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

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Preface 4. Information sources and the derivation of BAT This document is based on information collected from a number of sources, in particular through the TWG that was established specifically for this task in order to participate in the exchange of information under Article 13 of the Directive. The information has been collated and assessed by the European IPPC Bureau (of the Commission's Joint Research Centre) who led the work on determining BAT, guided by the principles of technical expertise, transparency and neutrality. The work of the TWG and all other contributors is gratefully acknowledged. The BAT conclusions have been established through an iterative process involving the following steps: identification of the key environmental issues for the sector; examination of the techniques most relevant to address these key issues; identification of the best environmental performance levels, on the basis of the available data in the European Union and worldwide; examination of the conditions under which these environmental performance levels were achieved, such as costs, cross-media effects, and the main driving forces involved in the implementation of the techniques; selection of the best available techniques (BAT), their associated emission levels (and other environmental performance levels) and the associated monitoring for this sector according to Article 3(10) and Annex III to the Directive. Expert judgement by the European IPPC Bureau and the TWG has played a key role in each of these steps and in the way in which the information is presented here. Where available, economic data have been given together with the descriptions of the techniques presented in Chapter 4. These data give a rough indication of the magnitude of the costs and benefits. However, the actual costs and benefits of applying a technique may depend strongly on the specific situation of the installation concerned, which cannot be evaluated fully in this document. In the absence of data concerning costs, conclusions on the economic viability of techniques are drawn from observations on existing installations. 5. Review of BAT reference documents (BREFs) BAT is a dynamic concept and so the review of BREFs is a continuing process. For example, new measures and techniques may emerge, science and technologies are continuously developing and new or emerging processes are being successfully introduced into the industries. In order to reflect such changes and their consequences for BAT, this document will be periodically reviewed and, if necessary, updated accordingly. 6. Contact information All comments and suggestions should be made to the European IPPC Bureau at the Institute for Prospective Technological Studies at the following address: WORKING DRAFT IN PROGRESS European Commission Institute for Prospective Technological Studies European IPPC Bureau Edificio Expo c/ Inca Garcilaso, 3 E-41092 Seville, Spain Telephone: +34 95 4488 284 Fax: +34 95 4488 426 E-mail: JRC-IPTS-EIPPCB@ec.europa.eu Internet: http://eippcb.jrc.ec.europa.eu ii December 2011 TB/EIPPCB/CAK_Draft_1
Reference Document on Best Available Techniques for the Production of Chlor-alkali PREFACE....................................................................................................................................................I SCOPE ...................................................................................................................................................XIII 1 GENERAL INFORMATION........................................................................................................... 1 1.1 Industrial and economical development of the chlor-alkali sector............................................. 1 1.2 Industry size and geographic distribution of chlor-alkali production sites in EU-27 and EFTA countries Europe.............................................................................................................. 4 1.3 Techniquesologies in use ........................................................................................................... 6 1.4 Chlor-alkali products and their use ............................................................................................ 9 1.4.1 Consumption of chlorine.................................................................................................. 9 1.4.2 Consumption of sodium hydroxide................................................................................ 10 1.4.3 Chlorine/sodium hydroxide: a delicate balance ............................................................. 11 1.4.4 Consumption of potassium hydroxide............................................................................ 12 1.4.5 Consumption of hydrogen.............................................................................................. 13 1.5 Environmental relevance of the chlor-alkali industry .............................................................. 14 2 APPLIED PROCESSES AND TECHNIQUES ............................................................................ 17 2.1 Overview.................................................................................................................................. 17 2.2 The mercury cell technique process ......................................................................................... 23 2.2.1 General description ........................................................................................................ 23 2.2.2 The cell and the decomposer mercury cathode electrolyser........................................... 24 2.2.3 Decomposition of the amalgam ..................................................................................... 26 2.3 The diaphragm cell technique process ..................................................................................... 27 2.3.1 General description ........................................................................................................ 27 2.3.2 The cell .......................................................................................................................... 28 2.3.3 Activated cathodes ......................................................................................................... 29 2.3.4 Diaphragm without asbestos .......................................................................................... 29 2.4 The membrane cell technique process...................................................................................... 31 2.4.1 General description ........................................................................................................ 31 2.4.2 The cell .......................................................................................................................... 33 2.4.3 Monopolar and bipolar electrolysers.............................................................................. 35 2.5 Brine supply ............................................................................................................................. 39 2.5.1 Sources, qualities and storage of salt Salt unloading and storage .................................. 39 2.5.2 Brine preparation............................................................................................................ 40 2.5.3 Brine purification ........................................................................................................... 40 2.5.3.1 General description ................................................................................................ 40 2.5.3.2 Primary purification ............................................................................................... 40 2.5.3.3 Secondary purification: membrane cell technique circuit ...................................... 41 2.5.3.4 Control of nitrogen compounds in the brine trichloride (NCl3) ............................. 46 2.5.4 Brine dechlorination and resaturation and dechlorination.............................................. 46 2.5.5 Chlorate destruction: membrane cell technique ............................................................. 47 2.6 Chlorine processing production, storage and handling ............................................................ 48 2.6.1 General description ........................................................................................................ 48 2.6.2 Materials ........................................................................................................................ 48 2.6.3 Cooling........................................................................................................................... 48 2.6.4 Cleaning of wet chlorine ................................................................................................ 49 2.6.5 Drying ............................................................................................................................ 49 2.6.6 Cleaning of dry chlorine ................................................................................................ 49 2.6.7 Compression .................................................................................................................. 50 2.6.8 Liquefaction ................................................................................................................... 50 2.6.9 Handling and storage ..................................................................................................... 52 2.6.10 Vaporisation................................................................................................................... 52 2.6.11 Dealing with impurities.................................................................................................. 53 2.6.11.1 General description ................................................................................................ 53 2.6.11.2 Water...................................................................................................................... 53 2.6.11.3 Hydrogen................................................................................................................ 53 2.6.11.4 Nitrogen trichloride................................................................................................ 53 2.6.11.5 Bromine.................................................................................................................. 54 2.6.12 The chlorine absorption unit .......................................................................................... 55 WORKING DRAFT IN PROGRESS TB/EIPPCB/CAK_Draft_1 December 2011 iii
Page 1 and 2: EUROPEAN COMMISSION JOINT RESEARCH
Page 3: PREFACE 1. Status of this document
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 and 16: SCOPE WORKING DRAFT IN PROGRESS Sco
Page 17 and 18: 1 GENERAL INFORMATION 1.1 Industria
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
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2.5 Brine supply 2.5.1 Sources, qua
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Chapter 2 centrifuges before dispos
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Source: [ 29, Asahi Glass 1998 ] (p
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Impurity Source Upper limit of brin
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Chapter 2 No such dechlorination tr
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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.,
Page 323 and 324:
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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