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

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Chapter 4 Solid salt Brine resaturation Secondary dechlorination Purification I Chlorine processing Brine circuit Primary Dechlorination Fine purification II Power supply Cell room building Caustic soda circulation Hydrogen processing Caustic Evaporation units that have to be added for the conversion from the mercury to the membrane cell technique Source: [ 211, Dibble and White 1988 ] Based on [Dibble-White, 1988] Figure 4.1: Mercury cell plant conversion to a membrane cell plant technology 50 wt-% liquid caustic soda The main changes to an existing plant when converting from the mercury to the membrane cell technique technology include: 1. The brine system The main concern is the purity of the brine feed to the existing cell room system. As mentioned in Chapter 2 Section 2.5.3, membrane cells electrolysers need purer brine than do mercury cells. Practical experience has experiences have shown that the mercury brine system can be reused after a careful cleaning of the whole system [ 211, Dibble and White 1988 ]. demercurisation and a careful clean-out of the whole system. The brine has to be drained out and the whole system has to be cleaned to remove impurities, deposits and solubilise mercury to recover it. For good performance of the membrane cells, a secondary brine purification step must also be added, usually using ion exchange units. In most cases it is also necessary to add a polishing filtration step to remove particles from the brine [ 232, Euro Chlor 2010 ]. Some materials, such as rubber linings, plastics and gasket materials containing calcium and magnesium, may need to be changed to avoid contamination of the ion exchange unit [ 211, Dibble and White 1988 ]. Additional brine treatment units to remove or reduce the levels of sulphate, chlorate and iodine may be necessary depending on the site [ 232, Euro Chlor 2010 ]. WORKING DRAFT IN PROGRESS A new high-performance brine dechlorination facility is required to reduce the residual chlorine to levels below those which could deactivate the ion exchange resins of the secondary brine purification step. Generally, either chemical reduction using sodium sulphite (for example Solvay in Jemeppe, Belgium), catalytic reduction or activated carbon adsorption are is used, depending on the type of salt and the overall economics [ 211, Dibble and White 1988 ]. There is a difference in the water balance between membrane and mercury the brine circuits of mercury and membrane cell plants (see Section 4.3.2.3.7). There is also a difference in mass flow rates, the brine recirculation being higher in mercury cell plants than in membrane cell 148 December 2011 TB/EIPPCB/CAK_Draft_1
Chapter 4 plants at comparable capacities (see Section 2.4.1). Both the water balance and the mass flow rates need to be taken into account in any conversion. Very pure hydrochloric acid (HCl) is needed for brine acidification and an HCl production unit (H2/Cl2 burner) might need to be installed. Large amounts of HCl are consumed if chlorate levels in the brine are reduced by acidification (see Section 4.3.6.4.2) or acidic reduction (see Section 4.3.6.4.3) [ 232, Euro Chlor 2010 ]. 2. The cell room building It is reported that existing cell room buildings can be reused to accommodate membrane cell electrolysers. The saving of Space saving makes it theoretically possible to install up to 400 % more capacity with membrane technology in an existing building. However, a clean space is needed for the membrane cells. The decision to reuse an existing building will depend on [ 211, Dibble and White 1988 ]: the condition of the existing building; whether the availability of space for a new cell room is available; the extent of savings from reduced loss of production. Some old cell room buildings may be in a poor condition and thus may justify total replacement. Environmental concerns may also lead to the construction of a new building consideration of building replacement. This particularly applies to mercury contamination of existing concrete structures, where some emissions will continue even after replacement of the mercury cells [ 211, Dibble and White 1988 ]. In the conversion of the mercury cell plant of Associated Octel in Ellesmere Port (United Kingdom), the existing cell room was kept, but the preparation of the floor took eight weeks for the removal of the old concrete cell plinths and for filling in holes before resurfacing [ 225, Lott 1995 ]. has been kept, but mercury decontamination of the site and hygiene for the workforce were reported to be of paramount importance [Lott, 1995]. Some chlor-alkali plants have space available close to existing cell rooms. This allows the erection of a new cell room building whilst reusing other plant systems in situ [ 211, Dibble and White 1988 ]. Some companies, because they have plenty of space, succeed in having the two cell techniques technologies in the same cell room, mercury and membrane, without any problem of contamination of membranes or products [ 224, Bayer 1998 ][Bayer Uerdingen, 1998]. The construction of the building should also be able to support the normally higher weight density of membrane electrolysers. The major advantage of a new building is the ability to minimise production losses during conversion, since it can be erected construction can take place and the electrolyser system can be installed while production continues in the old building [ 211, Dibble and White 1988 ]. In 1997, Borregaard in Norway converted its Sarpsborg mercury cell chlor-alkali plant to a membrane cell plant, building a completely new cell room. The total production stoppage reported was 7 seven weeks [ 227, de Flon 1998 ]. [Dibble-White, 1988] reports a case where In another case, the building was reused and production could be maintained during the conversion by operation of other cell rooms elsewhere on the site. The penalty of production loss in this case was not significant, which is not the case if there is only a single cell room [ 211, Dibble and White 1988 ]. WORKING DRAFT IN PROGRESS 3. The electrolysers The design and operation of the electrolysers are essentially different and no old parts can be reused. TB/EIPPCB/CAK_Draft_1 December 2011 149
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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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Page 115 and 116: Chapter 3 in process and waste wate
Page 117 and 118: Chapter 3 produced per year has bee
Page 119 and 120: Chapter 3 Table 3.21: Emissions of
Page 121 and 122: Chapter 3 of chlorine capacity. The
Page 123 and 124: Table 3.23: Mercury emissions from
Page 125 and 126: Mercury emissions in g Hg/t Cl capa
Page 127 and 128: Chapter 3 Table 3.24: Mercury emiss
Page 129 and 130: Chapter 3 Table 3.25: Emissions of
Page 131 and 132: Chapter 3 KCl are higher than from
Page 133 and 134: Chapter 3 When concentrated solid c
Page 135 and 136: Chapter 3 Generally, storage of con
Page 137 and 138: Chapter 3 recycled brine systems si
Page 139 and 140: Process Maintenance To solid treatm
Page 141 and 142: 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: 4.1 Mercury cell plants 4.1.1 Overv
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 and 194: Driving force for implementation Th
Page 195 and 196: Chapter 4 4.2.3 Conversion of asbes
Page 197 and 198: Chapter 4 directly from the cells.
Page 199 and 200: 4.3 All Diaphragm and membrane cell
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Page 203 and 204: Chapter 4 removal of conductive com
Page 205 and 206: Chapter 4 Cross-media effects Plant
Page 207 and 208: Environmental performance and opera
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
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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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