(BAT) Reference Document for the Production of Chlor-alkali ...

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Scope Other reference documents which are of relevance for the sector covered in this document are the following: Reference document Subject Common Waste Water and Waste Gas Treatment/Management Systems in the Chemical Sector BREF (CWW) Economics and Cross-Media Effects (ECM) Common waste water and waste gas treatment/management systems Economics and cross-media effects of techniques Emissions from Storage (EFS) Storage and handling of materials Energy Efficiency (ENE) General aspects of energy efficiency Industrial Cooling Systems (ICS) Indirect cooling with water Large Combustion Plants (LCP) Combustion plants with a rated thermal input of 50 MW or more General Principles of Monitoring (MON) General aspects of emissions and consumption monitoring Waste Incineration (WI) Waste incineration Waste Treatments Industries (WT) Waste treatment In addition to covering the basic manufacturing activities, this document addresses the following substances, in Annex III of the Directive, which are associated with those activities and which could have an effect on emissions or pollution: Relating to air: 5. metals and their compounds (in particular mercury) 7. asbestos (suspended particulates, fibres) 8. chlorine and its compounds; 13. polychlorinated dibenzodioxins and polychlorinated dibenzofurans Relating to water: 1. organohalogen compounds and substances which may form such compounds in the aquatic environment 7. metals and their compounds (in particular mercury). Environmental and safety items not specifically related to the chlor-alkali sector are not covered in the document e.g. environmental aspects of cooling systems, emissions related to storage and handling of feedstock or special agents used as precipitants. The scope of the BREF does not include matters that only concern safety in the workplace or the safety of products because these matters are not covered by the Directive. They are discussed only where they affect matters within the scope of the Directive. WORKING DRAFT IN PROGRESS The high toxicity of chlorine is a major factor in the chlor-alkali industry, so the document does address: safety management procedures control of handling and loading and prevention of chlorine losses. xiv December 2011 TB/EIPPCB/CAK_Draft _1
1 GENERAL INFORMATION 1.1 Industrial and economical development of the chloralkali sector Chapter 1 In 1800, Cruickshank was the first to prepare chlorine electrochemically. The process was, however, of little significance until the development of a suitable generator and of synthetic graphite for anodes in 1892. These two developments made possible the electrolytic production of chlorine, the chlor-alkali process, on an industrial scale. About the same time, both the diaphragm cell process (Griesheim cell, 1885) and the mercury cell process (Castner-Kellner cell, 1892) were introduced. The membrane cell process was developed much more recently (1970). Currently, 95% of world chlorine production is obtained by the chlor-alkali process. [Ullmann’s, 1996] Since 1970 graphite anodes have been largely superseded by activated titanium anodes in the diaphragm and mercury cell processes. The newer membrane cell process uses only activated titanium anodes. [Ullmann’s, 1996] Production of chlorine was very low in the 1800s and chlorine was only used for bleaching. In 1887, annual world production was 115 tonnes [Le Chlore, 1996]. Chlorine production since the 1940s has risen enormously, on the back of the burgeoning demand for plastics, notably PVC [J. Ind. Ecology, 1997] and polyurethanes. The production of chloroaromatics (e.g. chlorobenzene for phenol synthesis), propylene oxide (chlorohydrin process), solvents containing chlorinated hydrocarbons, and inorganic chlorine compounds are also important factors behind the increased use of chlorine after 1940. The chlor-alkali industry sector produces chlorine with its co-products sodium/potassium hydroxide (also called caustic soda/potash) and hydrogen by electrolysis of brine. In 2008, more than 500 companies produced chlorine at over 650 sites worldwide, with a total annual capacity of approximately 62.8 Mt. Figure 1.1 shows the share of installed production capacities per region in 2008. On a global scale, 2007 was a record growth year for the chlor-alkali industry which then experienced a dramatic contraction in 2008 and 2009 due to the economic crisis. In 2010, the global industry was again on a growth path. Relatively little new capacity is however expected in the United States, Europe and Japan. More attractive growth is anticipated in the less developed regions of the world. For example, China increased its capacity from 2004 to 2008 by approximately 50 % and was the largest producer and consumer of chlorine and caustic soda worldwide in 2010 [ 4, SRI Consulting 2008 ], [ 5, CMAI 2010 ]. WORKING DRAFT IN PROGRESS TB/EIPPCB/CAK_Draft_1 December 2011 1
Page 1 and 2: EUROPEAN COMMISSION JOINT RESEARCH
Page 3 and 4: PREFACE 1. Status of this document
Page 5 and 6: Reference Document on Best Availabl
Page 7 and 8: 3.4.7 Emissions of noise ..........
Page 9 and 10: 4.3.6.3.3 Chemical reduction ......
Page 11 and 12: List of Tables Table 2.1: Main char
Page 13 and 14: List of Figures Figure 1.1: Share p
Page 15: SCOPE WORKING DRAFT IN PROGRESS Sco
Page 19 and 20: Chlorine production in Mt/yr 12 11
Page 21 and 22: Chapter 1 Figure 1.4 shows the annu
Page 23 and 24: Share of total capacity in % 70 70%
Page 25 and 26: 1.4 Chlor-alkali products and their
Page 27 and 28: Total consumption: 9 801 kt Miscell
Page 29 and 30: 1.4.5 Consumption of hydrogen Chapt
Page 31 and 32: Chapter 1 and hazardous waste incin
Page 33 and 34: 2 APPLIED PROCESSES AND TECHNIQUES
Page 35 and 36: Chapter 2 WORKING DRAFT IN PROGRESS
Page 37 and 38: Chapter 2 The main characteristics
Page 39 and 40: 2.2 The mercury cell technique proc
Page 41 and 42: Chapter 2 Characteristics of the ca
Page 43 and 44: 2.3 The diaphragm cell technique pr
Page 45 and 46: Source: [ 2, Le Chlore 2002 ] [USEP
Page 47 and 48: 2.4 The membrane cell technique pro
Page 49 and 50: Chapter 2 (carcinogenic) [ 76, Regu
Page 51 and 52: Chapter 2 The membranes used in the
Page 53 and 54: Table 2.2: Typical configurations o
Page 55 and 56: 2.5 Brine supply 2.5.1 Sources, qua
Page 57 and 58: Chapter 2 centrifuges before dispos
Page 59 and 60: Source: [ 29, Asahi Glass 1998 ] (p
Page 61 and 62: Impurity Source Upper limit of brin
Page 63 and 64: Chapter 2 No such dechlorination tr
Page 65 and 66: Chapter 2 The cooling water is gene
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Chapter 2 composition of the chlori
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2.6.11 Dealing with impurities 2.6.
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Chapter 2 amount of chlorine, and t
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2.6.12.2 Chemical reactions Chapter
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2.7 Caustic processing production,
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Chapter 2 2.8 Hydrogen processing p
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3 CURRENT PRESENT EMISSION AND CONS
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Chapter 3 Table 3.1: Overview of em
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3.3 Consumption levels of all cell
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3.3.3 Ancillary materials Ancillary
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Further materials and/or further us
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Chapter 3 current) and the efficien
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Chapter 3 distance means a higher f
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3.3.4.3.6 Production of caustic pot
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Chapter 3 hydrogen at low pressure
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28 kg of hydrogen is produced {Thes
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Chapter 3 depleted brine is recircu
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Chapter 3 Table 3.10: Emissions of
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Chapter 3 When measuring chlorine i
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Page 107 and 108:
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Chapter 3 concentrations of organic
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Chapter 3 3.4.3 Emissions and waste
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Chapter 3 {Please TWG provide infor
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Chapter 3 in process and waste wate
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Chapter 3 produced per year has bee
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Chapter 3 of chlorine capacity. The
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Table 3.23: Mercury emissions from
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Mercury emissions in g Hg/t Cl capa
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Chapter 3 Table 3.24: Mercury emiss
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Chapter 3 KCl are higher than from
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Chapter 3 When concentrated solid c
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Chapter 3 Generally, storage of con
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Chapter 3 recycled brine systems si
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Process Maintenance To solid treatm
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3.5.9.5 Graphite and activated Acti
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Chapter 3 Table 3.31: Yearly waste
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Chapter 3 The fact that the differe
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Chapter 3 3.6 Emissions Emission an
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Reported asbestos concentrations ar
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Chapter 3 3.7 Emissions Emission an
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{A list of techniques used on full
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3.8.3 PCDDs/PCDFs, PCBs, PCNs and P
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Chapter 3 The ‘dioxin’ pattern
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Chapter 4 4 TECHNIQUES TO CONSIDER
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Heading within the sections Cross-m
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4.1 Mercury cell plants 4.1.1 Overv
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Chapter 4 plants at comparable capa
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Chapter 4 Table 4.2: Data from the
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Chapter 4 environment can be expect
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4. Plant size Chapter 4 An increase
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Table 4.6: Comparison of reported c
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Chapter 4 Generally, conversion cos
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4.1.3 Decommissioning 4.1.3.1 Decom
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3. Emptying of the cells and handli
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Chapter 4 Table 4.7: Overview of co
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Table 4.8: Techniques for monitorin
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Chapter 4 Table 4.10: Decommissioni
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4.2 Diaphragm cell plants 4.2.1 Aba
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Source: [ 146, Arkema 2009 ] Figure
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Chapter 4 diaphragms [ 31, Euro Chl
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Driving force for implementation Th
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Chapter 4 4.2.3 Conversion of asbes
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Chapter 4 directly from the cells.
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4.3 All Diaphragm and membrane cell
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Chapter 4 non-standardised) will be
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Chapter 4 removal of conductive com
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Chapter 4 Cross-media effects Plant
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Environmental performance and opera
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Example plants Dow, Stade (Germany)
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Chapter 4 current density resulting
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Chapter 4 modifications to auxiliar
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Table 4.14: Cost calculation for th
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Chapter 4 membrane lifetimes range
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Chapter 4 Cross-media effects Some
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Chapter 4 The drawback of using fer
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Chapter 4 evaporation unit integrat
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Chapter 4 Environmental performance
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Chapter 4 Technical description The
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Chapter 4 Table 4.17: Monitoring te
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Chapter 4 Environmental performance
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Environmental performance and opera
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Chapter 4 Prevention of chlorine re
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Chapter 4 Good pipework design to m
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Chapter 4 was the solution at that
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differential pressure at inlet and
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Chapter 4 chlorine scrubber, immedi
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Chapter 4 Achieved environmental be
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{Please TWG provide more informatio
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environmental legislation; generati
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Chapter 4 Table 4.21: Examples of o
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Chapter 4 Driving force for impleme
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4.3.6.3.4 Catalytic decomposition r
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Chapter 4 In both cases, the spent
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Chapter 4 Example plants Thermal de
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Chapter 4 migration of hydroxide io
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eduction of chlorate emissions; red
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Example plants Solvin in Antwerp-Li
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eduction of costs related to equipm
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Chapter 4 Off-site reconcentration
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Chapter 4 b) closing of doors and w
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4.4 Membrane cell plants 4.4.1 High
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4.5.3 Containment Chapter 4 Descrip
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Chapter 4 Sections 4.5.4.2 and 4.5.
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Chapter 4 At this site, mercury con
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Chapter 4 However, the soil washing
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5 BEST AVAILABLE TECHNIQUES Scope
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General considerations In these BAT
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5.2 Decommissioning of mercury cell
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5.3 Environmental management system
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Chapter 5 The BAT-associated enviro
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Chapter 5 6. In order to reduce ene
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5.6 Monitoring of emissions Chapter
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[This BAT conclusion is based on in
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5.9 Generation of waste Chapter 5 1
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5.11 Site remediation Chapter 5 20.
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Chapter 5 inorganic chloramines, di
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6 EMERGING TECHNIQUES 6.1 Introduct
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Chapter 6 cooperation with the Japa
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Chapter 6 In December 1998 a test w
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6.3 Use of fuel cells in chlor-alka
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Chapter 6 hydrogen that is burnt to
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Chapter 7 7 CONCLUDING REMARKS AND
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REFERENCES References [1] Ullmann's
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References [63] Euro Chlor, Euro Ch
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References [112] Santorelli et al.,
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References [161] Germany, 'Verordnu
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[212] Florkiewicz, Long life diaphr
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References [259] Rappe et al., 'Lev
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GLOSSARY OF TERMS AND ABBREVIATIONS
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V. Units · VI. Chemical elements T
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VIII. Acronyms and definitions AC A
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EOX Extractable Organically-bound H
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Glossary Technique Ensemble of both
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ANNEX Annex {The CAK plant capaciti
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Euro Chlor No. Country code Company
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