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

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Chapter 3 These techniques generally reduce the mercury content to below 30 µg/m³ corresponding to approximately 0.01 g/t annual chlorine capacity [ 87, Euro Chlor 2006 ]. For example, one plant reports mercury concentrations of 1 – 185 Zg/m 3 in treated hydrogen corresponding to 0.0001 – 0.027 g/t annual chlorine capacity while another plant reports concentrations of 10 – 1600 Zg/m 3 in hydrogen not used corresponding to 0.00146 – 0.233 g/t annual chlorine capacity [ 57, EIPPCB 2011 ]. If the hydrogen is compressed before treatment, lower mercury concentrations of approximately 10 µg/m 3 can be achieved corresponding to approximately 0.003 g/t annual chlorine capacity [ 87, Euro Chlor 2006 ]. The lowest concentrations of < 1 Zg/m 3 can be achieved when adsorption on either copper on an aluminium oxide carrier or on silver on a zinc oxide carrier is used [ 1, Ullmann's 2006 ]. Further hydrogen streams are produced from end boxes, wash boxes and caustic storage tanks which are referred to as 'weak hydrogen'. They may be treated by using the same techniques as described above [ 86, Euro Chlor 2010 ], [ 87, Euro Chlor 2006 ]. A further hydrogen stream is produced from mercury cells during the wash operations performed on the mercury, on its entrance to, and exit from, the cell. It is called ‘weak hydrogen’. The quantities of hydrogen are much smaller, and are diluted with air to maintain the concentrations below explosive limits. This hydrogen stream also contains mercury, which may be treated by addition of chlorine or hypochlorite. The chlorine reacts with mercury to form Hg2Cl2 which deposits as a solid. Alternatively, the mercury can be adsorbed on activated carbon. The cleaned gas is vented to atmosphere. The mercuric chloride residue is washed with brine, which reacts to form HgCl4 2and is recycled to the electrolysis plant. During electrolysis, the HgCl4 2- complex produces mercury metal and chlorine [UK Guidance note, 1993]. Hydrogen/nitrogen mixtures emitted during plant start-up cannot be treated due to safety reasons (no pressure loss admitted), but generally result in very low mercury emissions. There are, however, particular exceptional occasions when hydrogen must be emitted directly from the cells or when the treatment unit must be bypassed. These streams may contain appreciable quantities of mercury [ 3, Euro Chlor 2011 ], [ 86, Euro Chlor 2010 ]. Any remaining mercury is emitted if hydrogen is burnt as fuel. In the event of irregular operation, hydrogen is blown off or flared, usually after (at least partial) mercury removal. Hydrogen blow-off before mercury removal is rare and only occurs in emergencies. It has been estimated at 0.005 g of mercury released per tonne of chlorine produced by BASF in Antwerp (Belgium). This figure is of course only representative of one company and may vary. This source of emission should nevertheless not be omitted. Other fugitive mercury releases from the amalgam process 3.5.6.3.5 Mercury Vents from storage The storage and handling of mercury-contaminated material may lead to diffuse emissions of mercury from the store houses. Emissions depend mainly on the type of storage (open/closed), the storage temperature and the amount of mercury-contaminated material in storage. Reported emissions from one plant are around 0.1 g Hg/tonne chlorine capacity. [Dutch report, 1998] WORKING DRAFT IN PROGRESS Metallic mercury is generally stored in closed containers or bottles in a separate storage area [ 87, Euro Chlor 2006 ]. Emissions from storage and handling can be reduced by using large containers instead of bottles. If mercury is stored, the emission will also depend on the type of containers (big containers of 600 kg avoid mercury handling and reduce emissions compared to bottles). Reported emissions from BASF in Antwerp (Belgium) are in the range of 0.004-0.005 mg/Nm 3 (period of measurement: January 1997 to April 1998, the storage contains bottles of 35 kg of mercury and the consumption of mercury is 2.636 g/tonne chlorine produced). . {Please TWG provide updated information and figures.} 118 December 2011 TB/EIPPCB/CAK_Draft_1
Chapter 3 Generally, storage of contaminated materials should be separate from storage of mercury, and there should be no emission from the latter [Euro Chlor]. 3.5.6.3.6 Mercury Exhausts and vents from the recovery retort In the mercury recovery retort, mercury-containing waste is distilled in order to reduce the mercury content of the waste. The flue-gas leaving the retort contains mercury in considerable concentrations and is usually treated like other process exhausts (see Section 3.5.6.3.1) [ 87, Euro Chlor 2006 ]. a small amount of mercury. In some cases these gases are passed through a mercury filter before they are emitted; in others, the flue-gases are directly emitted to the atmosphere. Emissions from the mercury recovery retorts should be controlled to ensure that they are insignificant. The ventilation air from the room where the recovery retort is installed may be an additional source of mercury emissions. One plant reports mercury concentrations of 2.6 – 23.4 Zg/m 3 corresponding to 0.00127 – 0.01139 g/t annual chlorine capacity [ 57, EIPPCB 2011 ]. 3.5.6.3.7 Vents from workshops Another emission source may be the ventilation air from workshops where equipment contaminated with mercury is handled. One plant reports mercury concentrations of 1 – 23.6 Zg/m 3 for this source corresponding to 0.00049 – 0.01149 g/t annual chlorine capacity [ 57, EIPPCB 2011 ]. 3.5.7 Emissions to water Water emissions 3.5.7.1 Overview Emissions to water specific to mercury cell plants relate to mercury and to ancillary materials used for its removal. Other emissions are described in Section 3.4 on emissions and waste generation of relevance for all three cell techniques. Mercury-contaminated waste water includes [ 1, Ullmann's 2006 ], [ 91, Euro Chlor 2011 ]: Waste water emissions consist of mercury and other substances in waste water streams, which are described in the paragraphs concerning outputs from the auxiliary processes. The releases of mercury are specific to the amalgam technology. Mercury emitted from mercury cell facilities mainly arises from: the process waste water: brine purge, (back)washing water bleed from brine purification, condensate and wash liquor from the treatment of chlorine and hydrogen, condensate from hydrogen drying, condensate from caustic soda concentration units, brine leakage, ion-exchange eluate from process-water treatment; the wash water from the cell cleaning operations: inlet and outlet boxes; the rinsing water from the electrolysis hall: cleaning of the floors, tanks, pipes and dismantled apparatuses; the rinsing water from maintenance areas outside the electrolysis hall, if they are cleaned with water. WORKING DRAFT IN PROGRESS Brine purge, filter washings and waste liquor from the brine purification plant The depleted brine from the cells contains some dissolved mercury. The largest part of this mercury is recirculated into the cells. Part of the mercury is discharged through the purge of the TB/EIPPCB/CAK_Draft_1 December 2011 119
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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
Page 83 and 84: 3.3 Consumption levels of all cell
Page 85 and 86: 3.3.3 Ancillary materials Ancillary
Page 87 and 88: Further materials and/or further us
Page 89 and 90: Chapter 3 current) and the efficien
Page 91 and 92: Chapter 3 distance means a higher f
Page 93 and 94: 3.3.4.3.6 Production of caustic pot
Page 95 and 96: Chapter 3 hydrogen at low pressure
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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: Chapter 3 When concentrated solid c
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 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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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.,
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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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