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

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Chapter 4 with PMX diaphragms. The Vulcan Chemicals plant personnel conducted a “make good” analysis after the complete conversion of their plant. They achieved the power cost savings as expected in their appropriation and reduced the chlorate content of their caustic product and the hydrogen content in the chlorine gas. Today Vulcan Chemicals maintains performance by using appropriate procedures on individual cells to reduce anolyte levels as necessary. They maintain the chlorate in caustic with occasional acid brine flushes of the complete circuit to remove accumulated brine impurities. The diaphragms achieve a life of more than three years and a cell liquor strength of 145 g/l. [Curlin] Hüls, Rheinfelden, Germany, operated for several years fully converted with PMX diaphragms before the plant was closed. [Dutch report, 1998] Elf Atochem in Fos sur Mer and in Lavera, both in France, are proceeding to full conversions of both sites. The conversions should be complete by 2002. The plant located in Fos sur Mer is equipped with OxyTech MDC-55 cells (chlorine capacity: 160 kt/y). The plant located in Lavera is equipped with OxyTech HC-4B (42 m 2 area) cells (chlorine capacity: 160 kt/y). Many other plants, mainly in USA, have tested PMX diaphragms in one or more of their cells and some of these cells are still operating, due to the long lifetime of the PMX diaphragm. PPG’s Tephram Diaphragm PPG Natrium, West Virginia, USA: full-scale demonstration of Columbia N6 and OxyTech MDC-55 electrolysers. PPG Lake Charles, Louisiana, USA: full-scale demonstration of PPG’s GlanorV-1244 electrolysers. On a trial basis, six plants outside of PPG are currently operating cells equipped with Tephram Diaphragms. Rhone Poulenc Chimie’s Asbestos Free Diaphragm ChlorAlp, Le Pont de Claix, Isère, France (chlorine capacity: 240 kt/y) is converting to asbestos-free diaphragms. In 1998 10% of the Hooker S3B cells in the industrial cell room were converted with this material; in 1999 30% were to have been converted; at the end of 2000 60% of the S3B and H4 cells were to have been converted and in 2001 the site will be fully equipped with Asbestos Free Diaphragms. [Perineau] Reference literature [ 1, Ullmann's 2006 ], [ 10, Kirk-Othmer 2002 ], [ 31, Euro Chlor 2010 ], [ 63, Euro Chlor 2010 ], [ 75, COM 2001 ], [ 118, Solvay 2011 ], [ 146, Arkema 2009 ], [ 212, Florkiewicz 1997 ], [ 213, Florkiewicz and Curlin 1992 ], [ 214, Dilmore and DuBois 1995 ], [ 215, German Ministry 2011 ], [ 216, O'Brien et al. 2005 ], [ 217, PPG 2010 ], [ 218, Ahmed and Foller WORKING DRAFT IN PROGRESS 2003 ], [ 219, Carbocloro 2008 ], [ 220, Polish Ministry 2011 ], [ 221, Florkiewicz 1998 ] [Curlin], [Dilmore-DuBois, 1995], [Dutch report, 1998], [Florkiewicz, 1997], [Florkiewicz- Curlin, 1991], [Foller et al, 1997], [Kuntzburger et al, 1995], [Perineau] 178 December 2011 TB/EIPPCB/CAK_Draft_1
Chapter 4 4.2.3 Conversion of asbestos diaphragm cell plants to membrane cell plants technology or to asbestos-free diaphragms {Please note that the paragraphs of the original text were reordered to be compatible with the current standard 10-heading structure.} Description This technique consists in converting asbestos diaphragm cell plants to membrane cell plants. A conversion to the membrane cell technique includes a change of electrolysers, additional brine purification, additional brine dechlorination, inclusion of a cell room caustic soda recirculation system as well as change of transformers and rectifiers. Converting to membranes Technical description The important changes to an existing plant when converting from diaphragm cells to membrane cells technology are included in the following list [ 31, Euro Chlor 2010 ], [ 211, Dibble and White 1988 ]. Change of electrolysers. Additional brine purification, including hardness removal ion exchange techniques. Modifications to brine treatment to control other impurities, such as sulphate, may also be required. Additional brine dechlorination to protect the ion exchange resin. It is necessary to complete the brine recirculation loop by adding primary and secondary dechlorination and possibly resaturation. Inclusion of a cell room caustic soda recirculation system. If 50 wt-% product is required, the existing diaphragm cell caustic soda evaporator must be modified and simplified to accept high-strength, salt-free caustic soda. Change of transformers and rectifiers electrolysers and details of the cell room system. At the BASF plant in Ludwigshafen (Germany), the conversion involved the following changes [ 31, Euro Chlor 2010 ]: addition of supplementary brine filtration unit and ion exchangers to remove calcium and magnesium (the sulphate and silica levels were controlled via purge); addition of a two-step brine dechlorination unit based on vacuum dechlorination and chemical dechlorination with sodium hydrogen sulphite; addition of some piping to close the brine loop; dismantling of all diaphragm cells and installation of new electrolysers in the same cell room where anolyte and catholyte tanks were installed; addition of a caustic loop; conversion of the old diaphragm cell liquor evaporation unit to produce vacuum salt; addition of a caustic evaporation unit. WORKING DRAFT IN PROGRESS At the Anwil plant in Wuocuawek (Poland), the conversion comprised the following changes [ 31, Euro Chlor 2010 ]: addition of a new brine purification unit; addition of a new brine dechlorination unit; addition of a new caustic soda evaporator; modification of the existing cell liquor evaporation unit to concentrate the diluted brine; replacement of the diaphragm electrolysers by bipolar membrane electrolysers. TB/EIPPCB/CAK_Draft_1 December 2011 179
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EUROPEAN COMMISSION JOINT RESEARCH
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PREFACE 1. Status of this document
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Reference Document on Best Availabl
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3.4.7 Emissions of noise ..........
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4.3.6.3.3 Chemical reduction ......
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List of Tables Table 2.1: Main char
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List of Figures Figure 1.1: Share p
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SCOPE WORKING DRAFT IN PROGRESS Sco
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1 GENERAL INFORMATION 1.1 Industria
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Chlorine production in Mt/yr 12 11
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Chapter 1 Figure 1.4 shows the annu
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Share of total capacity in % 70 70%
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1.4 Chlor-alkali products and their
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Total consumption: 9 801 kt Miscell
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1.4.5 Consumption of hydrogen Chapt
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Chapter 1 and hazardous waste incin
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2 APPLIED PROCESSES AND TECHNIQUES
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Chapter 2 WORKING DRAFT IN PROGRESS
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Chapter 2 The main characteristics
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2.2 The mercury cell technique proc
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Chapter 2 Characteristics of the ca
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2.3 The diaphragm cell technique pr
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Source: [ 2, Le Chlore 2002 ] [USEP
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2.4 The membrane cell technique pro
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Chapter 2 (carcinogenic) [ 76, Regu
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Chapter 2 The membranes used in the
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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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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
Page 143 and 144: Chapter 3 Table 3.31: Yearly waste
Page 145 and 146: Chapter 3 The fact that the differe
Page 147 and 148: Chapter 3 3.6 Emissions Emission an
Page 149 and 150: Reported asbestos concentrations ar
Page 151 and 152: Chapter 3 3.7 Emissions Emission an
Page 153 and 154: {A list of techniques used on full
Page 155 and 156: 3.8.3 PCDDs/PCDFs, PCBs, PCNs and P
Page 157 and 158: Chapter 3 The ‘dioxin’ pattern
Page 159 and 160: Chapter 4 4 TECHNIQUES TO CONSIDER
Page 161 and 162: Heading within the sections Cross-m
Page 163 and 164: 4.1 Mercury cell plants 4.1.1 Overv
Page 165 and 166: Chapter 4 plants at comparable capa
Page 167 and 168: Chapter 4 Table 4.2: Data from the
Page 169 and 170: Chapter 4 environment can be expect
Page 171 and 172: 4. Plant size Chapter 4 An increase
Page 173 and 174: Table 4.6: Comparison of reported c
Page 175 and 176: Chapter 4 Generally, conversion cos
Page 177 and 178: 4.1.3 Decommissioning 4.1.3.1 Decom
Page 179 and 180: 3. Emptying of the cells and handli
Page 181 and 182: Chapter 4 Table 4.7: Overview of co
Page 183 and 184: Table 4.8: Techniques for monitorin
Page 185 and 186: Chapter 4 Table 4.10: Decommissioni
Page 187 and 188: 4.2 Diaphragm cell plants 4.2.1 Aba
Page 189 and 190: Source: [ 146, Arkema 2009 ] Figure
Page 191 and 192: Chapter 4 diaphragms [ 31, Euro Chl
Page 193: Driving force for implementation Th
Page 197 and 198: Chapter 4 directly from the cells.
Page 199 and 200: 4.3 All Diaphragm and membrane cell
Page 201 and 202: Chapter 4 non-standardised) will be
Page 203 and 204: Chapter 4 removal of conductive com
Page 205 and 206: Chapter 4 Cross-media effects Plant
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Page 209 and 210: Example plants Dow, Stade (Germany)
Page 211 and 212: Chapter 4 current density resulting
Page 213 and 214: Chapter 4 modifications to auxiliar
Page 215 and 216: Table 4.14: Cost calculation for th
Page 217 and 218: Chapter 4 membrane lifetimes range
Page 219 and 220: Chapter 4 Cross-media effects Some
Page 221 and 222: Chapter 4 The drawback of using fer
Page 223 and 224: Chapter 4 evaporation unit integrat
Page 225 and 226: Chapter 4 Environmental performance
Page 227 and 228: Chapter 4 Technical description The
Page 229 and 230: Chapter 4 Table 4.17: Monitoring te
Page 231 and 232: Chapter 4 Environmental performance
Page 233 and 234: Environmental performance and opera
Page 235 and 236: Chapter 4 Prevention of chlorine re
Page 237 and 238: Chapter 4 Good pipework design to m
Page 239 and 240: Chapter 4 was the solution at that
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Page 243 and 244: 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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