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

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Chapter 3 3.5.8 Emissions via products Some of the mercury leaves the process via the produced chlorine, hydrogen and caustic and may therefore be emitted to the environment during subsequent uses. Hot, moist chlorine leaving the cells contains small amounts of mercury which is mostly washed out in the subsequent cooling process and may be fed back into the brine with the condensate. The residual mercury is mostly trapped in sulphuric acid during chlorine drying. Two plants report mercury concentrations of 0.085 and 10 mg/kg sulphuric acid. Mercury concentrations in cool and dry chlorine gas are low and typically < 1 Zg/kg [ 57, EIPPCB 2011 ], [ 86, Euro Chlor 2010 ], [ 87, Euro Chlor 2006 ]. Mercury emissions from hydrogen which is neither emitted nor burnt are included in the overall figures of emissions via products. Treatment techniques and residual mercury concentrations are described in Section 3.5.6.3.4. Caustic soda and potash are filtered to reduce mercury concentrations in the final product. A variety of filters are used including plate filters with carbon pre-coat as well as candle filters with or without carbon pre-coat. Although all types of filters can achieve very low levels of mercury in the product, the predominant technique is the plate filter with carbon pre-coat. Mercury concentrations in filtered caustic are typically about 50 Zg/kg in 50 wt-% caustic corresponding to emission factors of approximately 0.1 g/t annual chlorine capacity [ 87, Euro Chlor 2006 ]. Overall mercury emission factors via products in 2010 ranged from 0.01 – 0.43 g/t annual chlorine capacity, the median being 0.05 g/t annual chlorine capacity (Table 3.23). Mercury contained in caustic is usually the largest contributor to emissions via products. 3.5.9 Generation of wastes 3.5.9.1 Overview Wastes generated specific to mercury cell plants relate to those contaminated with mercury. The wastes described in Section 3.4 on emissions and waste generation of relevance for all three cell techniques usually fall under this category. Solid wastes can arise at several points in the process as shown in Figure 3.5, note that wastes from waste water treatments are not shown in the figure. WORKING DRAFT IN PROGRESS 122 December 2011 TB/EIPPCB/CAK_Draft_1
Process Maintenance To solid treatment Waste water treatment ( 1 ) Mercury removal Cooling Storage Brine purge Brine saturation Precipitation Filtration Electrolysis Mercury removal ( 1 ) Chemical agents Cooling Drying Compression Liquefaction Storage Chapter 3 WORKING DRAFT IN PROGRESS TB/EIPPCB/CAK_Draft_1 December 2011 123 Salt Amalgam Mercury Caustic Amalgam decomposer Hydrogen To solid Cooling treatment Customers To solid treatment Process exhaust Mercury removal ( 1 ) Chlorine CAUSTIC HYDROGEN CHLORINE ( 1 ) Not all techniques result in solid waste. Source: [ 87, Euro Chlor 2006 ][Euro Chlor] {The figure was updated.} Figure 3.5: Major solid waste sources in mercury cell chlor-alkali plants Solid waste sources in the mercury process Wastes containing mercury include [ 87, Euro Chlor 2006 ]: solids from brine purification (see Section 3.5.9.2) solids from caustic filtration (see Section 3.5.9.3) solids from waste water treatment (see Section 3.5.9.4) solids from sludge (sewer, traps, channels) activated carbon from the treatment of gaseous streams (see Section 3.5.9.5) graphite from decomposer packing (see Section 3.5.9.6) residues from retorts (see Section 3.5.9.7) wastes from maintenance and renewal (see Section 3.5.9.8). sludges from waste water treatment, solids generated during brine purification (filter residue), spent graphite from decomposer cells, sludges from caustic filters (spent caustic filters from the filtration of caustic solution such as graphite candles), etc. 3.5.9.2 Solids from brine purification (See Section 2.5.3). The quantities of precipitated solids depend on the purity of the salt used to make the brine (see Section 3.4.2.4). It should be noted that in In the case of plants using the once-through brine process, purification and filtration is are carried out prior to the cell and there is no contact of the purification sludges with mercury. In the case of plants using a brine recirculation process, the mercury-contaminated filter cakes are often washed to displace the residual mercury-containing brine. The sludge is then distilled at the plant, temporarily stored or
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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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Page 89 and 90: Chapter 3 current) and the efficien
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Page 95 and 96: Chapter 3 hydrogen at low pressure
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Page 99 and 100: Chapter 3 depleted brine is recircu
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Page 103 and 104: Chapter 3 When measuring chlorine i
Page 109 and 110: Chapter 3 concentrations of organic
Page 111 and 112: 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
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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 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: Chapter 3 recycled brine systems si
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
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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
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Page 187 and 188: 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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