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

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Chapter 3 The asbestos diaphragms in modern diaphragm chlor-alkali plants have a lifetime of approximately one year. After this period year the cell is taken out of operation and the old asbestos is removed from the cathode can. Reported figures are in the range of 0.09 kg solid residues per tonne of chlorine capacity (~ 13.5 tonnes of asbestos per year, with a chlorine capacity of 150000 tonnes) to 0.2 kg per tonne of chlorine capacity (~ 30 tonnes of asbestos per year, considering a chlorine capacity of 150000 tonnes). 0.1 kg per tonne chlorine capacity is the medium average reported by the industry. In 2008/2009, reported figures from three plants using asbestos diaphragms amounted to 0.16, 0.38 and 0 – 0.064 kg/t annual chlorine capacity [ 57, EIPPCB 2011 ]. Discarded cell parts are either landfilled on site or are sent off site for disposal, depending on the legislation of the country. WORKING DRAFT IN PROGRESS 134 December 2011 TB/EIPPCB/CAK_Draft_1
Chapter 3 3.7 Emissions Emission and consumption levels and waste generation from the membrane cell technique process 3.7.1 Consumption and emission levels Consumption and emission levels of membrane cell plants are fully described in Sections 3.3 and 3.4, respectively, which cover consumption and emission levels of relevance for all three cell techniques. Emissions from chlor-alkali plants using the membrane technology are, apart from chlorine, linked to the brine purification needed to avoid undesirable impurities in the membrane cell and solid wastes generated by the used membranes. Emissions coming from auxiliaries are described in the relevant paragraphs. 3.1.2.3.1 Water emissions Waste water from the membrane cell process originates from caustic evaporation, chlorine drying and wash water from the ion-exchange resin used to purify the brine. Membrane plants usually use a bleed from the brine circuit in order to prevent accumulation of contaminants. All these emissions are described in the Section about auxiliary processes. 3.7.2 Generation of wastes The generation of wastes specific to membrane cell plants relate to sludges generated during secondary brine purification as well as to scrapped cell parts including gaskets and membranes. Other types of waste generated are described in Section 3.4 on emissions and waste generation of relevance for all three cell techniques. Wastes are generated during the secondary brine purification and consist of used materials such as pre-coat and body feed material made of cellulose. The pre-coat filter sludge from the brine softener consists mainly of alpha-cellulose, contaminated with iron hydroxide and silica. In 2008/2009, reported figures from seven membrane cell plants amounted to 0.2 – 0.26, 0.23, 0.3, 0.26 – 0.39, 0.5, 0.5 and 0.56 kg/t annual chlorine capacity [ 57, EIPPCB 2011 ]. Membrane plants report a figure of 600 g/t for sludges from brine softening. Ion-exchange resins for secondary brine purification are very rarely changed. Resins are regenerated approximately about 30 times per year. In 2008/2009, reported figures for ion-exchange resin wastes from two membrane cell plants amounted to 4 and 5.6 – 6.7 g/t annual chlorine capacity [ 57, EIPPCB 2011 ]. Spent membranes and gaskets from membrane cells become waste after their service life. The membranes have a lifetime of between three and five 2 and 4 years. The waste from cell gaskets and membranes has been estimated at approximately about 60 g per tonne of chlorine produced (data from one membrane plant) [ 75, COM 2001 ]. In [Dutch report, 1998] other values are given: 3.3 g/t for gaskets and spent membranes respectively. Values reported for another plant amount to 3 g/t for gaskets [ 57, EIPPCB 2011 ] and approximately 3.3 g/t for membranes [ 17, Dutch Ministry 1998 ]. WORKING DRAFT IN PROGRESS TB/EIPPCB/CAK_Draft_1 December 2011 135
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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
Page 99 and 100: Chapter 3 depleted brine is recircu
Page 101 and 102: Chapter 3 Table 3.10: Emissions of
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
Page 113 and 114: Chapter 3 {Please TWG provide infor
Page 115 and 116: Chapter 3 in process and waste wate
Page 117 and 118: Chapter 3 produced per year has bee
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 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: Reported asbestos concentrations ar
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 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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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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