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

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4.1.3 Decommissioning .........................................................................................................161 4.1.3.1 Decommissioning plan .........................................................................................161 4.1.3.2 Mercury-containing wastes...................................................................................170 4.2 Diaphragm cell plants .............................................................................................................171 4.2.1 Abatement of asbestos emissions and discharges.........................................................171 4.2.2 Asbestos-free diaphragms Application of non-asbestos diaphragm material ...............171 4.2.3 Conversion of asbestos diaphragm cell plants to membrane cell plants technology or to asbestos-free diaphragms..........................................................................................179 4.3 All Diaphragm and membrane cell plants ..............................................................................183 4.3.1 Environmental management systems ...........................................................................183 4.3.2 Techniques to reduce consumption of raw materials....................................................185 4.3.2.1 Salt........................................................................................................................185 4.3.2.1.1 Choice of salt type ........................................................................................185 4.3.2.1.2 Techniques to reduce consumption of salt....................................................186 4.3.2.1.3 Recycling of waste water from other production processes..........................186 4.3.2.2 Water ....................................................................................................................188 4.3.2.2.1 Overview.......................................................................................................188 4.3.2.2.2 Brine recirculation ........................................................................................188 4.3.2.2.3 Recycling of other process streams...............................................................189 4.3.2.2.4 Closed-circuit direct cooling of chlorine and hydrogen with water..............190 4.3.2.2.5 Concentration of brine filtration sludges ......................................................191 4.3.2.2.6 Use of waste water for solution mining ........................................................192 4.3.2.2.7 Miscellaneous techniques .............................................................................193 4.3.2.2.8 Combination of techniques to reduce the generation of waste water............193 4.3.2.3 Energy...................................................................................................................194 4.3.2.3.1 Overview.......................................................................................................194 4.3.2.3.2 High-performance bipolar membrane cells...................................................194 4.3.2.3.3 High-performance membranes......................................................................200 4.3.2.3.4 High-performance electrodes and coatings...................................................202 4.3.2.3.5 High-purity brine ..........................................................................................203 4.3.2.3.6 Iron(III) meso-tartrate as anti-caking agent...................................................204 4.3.2.3.7 Once-through brine system...........................................................................206 4.3.2.3.8 Plate evaporators...........................................................................................208 4.3.2.3.9 Use of hydrogen as chemical reagent or fuel ................................................210 4.3.3 Metal anodes.................................................................................................................212 4.3.4 Techniques for monitoring of emissions ......................................................................212 4.3.4.1 Overview ..............................................................................................................212 4.3.4.2 Common issues of all monitoring techniques.......................................................212 4.3.4.3 Monitoring techniques and frequency ..................................................................212 4.3.4.4 Monitoring of chlorine and chlorine dioxide in air...............................................213 4.3.4.5 Monitoring of free oxidants in water ....................................................................215 4.3.4.6 Monitoring of halogenated organic compounds in water .....................................216 4.3.5 Techniques to reduce emissions to air ..........................................................................217 4.3.5.1 Techniques to reduce emissions of chlorine .........................................................217 4.3.5.1.1 Techniques to prevent accidents and incidents or to limit their environmental consequences Safety measures..............................................217 4.3.5.1.2 The chlorine absorption unit .........................................................................223 4.3.5.2 Scrubbing with hydrogen peroxide to reduce emissions of chlorine dioxide .......226 4.3.5.3 Carbon tetrachloride-free chlorine purification and recovery liquefaction and purification............................................................................................................228 4.3.5.4 Use of refrigerants without ozone depletion potential and with low global warming potential .................................................................................................230 4.3.6 Techniques to reduce emissions to water .....................................................................231 4.3.6.1 Techniques to reduce emissions of sulphate.........................................................231 4.3.6.1.1 Overview.......................................................................................................231 4.3.6.1.2 Precipitation of sodium sulphate...................................................................232 4.3.6.2 Techniques to reduce emissions of chloride .........................................................233 4.3.6.2.1 Overview.......................................................................................................233 4.3.6.2.2 Nanofiltration................................................................................................233 4.3.6.3 Techniques to reduce emissions of free oxidants Treatment of waste water containing free oxidants, including bleach destruction.........................................236 4.3.6.3.1 Overview.......................................................................................................236 4.3.6.3.2 Common issues of all techniques to reduce emissions of free oxidants........236 WORKING DRAFT IN PROGRESS vi December 2011 TB/EIPPCB/CAK_Draft_1
4.3.6.3.3 Chemical reduction ...................................................................................... 237 4.3.6.3.4 Catalytic decomposition reduction ............................................................... 239 4.3.6.3.5 Thermal decomposition................................................................................ 242 4.3.6.3.6 Acidic decomposition Recycling of hypochlorite ........................................ 243 4.3.6.4 Techniques to reduce emissions of chlorate and bromate .................................... 244 4.3.6.4.1 Overview...................................................................................................... 244 4.3.6.4.2 Brine acidification ........................................................................................ 244 4.3.6.4.3 Acidic reduction ........................................................................................... 246 4.3.6.4.4 Catalytic reduction ....................................................................................... 247 4.3.6.4.5 Use of brine purge for the production of sodium chlorate............................ 249 4.3.6.5 Techniques to reduce emissions of halogenated organic compounds .................. 250 4.3.7 Techniques to reduce generation of sulphuric acid waste ............................................ 251 4.3.7.1 Overview.............................................................................................................. 251 4.3.7.2 On-site Reconcentration of spent sulphuric acid.................................................. 251 4.3.8 Techniques to reduce emissions of noise ..................................................................... 253 4.3.8.1 Introduction.......................................................................................................... 253 4.3.8.2 Strategic planning of the location of equipment, units and buildings .................. 253 4.3.8.3 Primary techniques: reducing noise at source ...................................................... 254 4.3.8.4 Secondary techniques: noise abatement ............................................................... 256 4.4 Membrane cell plants ............................................................................................................. 257 4.4.1 High-performance membranes..................................................................................... 257 4.5 Techniques for the remediation of contaminated sites ........................................................... 257 4.5.1 Overview...................................................................................................................... 257 4.5.2 Site remediation plan ................................................................................................... 257 4.5.3 Containment................................................................................................................. 259 4.5.4 Decontamination .......................................................................................................... 260 4.5.4.1 Overview.............................................................................................................. 260 4.5.4.2 Thermal desorption .............................................................................................. 261 4.5.4.3 Soil washing......................................................................................................... 264 5 BEST AVAILABLE TECHNIQUES........................................................................................... 267 Scope ·.......................................................................................................................................... 267 Definitions............................................................................................................................................ 268 General considerations ......................................................................................................................... 269 BAT conclusions.................................................................................................................................. 270 5.1 Cell technique ........................................................................................................................ 270 5.2 Decommissioning of mercury cell plants............................................................................... 271 5.3 Environmental management system....................................................................................... 273 5.4 Water consumption ................................................................................................................ 274 5.5 Energy consumption............................................................................................................... 276 5.6 Monitoring of emissions ........................................................................................................ 279 5.7 Emissions to air...................................................................................................................... 280 5.8 Emissions to water ................................................................................................................. 281 5.9 Generation of waste................................................................................................................ 283 5.10 Emissions of noise.................................................................................................................. 284 5.11 Site remediation ..................................................................................................................... 285 Glossary................................................................................................................................................ 286 6 EMERGING TECHNIQUES ....................................................................................................... 289 6.1 Introduction............................................................................................................................ 289 6.2 Oxygen-depolarised cathodes in modified membrane cells ................................................... 290 6.3 Use of fuel cells in chlor-alkali plants.................................................................................... 295 6.4 Membrane for direct production of 50% caustic soda............................................................ 298 6.5 Built-in precathode diaphragm............................................................................................... 298 WORKING DRAFT IN PROGRESS 7 CONCLUDING REMARKS AND RECOMMENDATIONS FOR FUTURE WORK .......... 299 REFERENCES....................................................................................................................................... 301 GLOSSARY OF TERMS AND ABBREVIATIONS .......................................................................... 313 I. ISO country codes............................................................................................................................. 313 II. Monetary units................................................................................................................................. 314 III. Symbols commonly used in this document...................................................................................... 314 IV. Unit prefixes ................................................................................................................................... 314 V. Units ·....................................................................................................................................... 315 TB/EIPPCB/CAK_Draft_1 December 2011 vii
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: 3.4.7 Emissions of noise ..........
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
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
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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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