an appropriate separation technique, consideration should be given to such factors

as:
- current industry practice for the same or similar waste waters,

- ability to produce an effluent with the desired characteristics,
- characteristics of the concentrated solids that are produced,
- mechanical simplicity,
- reliability of equipment operation,
- controllability of the process,
- space requirements, and
- investment and operating costs.
4.1.4 Management of by-products and wastes

In chapter 2 general information on solid material arising from the production of copper in the
different process units are given and in chapter 3 detailed information is provided. In this
section, the treatment options for solid materials to minimise the amount of wastes are
summarised.
In copper production, only small amounts of waste material arise compared to the throughput
of raw materials because it has traditionally been the objective of the processing technology to
produce as many constituents as possible in a marketable form and thereby to close the
material cycle. This may be done within one company or in co-operation with other
companies. The various chemical and physical properties of the substances are used to extract
the individual constituents. These are, for example:
- distribution of substances between the molten and gas phase: in copper metallurgy, zinc,
lead, tin, cadmium, arsenic and their compounds, in particular, are volatilized, discharged
from the production process with the off-gas and collected in gas cleaning plants in the form
of flue dusts and extracted from the latter,
- different distribution coefficients of molten materials in non-miscible molten phases (for
example, matte and slag),
- non-miscibility and insolubility of solid phases in liquid phases: separation of solid
substances from melts (for example, liquations, dross, skimmings) or from aqueous solutions
(sludges, precipitations).
In this way, even traces of substances in the raw materials can be obtained in a marketable
form.
In primary production, the copper concentrate contains mainly copper, iron and sulphur. Silica
is added as a flux. Consequently, besides copper, iron silicate slag and sulphuric acid are
produced in quantities, which are even higher than the copper production. Sulphuric acid is
widely used e.g. in the chemical industry. The iron silicate slag is either granulated or
produced in the form of lumps, which may be crushed and screened according to the customer
demand. Granulated iron silicate is used as a quartz-free blasting agent or as a construction
material (as a substitute for special sand qualities). Iron silicate lumps are used for various
construction purposes, e.g. embankment construction of waterways, breakwaters, dams as well
as for road construction. In any case, slag production is carried out with regard to common
product standards, such as DIN EN ISO 11 126 Part 3 and VBG 48 for blasting materials as
well as [83] and different technical guidelines for construction materials. The same goes for
iron silica slag from secondary production, which has a similar chemical and mineral
composition and which can be used in the same fields of application.
Other by-products from primary and secondary copper production are noble metals, lead, tin
i.e. tin lead alloy, zinc oxide, nickel sulphate, selenium and other metals or metal compounds.
Metal wastes arise only if the demand is not sufficient, which is the case with arsenic. This is
why a surplus of arsenic compounds are safely disposed of in underground disposal sites.
Other wastes which cannot be avoided are sludges from the waste water treatment plants or
from the cooling water treatment, sweepings from paved areas and plants, used operation
materials such as filter materials, conveyor belts, pallet wood, paper, oils, emulsions, ion
exchangers from the boiler feed-water treatment, packaging materials, insulating materials,
furnace linings etc. If possible, those wastes should be used in recovery operations. Typically
sludges from the waste water treatment plant, sweepings from paved areas and plants, filter
materials and insulating materials are recirculated to the smelter. According to the European
guideline 75/442/EEC, recovery operations are
- Use as a fuel (other than in direct incineration) or other means to generate energy,
- Solvent reclamation / regeneration,
- Recycling / reclamation of organic substances which are not used as solvents, and
- Recycling / reclamation of metals and metal compounds, etc.
This means wastes can be utilised in a material manner or can be used for the generation of
energy. Priority should be given to this kind of utilisation with less environmental impact.
Only if recovery is not possible according to the rules and without causing damage, wastes
should be disposed of. This should be done in an approved manner in adequate facilities at the
production site or at the nearest available site and it should be specified how the accumulation
and storage of waste has to be controlled.
4.1.5 Energy aspects

In general, the optimal solution in terms of energy management depends on the specific
conditions existing at the site. An appropriate way of finding this solution is to draw up an
energy utilisation concept which combines technical and economic objectives and eliminates
information deficits. This general concept specifies economically feasible measures to be
taken to optimise energy use and is structured as follows:
1. Overview of the plants operated at the site and of their energy demand in terms of fuel and
power demand.
2. Information on energy use inside the plants prior to site-specific optimisation, particularly
- types and amounts of energy supplied to and removed from the plant, the most important
reactions and their enthalpies including main parameters,
- description of the plant; energy balance, flow charts.
3. Description of energy use inside the plant after its energetic optimisation (as under 2.
above), including description of envisaged measures.
In the copper production industry, several measures are applied in order to minimise energy
consumption or to recover the waste heat that is produced. To minimise the energy
consumption of the processes, the fuel value of the feed material is used to decrease the
amount of energy needed. Hot charging of intermediate products where possible or
continuously working plants minimise the additional energy supply, since the material has not
to be remelted in every process step. The surplus reaction heat can be used as a substitute for
fossil fuel or to melt additional scrap or internal reverts.
The utilisation of waste heat has a long tradition for some types of furnaces, but in some cases
it is difficult, with the result that no effective solutions exist today for various subregions. In
general the devices for using the waste heat are designed in order to maintain plant
availability, so they are not optimised with regard to maximising the energy efficiency.
In the case of fire-top blast furnaces or those with off-gas afterburning and also in the case of
anode reverberatory furnaces, the off-gas temperatures are between 1,000 °C and 1,200 °C, so
the heat in the off-gas can be used to generate steam in waste-heat boilers. In the Contimelt
plant an integrated concept for the utilisation of heat has been implemented to save fuel and
also to generate steam. The steam generated is generally used in-house, e.g. for heating the
electrolyte, for providing hot water in the washroom and for heating the building.
4.1.6 Noise aspects/abatement techniques

In the planning and operation of installations, all technical, structural, organisational and
planning-related measures must already be taken into account during the planning phase, in a
manner appropriate to the respective local operating situation and in consultation with
acoustic experts. Acoustic experts should be consulted throughout construction and their
advice should be taken into particular account. Use should primarily be made of technical and
planning-related noise prevention measures. In general the following measures have to be
considered:
Technical measures
- Obtaining information at an early stage about noise emissions of machinery, installations and
parts thereof, and of work and production processes,
- use of low-noise machines and processes,
- reduction of noise generation and transmission,
- reduction of sound emission of, e.g. by the use of sound absorbers, and
- maintenance of machinery and soundproofing equipment.
Structural measures
By means of secondary soundproofing measures, such as encapsulation, absorbing walls and
buildings, further noise reduction can be achieved. The absorption of air-borne sound by
space-enclosing structural components primarily depends on their surface mass and good
sealing. Structural measures to reduce the transmission of structure-borne sound (e.g. partition
joints, appropriate foundations) are necessary, if a high level of structure-borne sound is
expected to emanate from the building as a result of e.g. noise emission from machinery,
rolling operations or vibration.
Organisational and planning-related measures

Additional reductions in noise emissions as a function of local conditions can be achieved by
organisational and planning related measures, such as accumulating high-noise sources and
increasing the distance between noise sources and affected areas. In addition, operation
restrictions may have to be imposed in special cases to reduce noise emissions. The
exploration of suitable sites under consideration of the existing noise sources is of particular
importance. Noise emissions from traffic to and from installations, which arise in connection
with their operation, must likewise be taken into account.
4.1.7 Plant safety aspects

The general policy for the prevention of, preparedness for and response to industrial accidents
is based on the following principles:
Prevention principle
- The plant should be constructed and operated in such a way as to prevent the uncontrolled
development of normal operation,
- the plant should be constructed and operated in such a way that the consequences of
accidents are reduced, and
- the plant should be constructed and operated according to the best available safety
techniques (state of the art safety technology).
Consideration of complex systems in process industries

Complex systems can only be sufficiently examined by means of systematic, logical methods.
This is taken into account by applying:
- systemanalytical investigation methods,

- detailed safety analysis considering the conditions of the individual case.
Appropriateness of means
Safety requirements are graded according to "type and scope of hazards to be expected". To
this end, rules are set up for:
- substances relevant to accidents (substance criteria, list of substances),

- industrial activities relevant to accidents (list of plants).
The objective dependence of the disaster potential upon the quantity of hazardous substances
is considered by a quantity threshold concept that defines staged safety requirements as a
function of quantity.
4.1.8 Plant operation and decommissioning

Operational control plays an important role in the reduction of emissions. Special attention
should be paid to the maintenance of equipment, malfunctions and breakdowns as well as
supervision and training [88].
With regard to the cessation of activities, and in order to avoid any pollution risk and to return
the site of operation to a satisfactory state, soil protection is of major importance. An
integrated approach requires that at least measures should be taken:
1. To minimise the amount of soil that needs to be excavated or replaced due to construction
measures and to make sure that excavated soil material is treated carefully (in order to
avoid harmful changes of soil properties),
2. to minimise the additional input of substances into the soil during the operation phase of a
facility (e.g. additional input due to deposition of airborne substances should not lead to
precautionary soil levels being exceeded and spillages should be avoided);
3. to ensure a clean closure when a facility is shut down, e.g. clean up and rehabilitation or
securing of contaminated soil, soil securing, with regard to the future use of the area.
Natural soil functions should be safeguarded, if feasible.
4.2 Candidate BAT for copper production

Within the framework of integrated pollution prevention and control, first of all the above-
mentioned general techniques and rules as described in section 4.1 should be considered for
each plant operation. In this section the proposed emission guide values for BAT are given on
the basis of the explanations in chapter 3. Since this paper deals only with German techniques,
only German BAT are described which work within the emission guide values. They should
be seen as one possible combination of process unit and abatement technique, other
combinations in operation within Europe are not excluded.
The process units are described in a modular way, since the copper production industry is too
complex and primary and secondary plants are too closely connected to describe the
production line for primary and secondary copper production as a whole.
Table 4-5: Overview of section 4.2
Process unit Emission guide Emission guide values for German BAT for this
values cleaned gas from process unit
secondary hoods
Smelting and converting Table 4-13 Table 4-15 Outokumpu flash smelting
(primary plant) furnace and Pierce-Smith
converter
Fire refining including anode Table 4-8 Table 4-15 Rotary anode furnace
casting (primary plant)
Smelting of sulphidic Table 4-13 Table 4-15 Electric furnace
materials (secondary plant)
Smelting of oxidic materials Table 4-9 Table 4-15 Blast furnace
(secondary plant)
Table 4-13 Table 4-15 Electric furnace
Converting (secondary plant) Table 4-13 Table 4-15 Pierce-Smith converter

Scrap converting (secondary Table 4-10 Table 4-15 Pierce-Smith converter
plant)
Fire refining including anode Table 4-11 Table 4-15 Contimelt plant
casting (secondary plant) Reverberatory anode furnace
Anode hearth shaft furnace
with drum furnace
Electrolytic refining - - -
(primary and secondary
plant)
Sulphuric acid plant Table 4-13 - -
Tin-lead alloy plant Table 4-14 - Dörschel furnace
Secondary hood system Table 4-15 - -
Fabrication of semi-finished - - Table 4-16
products from copper and
copper alloys
Waste water treatment plant Table 4-17 - -
Primary copper production

In Figure 4-1 the flow sheet of a primary copper production plant including the principle
process units is shown. All flows ending inside the dotted line are processed within the plant.
The flows crossing the dotted line are sold as a product or for further processing.
Slag
Slag
Sulphidic
concentrates Fire refining Electrolytic
Smelting Converting (including casting to anodes)
refining Cathode
copper
Spent Anode
electrolyte slime
Slag Dust
Figure 4-1: Primary copper production plant
In Table 4-6 the German BAT for these process units including techniques for waste heat
recovery and off-gas cleaning are summarised.
Table 4-6: German candidates BAT for the primary copper production
Production step Process technique Applied techniques to Applied techniques for minimisation
prevent emissions of energy supply and waste heat
recovery
Smelting and Outokumpu flash smelting Secondary hood system, hot Waste heat boiler, pre-heating of
converting furnace gas ESP, sulphuric acid plant process air
Pierce-Smith converter Secondary hood system, ESP, Remelting internal reverts and copper
sulphuric acid plant scrap, air to gas cooler for pre-heating
of boiler feed water
Fire refining Anode furnace (rotary type) Post-combustion chamber -
(including including casting wheel (during poling), fabric filter
anode casting)
Electrolytic Electrolytic plant Mist collector for exhaust air -
refining from regulator tanks
Secondary copper production

In Figure 4-2 the flow sheet of a secondary copper production plant including the principle
processes is shown. All flows ending inside the dotted line are processed within the plant. The
flows crossing the dotted line are sold as a product or for further processing.
Slag Blister copper

copper scrap
Slag
Flue
dust
Sulphur containing Smelting of sulphur

raw materials Converting
containing raw materials
Slag
Cathode
copper
Fire refining Electrolytic
(including casting to anodes) refining
Oxidic raw Smelting of oxidic
materials raw materials
Spent Anode
electrolyte slime
Metallic Scrap
materials converterting
Flue dust
Figure 4-2: Secondary copper production plant
In Table 4-7 the German BAT for these process units including techniques for waste heat
recovery and off-gas cleaning are summarised.
Table 4-7: German candidates BAT for the secondary copper production
Production step Process technique Applied techniques to Applied techniques for minimisation
prevent emissions of energy supply and waste heat
recovery
Smelting Blast furnace Secondary hood system, Waste heat boiler, tubular cooler
settling chamber (serves also
as post-combustion chamber),
fabric filter
Electric furnace Secondary hood system, -
sulphuric acid plant
Converting Pierce-Smith converter Secondary hood system, ESP, Waste heat boiler if premitted by the
sulphuric acid plant temperatur conditions
Scrap converter, Pierce- Secondary hood system Waste heat boiler if premitted by the
Smith type temperatur conditions, tubular cooler
Fire refining Contimelt process Secondary hood system, post- Pre-heating of feedstock, waste heat
(including anode combustion chamber, boiler, pre-heating of process air
casting) adsorption filter, fabric filter
Reverberatory anode Secondary hood system, Waste heat boiler
furnace (hearth type) fabric filter
Combination of anode Secondary hood system, post- Pre-heating of process air
hearth shaft furnace and combustion chamber,
drum furnace adsorption filter, fabric filter
Electrolytic Electrolytic plant Mist collector for exhaust air -
refining from regulator tanks
In the following sections, reference emission limits are proposed for these units and German
BAT operating within these limits are summarised.
4.2.1 Smelting and converting (primary plant)

The off-gases of the smelting and converting units are sent to a sulphuric acid plant, so the
proposed emission guide values are given in Table 4-13. Both units should be equipped with a
secondary hood system to prevent fugitive emissions. The maximum efficiency of the
converters can be reached by optimising the capacity and number of the installed converter
units. The proposed emission guide values for the off-gases from the secondary hood system
are given in Table 4-15.
German BAT for the smelting and converting (primary plant): The Outokumpu flash
smelting furnace and the Pierce-Smith Converter
The Outokumpu flash smelting furnace achieves a comparatively high throughput rate with
one furnace. Since it is operated with oxygen enriched air to burn as much sulphur contained
in the raw material as possible, it has a high sulphur oxide content in the off-gas, the fuel
consumption is reduced and a high matte grade can be achieved (Cu content: 65 wt-%). The
furnace off-gas is used for heat generation in a waste heat boiler and to pre-heat the process
air. Then it is dedusted by a hot gas ESP and sent to a sulphuric acid plant. Hoods are installed
to prevent fugitive emissions. The produced slag is sent to an electric slag cleaning furnace to
lower its copper content.
The blowing time of the Pierce-Smith converter is very short, since a high matte grade can
already be achieved in the Outokumpu flash smelting furnace. The reaction heat produced in
the converter is used to remelt internal reverts and copper scrap. Before the converter off-
gases are dedusted in a hot gas ESP, the heat is used by an air to gas cooler to pre-heat boiler
feed water. A secondary hood system is installed to prevent fugitive emissions.
4.2.2 Fire refining including anode casting (primary plant)

Furnaces for fire refining should be equipped with secondary hoods to prevent fugitive
emissions. Proposed emission guide values for the off-gas from these hoods can be found in
Table 4-15. The following emission guide values are proposed for the cleaned furnace off-
gases:
Table 4-8: Proposed emission guide values for the cleaned off-gases from fire refining
plants (primary plant)
Substance Unit Proposed emission guide values
SOx (as SO2) mg/m³ 500**)
NOx (as NO2) mg/m³ 200
-
Cl (as HCl) mg/m³ 30
Ctotal mg/m³ 50***)
Particulate matter*) mg/m³ 10
*)
**)
Mean value of whole refining cycle
***)
if cold input material is used
German BAT for the fire refining (primary plant): The rotary anode furnace
The anode furnace (rotary type) is German BAT for fire refining of the converter copper, since
the rotary type is well suited for input materials that are charged in liquid form. During poling,
the furnace off-gas is afterburned in a post-combustion chamber and sent to a fabric filter after
being cooled in a gas cooler to protect the filter media. To prevent fugitive emissions, a
secondary hood system is installed.
4.2.3 Smelting of sulphur containing raw materials (secondary plant)

If the SO2 content exceeds 800 mg/m3, the furnace off-gases should be sent to a sulphuric acid
plant. Therefore the emission guide values of the off-gases can be found in Table 4-13. The
secondary hoods installed to prevent fugitive emissions are part of a central system. The
proposed emission guide values of these ventilation gases are given in Table 4-15.
German BAT for the smelting of sulphur containing raw materials (secondary plant): The
electric furnace
Since no fuel has to be burned for heat supply, the electric furnace produces comparatively
small amounts of off-gas and, if the raw material contains sulphur, a high concentration of
sulphur dioxide is reached in the off-gas, so it can be fed to a sulphuric acid plant. It is a
comparatively small and well enclosed unit, because it can be operated with only small
amounts of return slags, but the raw material has to be pretreated and it puts higher demands
on the physical properties than the blast furnace. The furnace off-gas is treated in a sulphuric
acid plant and fugitive emissions are prevented by the secondary hood system.
4.2.4 Converting (secondary plant)

To reach the maximum efficiency, the capacity and number of the installed converters should
be optimised. The off-gases of the converting units have a relatively high SO2content,
therefore they should be sent to a sulphuric acid plant. The units should be equipped with a
secondary hood system to prevent fugitive emissions. The proposed emission guide values for
the converter off-gas are shown in Table 4-13 and the emission guide values for the off-gas
from the secondary hood system are given in Table 4-15.
German BAT for the converting (secondary plant): The Pierce-Smith converter
The Pierce-Smith converters are used for further processing of the copper rich phase of the
electric furnace. The off-gas is used for pre-heating of the waste heat boiler feed water or for
steam generation in a waste heat boiler, dedusted in a hot gas ESP and sent to a sulphuric acid
plant. The fugitive emissions are reduced by secondary hoods.
4.2.5 Smelting of oxidic raw materials (secondary plant)

The smelter to process oxidic raw materials should be equipped with secondary hoods to
avoid fugitive emissions. The proposed emission guide values of this system are given in
Table 4-15. Proposed emission guide values for the cleaned furnace off-gas are shown in
Table 4-9.
Table 4-9: Proposed emission guide values in the cleaned off-gases for the smelting of
oxidic raw materials (secondary plant)
SOx (as SO2) mg/m³ 800
PCDD/PCDF ng/m³ < 0.5
*)
Particulate matter mg/m³ < 10
*)
German BAT for the smelting of oxidic raw materials (secondary plant): The blast furnace
The advantage of the blast furnace in secondary copper production is its high flexibility with
regard to the raw material processed. At existing plants, additional oxygen is injected into the
top area of the furnace that improves post-combustion to reduce the emission of dioxines and
furanes (PCDD/PCDF). At new plants, a specific post-combustion is applied in order to
reduce these emissions. The furnace off-gases pass a settling chamber that also serve as a
post-combustion chamber before the heat is used for steam generation in a waste heat boiler.
Then the gases are cooled by a tubular cooler and mixed with cold off-gas before they are
cleaned together with the ventilation gases of the secondary hood system installed to prevent
fugitive emissions in a fabric filter.
4.2.6 Converting of scrap (secondary plant)

The capacity and number of installed converters should be optimised in order to reach the
maximum efficiency. A secondary hood system should be installed to prevent fugitive
emissions. The proposed emission guide values of the ventilation gases from secondary hoods
are given in Table 4-15. The proposed emission guide values for the furnace off-gas are
shown in Table 4-10.
Table 4-10: Proposed emission guide values in the cleaned off-gases from a scrap
converter (secondary plant)
*)
*)
German BAT for the converting of scrap (secondary plant): The Pierce-Smith converter
A converter of the Pierce-Smith type is German BAT in the secondary copper production to
process black copper from the blast furnace as well as further raw material such as alloy
scraps and shredder material by using the Knudsen process. The off-gas is cleaned in a fabric
filter and secondary hoods are installed to reduce fugitive emissions.
4.2.7 Fire refining (secondary plant)

For fire refining, the emission guide values shown in Table 4-11 are proposed. The proposed
emission guide values for the off-gas from the secondary hood system that should be installed
to prevent fugitive emissions are given in Table 4-15.
Table 4-11: Proposed emission guide values for the cleaned off-gases for the fire refining
(secondary plant)
CO mg/m³ 500
*)
*)
German BAT for the fire refining (secondary plant): The Contimelt process
The Contimelt process is used for continuous melting and fire refining of the converter copper
from the electric furnace path and from the scrap converter. It comprises an anode shaft
furnace and a subsequent poling furnace, from which the copper is cast into anodes on a
casting wheel. The process is energy-saving, because the copper is melted and refined
continuously. An integrated concept for the utilisation of heat has been implemented in the
Contimelt plant. The hot off-gas from the hearth furnace travels in counterflow to the
feedstock materials so that its energy content is utilised to pre-heat the latter and save fuel.
After the anode shaft furnace off-gas has been combined with the hot off-gas from
downstream poling and casting furnace, the residual heat content is used for heat steam
generation in a waste heat boiler and to pre-heat the burner air. Then carbon containing lime is
injected into the off-gas (140,000 Nm3/h) to adsorb organic constituents before it is cleaned by
a fabric filter. To reduce the fugitive emissions, the furnaces are equipped with secondary
hoods.
German BAT for the fire refining (secondary plant): The reverberatory anode furnace
The reverberatory anode furnace (hearth type) is used for fire refining of converter copper and
additional copper scrap, since it is better suited for the melting of solid scrap than the rotary
type. A secondary hood system is installed to prevent fugitive emissions.
German BAT for the fire refining (secondary plant): The Anode hearth shaft furnace and
the drum furnace
In the anode hearth shaft furnace black copper is processed together with additional raw
copper material. It is an open-hearth furnace with a shaft stacked up. Oxygen enrichment of
the burner air is possible. The superheated melt is transferred to the refining furnace which is
a rotary drum furnace where reduction is applied by blowing in natural gas. The off-gases of
both furnaces are afterburned in post-combustion chambers. The off-gas from the refining
furnace is then used to pre-heat the burner air, before the gases of both furnaces are cooled in
a quench cooler. Afterwards they are treated in a gas cleaning plant that consists mainly of an
adsorption filter plant and a fabric filter. To avoid fugitive emissions, all holes at both
furnaces are equipped with hoods or enclosures.
4.2.8 Electrolytic refining (primary and secondary plant)

Electrolytic refining should be carried out in an electrolytic plant, whereby the ground should
be protected against acidic leakage. Therefore appropriate materials should be used (e.g. lead).
Storage tanks should be bunded or double wall tanks should be used. Bund capacities should
always have sufficient volume for the maximum storage. Any leakage from the plant as well
as scrubbing water from extraction systems should be fed back to the process.
The electrolyte should be conditioned in an appropriate way, e.g. when the copper content in
the electrolyte is reduced electrochemically, the copper content in the last process step with
the lowest copper content should be monitored permanently, and the electricity supply of the
process should be cut down automatically if the concentration of copper is less than 1.5 g/l.
4.2.9 Auxiliary plants

In the following section, facilities for further treatment of by-products and cleaning facilities
for waste water and off-gases are described.
4.2.9.1 Fabric filters

All furnace off-gases and off-gases from secondary hoods that do not pass the sulphuric acid
plant are cleaned in fabric filters. The proposed emission guide values for the dust content in
the filtered gas is given in the respective sections. In Table 4-12, the emission guide values for
the main constituents in dust are given. They are proposed for all fabric filters, since the
differences between single measurements at the same filter are more significant than the
differences of fabric filters cleaning the off-gases of different processes.
Table 4-12: Proposed emission guide values for the off-gases after treatment in a fabric
filter
Class I (TA-Luft)
Cd mg/m³ 0.2
Hg mg/m³ 0.2
Tl mg/m³ 0.2
Sum class I (TA-Luft) mg/m³ 0.2
Class II (TA-Luft)
As mg/m³ 1
Ni mg/m³ 1
Co mg/m³ 1
Se mg/m³ 1
Te mg/m³ 1
Sum class II (TA-Luft) mg/m³ 1
Class III (TA-Luft)
Sb mg/m³ 5
Pb mg/m³ 5
Cr mg/m³ 5
Cu mg/m³ 5
Sn mg/m³ 5
Sum class III (TA-Luft) mg/m³ 5
4.2.9.2 Sulphuric acid plant (double absorption contact plant)

As mentioned regarding process units above, some off-gas streams should be directed to the
sulphuric acid plant for further treatment. The sulphuric acid plant should have a conversion
rate higher than 99.6 %. The ground at the plant site as well as at the loading station for the
sulphuric acid should be protected in an appropriate way against acid leakages. Storage tanks
should be bunded or double wall tanks should be used. Bund capacities should always have
sufficient volume for the maximum storage. The proposed emission guide values for the off-
gas from a sulphuric acid plant are given in Table 4-13.
Table 4-13: Proposed emission guide values for the cleaned off-gases from a sulphuric
acid plant
SO3 mg/m³ 120
-
Cl (as HCl) mg/m³ 10
-
F (as HF) mg/m³ 4.5
Class I (TA-Luft)
Cd mg/m³ 0.2
Hg mg/m³ 0.2
Tl mg/m³ 0.2
Sum class I (TA-Luft) mg/m³ 0.2
Class II (TA-Luft)
As mg/m³ 0.5
Se mg/m³ 0.5
Sum class II (TA-Luft) mg/m³ 0.5
Class III (TA-Luft)
Sb mg/m³ 1
Pb mg/m³ 1
Cu mg/m³ 1
Sum class III (TA-Luft) mg/m³ 1
PCDD/PCDF ng ITE/m³ < 0.5
4.2.9.3 Tin-lead alloy plant

Collected flue dust from secondary copper production is processed in a tin-lead alloy plant.
Proposed emission guide values for this kind of plant can be seen in Table 4-14.
Table 4-14: Proposed emission guide values for the cleaned off-gases from a tin-lead
alloy plant
*)
*)
German BAT for TLA plants: The Dörschel furnace

Flue dusts with a high content of tin, lead and/or zinc are fed to a Dörschel furnace which is
heated by an oil burner. The zinc is transferred to the flue dust as zinc oxide and is collected
in fabric filters. The remaining phase consists mainly of tin and lead.
4.2.9.4 Secondary hood system

All furnaces should be equipped with a secondary hood system in order to prevent fugitive
emissions. The proposed emission guide values for off-gases from these systems are shown in
Table 4-15.
Table 4-15: Proposed emission guide values for the cleaned off-gases from secondary
hood systems
*)
*)
4.2.10 Fabrication of semi-finished products from copper and copper alloys

In Table 4-16 the German BAT for melting and casting in the fabrication of semi-finished
products from copper and copper alloys is given.
Table 4-16: German BAT for melting and casting in the fabrication of semi-finished
products
Equipment Feed Abatement
Shaft furnace (Asarco type) Scrap & cathodes Afterburner & fabric filter.
Cathodes Fabric filter.
Electric furnace Cathodes, Fabric filter.
Cathodes, scrap, alloy scrap, master Cyclones (spark arresting), fabric
alloys, alloy metals filter.
Rotary furnace Scrap, cathodes Fabric filter.
4.2.10.1 Waste water treatment plant

In the following Table, proposed emission guide values for pollutants in discharged waste
waters from both, primary and secondary plants, are given.
Table 4-17: Proposed emission guide values for pollutants in discharged waste waters
(primary and secondary plant)
Substance Cu Pb As Ni Cd Zn
Proposed
emission guide 0.5 0.5 0.1 0.5 0.2 1
values[mg/l]
368 References
5 References
[1] 1. Allgemeine Verwaltungsvorschrift zum Bundesimmissionsschutzgesetz (Technische Anleitung zur

Reinhaltung der Luft – TA Luft) vom 27. Februar 1986, in: GMBl, p. 95, 1986
[2] 2. Allgemeine Verwaltungsvorschrift zum Abfallgesetz (TA Abfall, Teil 1: Technische Anleitung zur
Lagerung, chemisch/physikalischen und biologische Behandlung und Verbrennung von besonders
überwachungsbedürftigen Abfällen) vom 12. März, in: GMBl, p. 169, 1990
[3] 3. Allgemeine Verwaltungsvorschrift zum Abfallgesetz (TA Siedlungsabfall, Technische Anleitung zur
Verwertung, Behandlung und sonstigen Entsorgung von Siedlungsabfällen) Bekanntmachung des
Bundesumweltministeriums vom 14. Mai 1993, in: BAnz Nr. 99a vom 29. Mai 1993
[4] Allgemeine Verwaltungsvorschrift über genehmigungsbedürftige Anlagen nach § 16 der
Gewerbeordnung (TA Lärm: Technische Anleitung zum Schutz gegen Lärm, Beilage), in: BAnz Nr. 137
vom 26. Juli 1968, as at 1994
[5] Arpaci, E.; Vendura, T.: Recycling von Kupferwerkstoffen - Klassische und neue
Wiedergewinnungsverfahren, Metall 47, Heft 4, S. 340 - 345, April 1993
[6] Basel Convention on the Control of Transboundary Movements of Hazardous Waste and their Disposal,
published in Official Journal of the European Community, 16. February 1993
[7] Benz; Birle; Günther; Ulbrich: Umweltschutzanforderungen in der Metallindustrie, 3rd edition, Verband
Deutscher Maschinen- und Anlagenbau e.V., Frankfurt/M., (1995)
[8] Biswas, A.K.; Davenport, W.G.: Extractive Metallurgy of Copper, third edition, Pergamon Press, 1994
[9] Bundesamt für Wirtschaft: Erhebungsergebnisse der NE-Metallfachstatistik, Berichtsjahr 1995, Teil II,
Eschborn (Germany)
[10] Bundesamt für Wirtschaft: Erhebungsergebnisse der NE-Metallfachstatistik, Berichtsjahr 1996, Teil I,
Eschborn (Germany)
[11] Bundesimmissionsschutzgesetz (BimSchG) mit Durchführungsverordnungen sowie TA Luft und TA
Lärm, 6. Auflage, Deutscher Fachschriftenverlag, Wiesbaden, 1988
[12] Bundesminister für Umwelt, Naturschutz und Reaktorsicherheit und Länderarbeitsgemeinschaft Wasser
(eds.): Mindestanforderungen an das Einleiten von Abwasser in Gewässer (§ 7a WHG) Nichteisen-
metallherstellung - Hinweise und Erläuterungen zu Anhang 39 der Rahmen-Abwasser VwV,
Bundesanzeiger Verlag, Köln, 1993
[13] Burgert, P.: Dezincing galvanized-steel scrap, in: New Steel, 2/1997, p.62-63
[14] Bußmann H.; Schulz, D.: Verbesserung der Nachverbrennung beim Schachtofen mit heißer Gicht durch
Sauerstoffeinsatz, Erzmetall 44, Nr. 12, S. 600 - 603, 1991
[15] Caspari, R.: Die Verwendung der Mansfelder Kupferschlacke, Erzmetall 49, Nr. 1, S. 50 - 56, 1996
[16] Council of European Communities (CEC) (1975): Council Directive on Waste (75/464/EEC), Official
Journal L194/39, 25 July 1975
[17] Council of European Communities (CEC) (1991a): Amendment to Council Directive on Waste
(75/464/EEC), Official Journal L78/32, 26 March 1991
[18] Council of European Communities (CEC) (1991c): Council Directive amending Council Directive
(75/464/EEC) on Waste (91/689/EEC), Official Journal L78/32, 26 March 1991
[19] Davids, P.; Lange, M.: Die TA Luft '86 - Technischer Kommentar, VDI Verlag, Düsseldorf, 1986
[20] Deutsches Kupfer-Institut (ed.): Sachbilanz einer Ökobilanz der Kupfererzeugung und -verarbeitung,
DKI-Sonderdruck, Düsseldorf, 1995
[21] DIN EN 1948: Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von
PCDD/PCDF
References 369
[22] Dobner, R.F.: Bleed-off treatment at HK's secondary copper electrorefinery, EPD Congress 1997, p.
413 - 425, held at the Annual Meeting of The Minerals, Metals & Materials Society, February 9 - 13,
Florida, 1997
[23] Dobner, R.F.; Schwill, M.: Kupferraffination - Erweiterung und Modernisierung einer konventionellen
Elektrolyse, Erzmetall 48, Nr. 4, S. 272 - 276, 1995
[24] European Commission, DG XI (Ed.): Study on technical and economic aspects of measures to reduce
(on the basis of BAT) the pollution of water and other environmental areas from the non-ferrous metal
industry, Report Nr. CO 3400/1, September 1993
[25] Fabian, H.: Copper in Ullmann´s Encyclopedia of Industrial Chemistry, Vol. A 7, VCH
Verlagsgesellschaft, pp. 471 - 523, 1986
[26] Flemming, H.-C.: Kupfer und Umwelt, Metall 47, Heft 11, S. 1020 - 1027, November 1993
[27] GDMB Gesellschaft Deuscher Metallhütten- und Bergleute e.V. (eds.): Abfallstoffe in der Nichteisen-
Metallurgie - Wiederverwertung oder Deponie?, VCH Verlagsgesellschaft, Weinheim, 1986
[28] Gernerth - Mautner Markhof, S.: Verminderung der Emissionen an Staub, Schwermetallen und Arsen in
der Rohhütte Werk Ost, Abschlußbericht eines Forschungsvorhabens im Rahmen des Programs
Investitionen zur Verminderung von Umweltbelastungen, Bundesminister für Umwelt, Naturschutz und
Reaktorsicherheit, Luftreinhaltung, Nr.1131, Hamburg, 1997
[29] Gesetz über Abgaben für das Einleiten von Abwasser in Gewässer (Abwasserabgabengesetz - AbwAG)
in der Fassung der Bekanntmachung vom 3. November 1994, in: BGBl I, p. 3370, (1994)
[30] Gesetz zur Förderung der Kreislaufwirtschaft und Sicherung der umweltverträglichen Beseitigung von
Abfällen (Kreislaufwirtschafts- und Abfallgesetz – KrW-/AbfG) vom 27. September 1994, in: Bundes-
gesetzblatt BGBl I, Bonn, p. 2705, (1994)
[31] Gesetz zur Ordnung des Wasserhaushalts (Wasserhaushaltsgesetz - WHG) vom 27. Juli 1957, in der
Neufassung vom 12. November 1996, in: Bundesgesetzblatt BGBl I, p.1696, Bundesanzeiger Verlag,
Köln
[32] Gesetz zur Vermeidung, Verwertung und Beseitigung von Abfällen vom 27.9.1994, in Bundesgesetzblatt
BGBl I, Bonn, p.2705 (1994)
[33] Graf, G.G.: Zinc in Ullmann´s Encyclopedia of Industrial Chemistry, Vol. A 28, VCH Verlagsgesell-
schaft, Weinheim, pp. 509 - 543, 1996
[34] Her Majesty´s Inspectorate of Pollution (ed.): Chief Inspector´s Guidance to Inspectors - Processes for
the Production of Copper and Copper Alloys, London, 1994
[35] Her Majesty´s Inspectorate of Pollution (ed.): Chief Inspector´s Guidance to Inspectors - Processes for
the Production of Zinc and Zinc Alloys, London, 1994
[36] Hoffmann, M.: Recovery of Zinc and Lead from Electric Arc Furnace Steel Dust, in: Congress
Proceedings R´97, Vol. 5, Geneva, Switzerland, 4-7 February, 1997
[37] Hüttenwerke Kayser AG, Company information, Lünen, 1998
[38] Isenrath, P.: Recycling von kupferhaltigen Materialien - Stand der Technik und Entwicklungen, Metall
47, Heft 2, S. 184 - 187, Februar 1993
[39] Jockel, W; Hartje, J.: Die Entwicklung der Schwermetallemissionen in der Bundesrepublik Deutschland
von 1985 bis 1995, unpublished research report, UBA no. 94-104 03 524, Berlin, 1995
[40] Kersten, L.; Kramer, U.; Velten, H.-J.: Einsatz der Elektroofentechnologie zur Verarbeitung NE-
metallhaltiger Sekundärmaterialien: Integrierter Umweltschutz, Metall 48, Nr. 4, S. 274 - 275, 1994
[41] Kola, R.; Tack, K.; Steil, H.-U.: Staubfreie Entladung von Sekundärstoffen für die NE-Metallerzeugung,
Abschlußbericht eines Forschungsvorhaben im Rahmen des Programs Investitionen zur Verminderung
von Umweltbelastungen, Bundesminister für Umwelt, Naturschutz und Reaktorsicherheit, Luftrein-
haltung, Nr.1104, März 1992
370 References
[42] Kopke, M.: Verminderung der Emissionen, insbesondere schwermetallhaltiger Stäube von Rohkupfer-
Anodenöfen, Altanlagensanierungsprogramm des Bundesministerium des Inneren, Nr. 1079, Hamburg,
1985
[43] Krol, W.; Steil, H.U.: Bestandsaufnahme internationaler Umweltschutz-Aktivitäten und deren
Auswirkungen auf die deutsche NE-Metallindustrie, Metall, 51 Jg., Nr.3 (1997)
[44] Krüger, J.: Energiebedarf für verschiedene Verfahren der NE-Metallurgie in: GDMB_Seminar Nr. 16,
Einsparung im Hüttenwesen, 1985
[45] Krüger, J.: Sachbilanz einer Ökobilanz der Kupfererzeugung und -verarbeitung in Metall, Vol. 4/5/6,
1995
[46] Länderarbeitsgemeinschaft Abfall (Ed.): LAGA – Informationsschrift Abfallarten, 4. durchgesehene
Auflage, Erich Schmitt Verlag, Berlin, (1992) (Abfallwirtschaft in Forschung und Praxis; Bd. 41)
[47 Länderarbeitsgemeinschaft Abfall (Ed.): Zuordnung LAGA – Abfallschlüssel zum Europäischen
Abfallkatalog und zu den OECD-Codes, Erich Schmitt Verlag, Berlin, (1996) (Abfallwirtschaft in
Forschung und Praxis; Bd. 93)
[48] Langner, E.: Recycling von Kupfer, in Recyclinghandbuch, Strategien - Technologien - Produkte,
Werner Nickel (ed.), VDI-Verlag, Düsseldorf, 1996
[49] Langner, E.: Technology of copper production - smelting and refining in the World of Metals: Copper,
Metallgesellschaft (eds) Frankfurt a. M., 1994
[50] Malorny, U.: Die Verordnungen zur Einführung des Europäischen Abfallkatalogs, zur Bestimmung von
besonders überwachungsbedürftige Abfälle und zur Bestimmung von überwachungsbedürftige Abfälle
zur Verwertung, in: Referatesammlung des 17. Abfallwirtschaftlichen Fachkolloquiums „Umsetzung und
Auswirkungen des Kreislaufwirtschaftsgesetzes in die Praxis“ am 25-26 February 1997, Saarbrücken
(1997)
[51] Meyer-Wulf, C.: Verminderung der Emissionen traditioneller Kupfer-Schachtöfen durch
Sauerstoffeindüsung und anderer Maßnahmen im Bereich der Gicht, Erzmetall 47, Nr. 11, S. 658 - 664,
1994
[52] Meyer-Wulf, C.; Nolte, A.: Recycling of Copper in the Framework of low Waste Cycle Management, 8th
International Symposium on Mineral Resources, Hannover, 21 - 23 October 1997
[53] Moulins, J. (ed.): Copper Smelting, Metallurgical Industry, p. 624 - 632
[54] Nolte, A.: Metallurgical Utilisation of Reusable Products from the Recycling Industry In a Secondary
Copper Smelter, EPD Congress 1997, p. 377 - 400, held at the Annual Meeting of The Minerals, Metals
& Materials Society, February 9 - 13, Florida, 1997
[55] Norddeutsche Affinerie AG, Company information, Hamburg, 1998
[56] Oslo and Paris Commission (ed.): Description of Best Available Techniques for the Primary Production
of Non-Ferrous Metals (Zinc, Copper, Lead and Nickel), 1996
[57] Pawlek, F.: Metallhüttenkunde Verlag Walter de Gruyter, Berlin, p.500 ff., 1983
[58] Rentz, O. et al.: Emission Control at Stationary Sources in the Federal Republic of Germany Volume I:
Sulphur oxide and nitrogen oxide emission control, 1996
[59] Rentz, O. et al.: Emission Control at Stationary Sources in the Federal Republic of Germany Volume II:
Heavy Metal emission control, 1996
[60] Rentz, O. et al.: Stoffstrommanagement in der Eisen- und Stahlindustrie: Konkretisierung des
Paragraphen 5 Abs.1 Nr. 3 BImSchG, Erich-Schmidt Verlag, Berlin, ISBN: 3-503-03980-5, 1996
[61] Rich, V.: The international lead trade, Woodhead Publishing Ltd., Cambridge England, 1994
[62] Schmidt-Tegge, J.; Wuttke, J.: The new German Recycling Management and Waste Act - a step towards
integrated waste management, R’97 Congress Proceedings, Geneva (Switzerland), February 4-7, 1997
[63] Steil, H.-U.: Andere Schwermetalle (Kapitel 6.3.1) in Nickel, W. (ed.): Recycling-Handbuch,
Strategien, Technologien, Produkte , VDI-Verlag, Düsseldorf, 1996
[64] Stelter, M.: Material Recycling in the Case of Copper, in: Proceedings of 1st Freiberger European
Symposium Resources for Tomorrow - Materials Recycling“, 2. - 5. December 1997
References 371
[65] Sutherland et al.: Lead in Ullmann´s Encyclopedia of Industrial Chemistry, Vol. A15, VCH
Verlagsgesellschaft, pp., 1990
[66] Traulsen, H.: Fabrication of Semi-Finished Products From Copper and Copper Alloys,
EUROMETAUX Copper Industry, 1998
[67] Traulsen, H.: Personal communication, MCT Metallurgical Consulting Traulsen GmbH, Reinbek 1998
[68] Übereinkommen zum Schutz des Rheins gegen chemische Verunreinigungen vom 3. Dezember 1976,
ratifiziert durch Gesetz vom 11. August 1978, in: BGBl II, p. 1053, (1976)
[69] Umweltbundesamt (ed.): Richtlinien zur Emissionsminderung in Nicht-Eisen-Metall-Industrien -
Ergebnisse der UN-ECE Task Force for the Developments of Guidelines for the Control of Emissions
from the Non-Ferrous Metallurgical Industries, Erich Schmidt Verlag Berlin, ISBN 0353 018972, 1980
[70] Umweltministerium Baden-Württemberg: Verordnung über das Einleiten von Abwasser in öffentliche
Abwasseranlagen (Indirekteinleiterverordnung) vom 12. Juli 1990, GBl. S. 258, (1990)
[71] United Nations Economic Chamber of Europe, Umweltbundesamt Wien (ed.): Status Report: Task
Force „By-Product Utilization from Stationary Installations“, Vienna (Austria), 1996
[72] Velten, H.J.: Einsatz integrierter Umwelttechnik zur Emissionsminderung in Kupferhütten, Vortrag an
der UTECH 1993, Berlin in Moderne Techniken einer umweltfreundlichen Metallindustrie
[73] Verein Deutscher Ingenieure (ed.): Elektrofilter - Prozeßgas- und Abgasreinigung, VDI-Richtlinie 3678,
Beuth-Verlag GmbH, Berlin, September 1998
[74] Verein Deutscher Ingenieure (ed.): Emissionsminderung Schwefelsäureanlagen, VDI-Richtlinie 2298,
Beuth-Verlag GmbH, Berlin, September 1984
[75] Verein Deutscher Ingenieure (ed.): Emissionsminderung Sekundärkupferhütten, VDI-Richtlinie 2102 (8.
Vorentwurf), Beuth-Verlag GmbH, Berlin, Januar 1998
[76] Verein Deutscher Ingenieure (ed.): Messen von Emissionen, VDI-Richtlinie 3499 (Entwurf), Beuth-
Verlag GmbH, Berlin
[77] Verein Deutscher Ingenieure (ed.): Messen von Partikeln, VDI- Richtlinie 2066, Beuth-Verlag GmbH,
Berlin
[78] Verein Deutscher Ingenieure (ed.): Messung gasförmiger Emissionen, VDI- Richtlinie 3481, Beuth-
Verlag GmbH, Berlin
[79] Verein Deutscher Ingenieure (ed.): Messung gasförmiger Emissionen, VDI-Richtlinie 2462, Beuth-
Verlag GmbH, Berlin
[80] Verein Deutscher Ingenieure (ed.): Planung von stichprobenartigen Emissionsmessungen an geführten
Quellen, VDI- Richtlinie 2448, Beuth-Verlag GmbH, Berlin
[81] Verein Deutscher Ingenieure (ed.): Stoffbestimmung an Partikeln, VDI- Richtlinie 2268, Beuth-Verlag
GmbH, Berlin
[82] Verein Deutscher Ingenieure (ed.): Umweltmeteorologie - Emissionen von Gasen, Gerüchen und
Stäuben aus diffusen Quellen - Lagerung, Umschlag und Transport von Schüttgütern, VDI-Richtlinie
3790, Beuth-Verlag GmbH, Berlin
[83] Verein Deutscher Ingenieure (ed.): VDI-Richtlinie 4301: Ferrous and non-ferrous metallurgical slag
for civil engineering and building construction use, Beuth-Verlag GmbH, Berlin, 1981
[84] Verordnung über Anforderungen an das Einleiten von Abwasser in Gewässer (Abwasserverordnung)
vom 21.März 1997, geändert durch die Verordnung vom 3.Juli 1998 (BGBL I, S.1795) und die zweite
Verordnung vom 22.12.1998 – Bundesgesetzblatt Jahrgang 1998, Teil I Nr.86, ausgegeben zu Bonn am
29.12.1998
[85] Wiegand, V.: Verminderung diffuser Schwermetall-Emissionen in einer Rösthütte durch prozeß- und
abscheidetechnische Maßnahmen sowie durch Verminderung unkontrollierter thermischer
Raumströmungen, Abschlußbericht eines Forschungsvorhaben im Rahmen des Programms Investitionen
zur Verminderung von Umweltbelastungen, Bundesminister für Umwelt, Naturschutz und
Reaktorsicherheit, Luftreinhaltung, Nr.1106, November 1993
372 References
[86] Winnacker, K.; Küchler, L.: Chemische Technologie, Metallurgie (Band 6); Carl Hanser Verlag,
München, 1986
[87] Wirtschaftsvereinigung Metalle e.V. (ed.): Metallstatistik 1995 - Bundesrepublik Deutschland,
Düsseldorf 1996
[88] Zierock, K.H.: Technical note on Best available technologies not entailing excessive costs for heavy
metal emissions from non-ferrous industrial plants, Final Report, ENVICON, Berlin, May 1991
References 373
374 Annex
6 Annex
6.1 Information on current legislation relevant to the copper production

industry
6.1.1 Introduction
Various regulations concerning environmental standards have to be complied with related to
the erection and operation of copper production plants, since the copper production industry is
a consumer of energy and a potential source of air and water pollution as well as solid wastes.
Consequently, the immediate environmental concerns are the usage of energy, control of air
pollution (particularly CO, SOx, NOx and heavy metals), solid waste disposal and recycling,
waste water emissions and - more recently with the increased amounts of recycled
contaminated scrap metals - also harmful organic emissions. Existing regulations lay down
standards for
- the use of raw materials,

- energy consumption and usage of waste heat,
- air quality,
- water quality,
- waste management and disposal of hazardous materials, and
- noise quality, vibration, smell.
Since this report deals only with the German copper production, the following sections give a
brief overview of the current German legislation for copper production plants. In addition, a
rough overview of important regulations on an international level is given. Legislation on a
European level is excluded.
6.1.2 Regulations on a German level17

Important regulations relevant for copper production plants in Germany are laid down in the
BImSchG (Federal Immission Control Act), the WHG (Federal Water Act) and the
KrW-/AbfG (Federal Recycling and Waste Management Act). Germany uses a segregated
media permitting system for different environmental media, but the final decision on an
application is reached by the assessment of environmental impacts on all media by the local
authorities. Also noise requirements are considered in the licensing procedure Germany aims
at favouring pollution prevention. The „precautionary principle“ has a legal status which
17
This section summarises information on the German legal framework. However, a complete discourse on all
the regulations is not intended in this study. The regulations may be found in corresponding laws, ordinances,
or other documents.
Annex 375
permits the settings of standards. Legal standards are not subject to any negotiation in the
licensing process in Germany.
In compliance with the federal structure of Germany, the implementation of environmental

laws and decrees is under the responsibility of the federal states (Bundesländer), which may
take into account local requirements and implement the administrative procedure differently.
For new plants and also for major changes of existing plants a permission procedure with
participation of the public has to be fulfilled. During the licensing procedure also an
environmental impact assessment may be required (c.f. Gesetz über die
Umweltverträglichkeitsprüfung (UVPG)).
Table 6-1 gives an overview of the German legal basis and regulations for environmental
protection in Germany alongside the production line. In the following, a selection of the most
important acts, regulations and requirements are presented.
Table 6-1: Legal basis and main regulations alongside the production line
Area Legal basis Regulations and ordinances
Authorisation Genehmigungsrecht Bundes-Immissionsschutzverordnungen, ...
Transport Verkehrsrecht - Gefahrgutverordnung Straße
- Gefahrgutverordnung Schiene
- Gefahrgutverordnung Binnenschifffahrt
Health and safety at work Chemikaliengesetz (ChemG) - Chemikalienverbotsordnung
- Gefahrstoffverordnung
Gewerbeordnung - TA Lärm
- Arbeitsschutzgesetz
- Arbeitsstättenverordung und -richtlinien
Emissions Bundes-Immissionsschutzgesetz - Bundes-Immissionsschutzverordnungen
(BImSchG) - Bundes-Immissionsschutzverwaltungsvorschriften
(TA Luft, TA Lärm)
Wasserhaushaltsgesetz (WHG) - Abwasserverordnung (AbwV)
- Indirekteinleiterverordnungen oder
Abwassergesetze der Länder
- Anlagenverordnungen der Länder
- Katalog wassergefährdender Stoffe
- Lagerung und Transport wassergefährdender
Stoffe (VAWS)
Waste Prevention and Kreislaufwirtschaftsgesetz TA Abfall
Treatment (KrW.-/AbfG) TA Siedlungsabfall
Environmental Öko-Audit
management ISO 14000
6.1.2.1 German regulations concerning the air quality

The basic law for air pollution control is the Federal Immission Control Act (Bundes-
Immissionsschutzgesetz BImSchG). It primarily aims towards the protection of the medium
air, but it also applies to the media water and soil in case pollution is transferred via the
medium air. The BImSchG is specified by 21 ordinances and the Technical Instructions on Air
376 Annex
Quality (TA Luft). Especially the TA Luft as a prescription for the authorities specifies in
more detail requirements to be met by installations subject to licensing.
Federal Immission Control Act (Bundes-Immissionsschutzgesetz, BImSchG)

The BImSchG is the legal instrument for monitoring air pollution. Immission as defined
within the law comprises air pollutants, and also noise, vibration, light, heat, radiation and
associated factors affecting humans as well as animals, plants or other things. This concept
already implements the idea of cross-media effects to a certain extent. The BImSchG requires
federal authorities to issue ordinances identifying the types of facilities, which are subject to
licensing, set licensing requirements for these facilities, and impose emission limit values and
technical control requirements for all facilities, whether licensed or not.
Especially article 5(1)3 BImSchG aims at the avoidance and minimisation of wastes and
residues. The paragraph emphasises the cross-media effects of industrial production. The
concept of "state of the art technology" defined in the BImSchG is similar to the one of BAT:
State of the art as used herein shall mean the state of development of advanced processes of
facilities or modes of operation which is deemed to indicate the practical suitability of a
particular technique for restricting emission levels. When determining the state of the art,
special consideration shall be given to comparable processes, facilities or modes of operation
that have been successfully proven in practical operation. (Article 3 paragraph 6 BImSchG)
In principle, "state of the art technology" is stated in terms of emission limits set by the
licensing authority, the choice of technology to comply with the emission limit levels is left to
industry. Necessary precautions against harmful effects on the environment are to be taken in
particular by using control measures corresponding to the state of the art. Depending on the
mass flow, some substances have to be measured continuously (eg. SOx, NOx, and
particulates).
Technical Instructions on Air Quality (TA Luft):

The Technical Instructions on Air Quality (TA Luft) [1] have been set up as general
administrative regulations in connection with the §48 BImSchG [cf. 19]. The TA Luft further
specifies the requirements to be met by installations subject to licensing if not specified in one
of the other regulations. Therefore, it prescribes limit values for virtually all air pollutants as
well as structural and operational requirements designed to limit diffuse emissions. It
establishes standards as well as assessment procedures for immissions (as suspended particles
in [mg/Nm³] and as dust deposition [g/(m² d)]) and emissions [1]. Existing melting plants had
to comply with the TA Luft (as at 1986) requirements by 1994. For the new federal states, the
requirements had to be met before 1996, and in special cases by 1999. Table 6-2 shows the
limits for main emission control requirements or, if specific regulations for non-ferrous metal
production plants exist, it gives the corresponding more specific requirements laid down in the
TA Luft, which are aimed at the avoidance and minimisation of air pollution.
Annex 377
The potentially emitted substances are split into 3 classes, whereby class I substances are the
most toxic and while Class III are the least harmful. The emission limit values contained in
the TA Luft represent the BAT for technical measures for reducing emissions (dating from
1986). These quality values were developed referring to scientific findings and research taking
into account toxicological, bioaccumulative and epidemiological aspects. The required
concentration limits are given in mass of emitted substances related to the volume of emitted
gas under standard conditions (0°C, 1013 mbar) after subtraction of the water vapour content
and for a prescribed measuring time and statistic evaluation.
Table 6-2: Emission control requirements laid down in the TA Luft
Emitted Class Substances Mass flow Concentration
substance threshold limit
(TA Luft section) [g/h] [mg/Nm³]
Dust containing waste dust containing waste gases are to be captured as far as possible and to be fed to a
gases (3.3.3.3.1 a)) gas cleaning system, if necessary to comply with further requirements.
Inorganic dust I (e.g. Cd, Hg, Tl) sum of substances 1 0.2
particles II (e.g. As, Co, Ni, Te, Se) -"- 5 1
(3.1.4) III (e.g. Sb, Pb, Cr, F, Cu, Mn, -"- 25 5
Pt, Pd, Rn, V, Sn)
I+II -"- 1
I+III, II+III -"- 5
Vaporous or I (e.g. AsH3) per substances > 10 1
gaseous inorganic II (e.g. HF, Cl2, H2S) -"- > 50 5
substances III (e.g. Cl-compounds as HCl) -"- > 300 30
(3.1.6) IV (e.g. SO2, NO + NO2 as -"- > 5.000 500
NO)
Organic substances I (e.g. Chlormethane) Classification > 100 20
(3.1.7) II (e.g. Chlorbenzene) according to > 2.000 100
III (e.g. Alkylalcohols) Annex E of TA Luft > 3.000 150
Carcinogens I (e.g. asbestos, benzo(a)pyren) ≥ 0.5 0.1
II (e.g. arsenic trioxide, dimethylsulfate) ≥5 1
III (e.g. Acrylonitrite, benzene) ≥ 25 5
Carbon monoxide should be utilised or burned as far as possible.
(3.3.3.3.1)
If inorganic dust particles of several classes are present, the mass concentration in the emitted
gas should not exceed a total of 1 mg/Nm3 for coinciding class I and II substances as well as a
total of 5 mg/Nm3 for coinciding class I and III or class II and III substances.
If organic substances in several classes are present, the mass concentration in the emitted gas
should not exceed a total of 0.15 g/Nm3 with a total mass flow of 3 kg/h or more.
Furthermore, for facilities producing non-ferrous unrefined metals, particle emissions in the
emitted gases at a mass flow of 0.2 kg/h and more should not exceed 20 mg/Nm3. Sulphur
378 Annex
dioxide and sulphur trioxide in the emitted gas should, indicated as sulphur dioxide, should
not exceed 0.80 g/Nm3 at a mass flow of 5 kg/h or more18. When using solid or liquid fuels, a
sulphur mass content of 1 %, which is given for solid fuels with a lower calorific value of
29.3 MJ/kg, should not be exceeded.
No daily mean value of the respective emitted substances should exceed the required emission
limits, 97 % of all half-hourly mean values should not exceed 6/5 of the required emission
limits, and all half-hourly mean values should not exceed the required emission limits by more
than twice.
Since the TA Luft stems from 1986, the local authorities demand stricter emission limit
values.
Ordinance on installations subject to licensing (4. BImSchV)

In addition to these emission limits for certain substances shown in Table 6-2, special
requirements for copper production plants are laid down in section IV of the Bundes-
Immissionsschutzgesetz (Verordnung über genehmigungsbedürftige Anlagen, 4. BImSchV)
[11] for:
- Roasting and sintering of copper ores,

- Production of copper crude metal, and
- Electrolytical production of copper.
Technical Instruction on Noise Abatement:

The Technical Instruction on Noise Abatement (TA Lärm) [4] sets the limits for noise
emissions from the operation of a facility permitted in various areas. Permission for the
construction, operation or altering of a facility is granted only if the emission limits allowed
for a specific area are not exceeded and if state-of-the-art noise protection measures are
employed.
6.1.2.2 German regulations concerning the water quality

With respect to water management, each discharge, wherever it is located, has to comply with
the Federal Water Act (Wasserhaushaltsgesetz, WHG [31]). The WHG is the legal instrument
for water management, analogous to the BImschG for air pollution control. It applies to waste
water generated by various industrial processes, including the non-ferrous metal industry.
According to the WHG, the use of surface, coastal, and ground waters requires the approval of
18
Sulphuric acid plants are dealt with in a different section of the TA Luft. A conversion factor of at least
99.5 %/99.6 % for varying/constant gas conditions should be maintained. In addition, a sulphur trioxide limit
value in the off-gas of 60 mg/Nm³ for constant gas conditions resp. 120 mg/Nm³ in all other cases should not
be exceeded [1].
Annex 379
the competent authority. Water protection legislation in Germany is implemented by the

Ordinance on Waste Water (Abwasserverordnung, AbwV) Besides the minimum require-
ments concerning waste water treatment (c.f. Table 6-3), requirements concerning techniques
of analysis and measurement as well as limits for the content of specific substances are laid
down in the Annexes of the AbwV for different industries. The production of copper as part of
the non-ferrous metal industry is dealt with in Annex 39 of this regulation [84]. In addition,
the Federal Ministry of Environment has published explanations and comments on this Annex
[12]. Depending on the local conditions, more stringent requirements can be established by
the authorities.19 Table 6-3 gives the main restrictions established in Annex 39 of the AbwV,
especially for copper production plants.
Table 6-3: Limit values for discharges into water for copper production plants
Limit value**) Load limit value***)
[mg/l] [g/t tonne produced]
Cadmium 0.2 3*)
Mercury 0.05 1*)
Zinc 1 30*)
Lead 0.5 15*)
Copper 0.5 10*)
Arsenic 0.1 2*)
Nickel 0.5 15*)
Thallium 1 -
Chromium, total 0.5 10*)
Chromium VI****) 0.1 -
Cobalt 1 -
Silver 0.1 -
Tin 2 -
****)
Cyanide (freely available) 0.1 -
Sulphide (dissolved) 1 -
AOX 1 -
Fish toxicity as thinning factor Gf 4 -
COD - 1,500
Iron - 100
*)
Only valid for plants with a daily production capacity of more than 10 tons.
**)
Qualified random sample or 2 hours composite sample; three from four samples have to comply with the
limit and no value more than 100% exceeding the limit value
***)
The load limit is calculated with the permitted production capacity and the limit values given by
permission
****)
This limit value is valid for the location where the waste water arises (c.f. [84]) .
Source: Annex 39, Abwasserverordnung [12]
19
Each of the 16 Federal states has its own legislation which both the Federal Law and adds to it.
380 Annex
The required load values shall be production-specific loads in relation to the production
capacity on which the water discharge licence is based. It shall be determined by the 2 hours
composite sample or the qualified random sample. The qualified random sample shall refer to
a composite sample of at least five random samples taken over a maximum period of two
hours at intervals of no less than two minutes, and blended. A composite sample shall refer to
a sample which is taken continuously over a given period, or a sample consisting of several
samples taken either continuously or continuously over a given period and blended. A random
sample shall refer to a single sample taken from a waste water flow.
Waste water from cooling systems for the indirect cooling of industrial processes is excluded
from this regulation and subject to the provisions laid down in Annex 31, AbwV [12]. Table
6-4 gives the relevant requirements for discharges from cooling circuits in Annex 31 [84]. If
the stated values are not observed, approval for the discharge of waste water will be denied.
Table 6-4: Requirements for discharges from cooling circuits of industrial processes
Hazardous Substances Minimal Requirements*)
COD 40 mg/l
Phosphor compounds, given as P 3 mg/l
Zinc 4 mg/l
AOX 0.15 mg/l
Available residual chlorine 0.3 mg/l
Chromium compounds must not be contained
Mercury compounds must not be contained
Nitrite must not be contained
Metal organic Compounds (Metal-Carbon-Compound) must not be contained
*)
Qualified random sample or 2 hours composite sample
Source: Annex 31, Abwasserverordnung [12] or [84]
The WHG is furthermore complemented by the waste water levy act (Abwasserabgaben-
gesetz: AbwAG) [29]. The tariffs are related to the mass and possible hazard of the discharged
waste water according to Table 6-5. For the discharge of sewage, that exceeds the mentioned
threshold values for concentrations or annual freights, the discharging party has to pay a fee
related to the given units of measurement.20
20
Currently a levy of 70 DM per unit of hazards has to be paid
Annex 381
Table 6-5: Thresholds according to the waste water levy act

Hazardous Substances Units of measurement Threshold values
(relating to a unit of
hazard)
Concentrations Annual freights
Oxydizable substances (given as COD) 50 kg Oxygen 20 mg/l 250 kg
Phosphor 3 kg 0.1 mg/l 15 kg
Nitrogen 25 kg 5 mg/l 125 kg
Organic Halogen compounds as AOX 2 kg Halogen, calculated 100 µg/l 10 kg
as Cl
Mercury & compounds. 20 g 1 µg/l 0.1 kg
Cadmium & compounds 100 g 5 µg/l 0.5 kg
Chromium & compounds 500 g 50 µg/l 2.5 kg
Nickel & compounds 500 g 50 µg/l 2.5 kg
Lead & compounds 500 g 50 µg/l 2.5 kg
Copper & compounds 1000 g 100 µg/l 5 kg
3
Fish toxicity 3,000 m discharges GF =2 (dilution factor for non-lethal
divided by GF quantity for fish from the discharge)
Source: Abwasserabgabengesetz [29]
6.1.2.3 German regulations concerning the waste management and disposal of

hazardous materials
Waste legislation in Germany is laid down in the Act on Waste Prevention and Treatment
(Gesetz zur Vermeidung, Verwertung und Beseitigung von Abfällen, GVVB [32]). It is
applied to the use and storage of waste, i.e. to substances to be disposed of by the processor or
to substances whose proper treatment is necessary to protect the environment. Additional
requirements refer to waste from particular installations.
Legislation laying down measures aiming towards “avoidance, utilisation and disposal” of
waste is set down in the Recycling and Waste Management Act (Kreislaufwirtschafts- und
Abfallgesetz, KrW-/AbfG [30]), which came into force in October 1996 and is the most
important part of the new GVVB. It broadens the entire national waste concept and sets new
priorities with regard to the avoidance of and the duty to utilise waste. The KrW-/AbfG also
codifies manufacturer’s product responsibility.
For administrational procedures, technical guidelines on waste (TA Abfall) [2] and on
municipal waste (TA Siedlungsabfall) [3] are of relevance. The TA Abfall regulates planning,
licensing, construction and operation of waste disposal facilities [62]. Facilities for treating
waste have to fulfil requirements regulated in special decrees, based on Art. 5 BImSchG.
A working group of the federal states on waste (Länderarbeitsgemeinschaft Abfall, LAGA)

issued a categorisation of waste types, comprising 589 types of waste, of which 333 have
382 Annex
priority for control [46] (LAGA-Abfallartenkatalog). This catalogue was valid till 12/31/1998
and has been replaced by the European waste catalogue (EWC) in the following [50]. To
facilitate the change from the LAGA catalogue to the EWC, the German LAGA worked out an
interim catalogue (LAGA-Umsteigekatalog) [47]. Following this categorisation, the following
types of waste may arise within the copper production industry (cf. [46, 47]):
- Slag from non-ferrous metal melting,

- Plant residues (runner breaks, ladle breaks, converter breaks, refractory breaks, etc.),
- Sludges from non-ferrous metallurgy,
- Filter dust.
6.1.2.4 International regulations (overview)21

In this section, a rough overview of important regulations on an international level effecting
the copper production industry is given. International regulations and agreements have been
worked out on different levels. Besides the European level, which is not further considered in
this chapter, the different international committees of the United Nations like UNEP,
UNCED, UNECE, WHO, IFCS have to be mentioned. In addition, the OECD is working in
the field of environmental protection. Important international regulations, effecting the
pollution of the different environmental media are e.g.:
Long Range Treaty on Air Pollution (LRTAP):

International efforts to reduce the adverse effects of the transboundary acidification on forests,
aquatic ecosystems, and human health, by way of internationally co-ordinated emission
reductions, were undertaken in the 1979 Convention on Long Range Transboundary Air
Pollution (LRTAP). After coming into force in 1983, the LRTAP Convention was augmented
by (1) the 1984 Protocol on long-term financing; (2) the 1985 Helsinki Protocol reducing
sulphur emissions or their transboundary fluxes by at least 30%; (3) the 1988 Sofia Protocol
on the freezing of the emission of nitrogen oxides; (4) the 1991 Geneva Protocol on the
control of the emission of volatile organic compounds; and (5) the 1994 Oslo Protocol on the
further reduction of the emission of sulphur dioxide.
Basel Conventions:
The Basel Conventions declare the responsibility of OECD states regarding the control of
transboundary movements of hazardous wastes and their disposal. It was adopted in March
1989 and entered into force in May 1992. In 1996, more than 100 countries plus the EC are
parties to the Convention. The conventions comprise Technical Guidelines for waste
management activities. In this guidelines materials are divided into substances with a ban for
21
This section summarises information on international regulations effecting the non-ferrous metal industry.
However, a complete discourse on all the regulations is not intended in this study. The regulations may be
found in corresponding laws, ordinances, or other documents. A more detailed summary can be found in [43]
Annex 383
export (list A) and substances which still can be exported to non-OECD countries. A decision
adopted by the parties in 1994 prohibits with immediate effect the export from OECD
countries of hazardous wastes destined for final disposal in non-OECD countries. The
decision also phased out similar exports destined for recycling or recovery operations before
banning them completely on 31 December 1997.
OECD-Council decision on Transfrontier Movements of Hazardous Wastes:

As a reaction of the "Basel Convention" of the United Nations, the council of the OECD
ratified the council decision C 88(90). A three-tiered system was proposed to delineate
controls to be applied to transfrontier movements: Wastes destined for recovery operations
included on the green list would move among OECD Member countries toward recovery
operations subject to all existing controls normally applied in commercial transactions. A
notification procedure would exist for wastes destined for recovery operations included in the
yellow list and wastes destined for recovery operations included in the amber list or red list
would be subject to stricter or more rigorous controls.
Protection of the aquatic environment:

There are several international activities concerning the protection of the aquatic environment.
The most important ones are the the Oslo Paris Commission (OSPARCOM) for the protection
of the maritime environment of the North Sea and the Northeast Atlantic and the Helsinki
commission of the countries bordering the East Sea (HELCOM) for the protection of their
maritime environment.
In addition, there exist several international agreements on the pollution prevention of the
main European seas (Nordseeschutzkonferenz), lakes (Bodensee) and rivers (e.g. Rhine
(IKSR), Elbe(IKSE), Donau (IKSD), Oder (IKSO)) [43]. For example, there are two
international agreements dating from 1978 concerning the pollution prevention of the River
Rhine referring to chemical contamination and chlorides [68].
Global Environment Monitoring System (WHO/UNEP)

UNEP and WHO operate the GEMS (Global Environment Monitoring System) environmental
pollution monitoring programmes for urban air quality (AIR), food, human exposure
assessment location (HEAL), and water. The objectives of GEMS as defined at its inception
are:
- to strengthen monitoring and assessment capabilities in the participating countries,
- to increase the validity and comparability of environmental data and information,
- top produce global/regional assessments in selected fields and compile environmental
information at a global level.

2560

Uploaded by

Copyright:

Available Formats

2560

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

2560

Uploaded by

Copyright:

Available Formats

Report on Best Available Techniques (BAT)

Deutsch-Französisches Institut für Umweltforschung (DFIU)

Karlsruhe, March 1999

On behalf of the German Federal Environmental Agency, Berlin (UBA)

1 GENERAL INFORMATION........................................................................................................................ 233

2 APPLIED PROCESS TECHNOLOGY AND ABATEMENT TECHNIQUES IN COPPER

3 PROCESS TECHNOLOGY, ABATEMENT TECHNIQUES AND PRESENT

4 GERMAN CANDIDATE BEST AVAILABLE TECHNIQUES (BAT) FOR INTEGRATED

5 REFERENCES ............................................................................................................................................... 368

The document is structured as follows:

Mr Albrecht, Landesamt für Umweltschutz des Landes Sachsen-Anhalt

1.1 Production and use of copper

Table 1-2: Industrial use of copper in Germany (1996)

Figure 1-1: Main fields of application of copper products in Germany

Figure 1-2: Average service life of copper materials in various applications

1.2 First indication of environmental concerns regarding the production of

1.2.1 Emissions into the atmosphere

1.2.2 Potential releases into water

- wet gas cleaning,

1.2.3 Solid materials generated

2 Applied process technology and abatement techniques in copper

2.1 Introduction and scope of the study

2.2 Basic description of copper production

2.2.1 Primary copper production

2.2.1.1 General process description

Inputs for primary copper production

Production units in primary copper producing plants

Figure 2-1: Primary copper production route

Table 2-1: Composition of matte and slag from smelting operation

Table 2-2: Technical data for different copper smelting processes

Table 2-4: Current copper smelting processes

Source: Osparcom [56]

Off-gas Gas cleaning

Figure 2-2: Pierce-Smith converter

Figure 2-3: Double absorption contact plant

Anode: Cuo → Cu2+dissolved + 2e- Eo = +0.34 V

Anode: H2O → ½ O2 + 2H+ + 2e-

The potential sources of water pollution are summarised in Table 2-7.

2.2.2 Secondary copper production

2.2.2.1 General process description

Blast furnace Flue dust

Bronze, Converter Flue dust

Wire rod production Cathodes

Figure 2-5: Flowsheet for secondary copper production

Inputs for secondary copper production

- mainly metallic, oxidic and sulphidic raw materials,10

Production units in secondary copper producing plants11

Figure 2-6: Treatment of blast furnace off-gas (secondary copper production)

The Contimelt process, developed by Norddeutsche Affinerie and Union Minière, is an

2.2.2.2 Main outputs and environmental concerns of secondary copper producing

2.2.3 Further processing of copper cathodes

2.2.3.1 Fabrication of wire rod

Shaft Rolling mill Wire

Figure 2-7: Wire rod plant

Copper cathodes from

Mill Pickler Coiler

Figure 2-8: Basic concept of the CONTIROD process

2.2.3.2 Fabrication of semi-finished products from copper and copper alloys13

- Raw material processing,

Hot & cold working