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

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Chapter 3 Substance Emission in kg/tonne chlorine capacity Sulphate 0.3-0.7 15 (Vacuum salt) (rock salt) Strictly depends on the purity of the incoming salt Chloride 4–25 Free oxidants 0.001–1.5 (1) Chlorate 0.14-4 (2) Metals Depends on the purity of the incoming salt Chlorinated hydrocarbons 0.03-1.16 (3) g/tonne Cl2 capacity (measured as EOX) Generally treated before discharging 1) Higher figure from a plant that destroy the produced bleach in a chlorine destruction unit and releases the remaining liquid. In this case, a value of 1.5 kg/tonne chlorine capacity is reported. 2) Values will depend on the presence or not of a chlorate decomposer. 3) Higher figure from a plant that destroy the produced bleach in a chlorine destruction unit andreleases the remaining liquid. In this case, a value of 1.16 g/tonne chlorine capacity is reported Table 3.6: Releases into water from the brine circuit using a recirculation process {This table is completely contained in the summary Table 3.1 and therefore is proposed to be deleted.} 3.4.2.3.2 Sulphate {For each of the following pollutants, it is proposed to describe in the following order (if appropriate): source, relevance for the process, definition in the case of sum parameters, current emission levels, factors which influence the emission levels including a brief mentioning of techniques to reduce emission levels, and a brief mentioning of the relevance for the environment.} Brine is generally purged from cells to reduce the levels of sodium sulphate and/or sodium chlorate in the cells. The source of sulphate in brine is the salt used. Sulphate has a negative effect on the electrolysis process (damages the anode coating) and its level is carefully controlled. This is normally done by a bleed purge from the brine treatment system for mercury amalgam and membrane cell plants processes and by purge from in the caustic evaporator for from diaphragm cell chlor-alkali plants. Sulphate emissions may also be due to the neutralisation and discharge of spent sulphuric acid from chlorine drying. In addition, (hydrogen) sulphite is frequently used for complete dechlorination of the brine in the membrane cell technique as well as for the treatment of waste water containing free oxidants. In both cases, (hydrogen) sulphite is converted to sulphate. Reported emission concentrations and factors are summarised in Table 3.10. WORKING DRAFT IN PROGRESS 84 December 2011 TB/EIPPCB/CAK_Draft_1
Chapter 3 Table 3.10: Emissions of sulphate to water from chlor-alkali plants in EU-27 and EFTA countries in 2008/2009 Sulphate emission concentrations in g/l ( 1 ) ( 2 ) ( 3 ) Value reported ( 4 ) Min. 10th percentile 25th percentile Median 75th percentile 90th percentile Max. Min.( 5 ) 0.030 0.050 0.054 0.44 2.1 3.8 9.0 Max. ( 6 ) 0.070 0.53 1.2 5.0 7.8 24 75 Average ( 7 ) 0.42 and 1.8 Sulphate emission factors in kg per tonne of annual chlorine capacity ( 1 ) ( 3 ) Value reported ( 4 ) Min. 10th percentile 25th percentile Median 75th percentile 90th percentile Max. Min.( 8 ) 0.12 ND 0.24 0.26 0.39 ND 4.3 Max. ( 9 ) 0.13 ND 0.20 0.55 1.0 ND 10 Average ( 10 ) 0.21 0.28 0.44 0.72 1.1 1.3 1.4 ( 1 ) Coverage: all three cell techniques; both brine recirculation and once-through brine plants. ( 2 ) Data refer to the outlet of the electrolysis plant prior to mixing with other waste water. ( 3 ) Most of the reporting plants perform periodic measurements (daily, weekly, semi-monthly, monthly) while a few perform continuous measurements. Averaging periods reported were daily, weekly, monthly and yearly. ( 4 ) Some plants reported ranges with minimum and maximum values, some reported average values and some reported both. ( 5 ) 16 data from 16 plants. In addition, 4 plants reported values below the detection limit. ( 6 ) 2 data from 2 plants. ( 7 ) 20 data from 20 plants. ( 8 ) 5 data from 4 plants. 1 of these plants provided separate data for different electrolysis units. In addition, 3 plants reported values below the detection limit. ( 9 ) 8 data from 7 plants. 1 of these plants provided separate data for different electrolysis units. ( 10 ) 13 data from 12 plants. 1 of these plants provided separate data for different electrolysis units. NB: ND = not enough data. Source: [ 57, EIPPCB 2011 ] Plants using solely vacuum salt show sulphate emission factors in the range of 0.21 – 1.3 kg/t annual Cl2 capacity. In general higher values, up to 10 kg/t annual Cl2 capacity, were reported by plants using rock salt (individually or in combination with other salts) [ 57, EIPPCB 2011 ]. The figures reported show that independently of the capacity of the plant, releases of sulphate are in the range of 0.3 – 0.7 kg per tonne chlorine produced if vacuum salt is used (corresponding to about 34 tonnes a year for production of 100 kt) and around 15 kg per tonne chlorine produced if rock salt is used. This The discharge of sulphate may be considered problematic depending on where the releases occur. 3.4.2.3.3 Chloride In the case of mercury and membrane cell plants, during purification of the brine, approximately about 3 – 4 % is purged to avoid the build-up of undesired components. This purge usually WORKING DRAFT IN PROGRESS contains can have a high concentration of chloride. Generally, after treatment to remove free oxidants, the purge is discharged into the site's waste water system the ambient water. In the case of diaphragm cell plants, chloride emissions result from the purge of the condensers for chlorine cooling and caustic concentration. Reported emission concentrations and factors are summarised in Table 3.11. Emissions reported are in the range of 4 – 20 kg/tonne chlorine produced. TB/EIPPCB/CAK_Draft_1 December 2011 85
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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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Page 51 and 52: Chapter 2 The membranes used in the
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Page 57 and 58: Chapter 2 centrifuges before dispos
Page 59 and 60: Source: [ 29, Asahi Glass 1998 ] (p
Page 61 and 62: Impurity Source Upper limit of brin
Page 63 and 64: Chapter 2 No such dechlorination tr
Page 65 and 66: Chapter 2 The cooling water is gene
Page 67 and 68: Chapter 2 composition of the chlori
Page 69 and 70: 2.6.11 Dealing with impurities 2.6.
Page 71 and 72: Chapter 2 amount of chlorine, and t
Page 73 and 74: 2.6.12.2 Chemical reactions Chapter
Page 75 and 76: 2.7 Caustic processing production,
Page 77 and 78: Chapter 2 2.8 Hydrogen processing p
Page 79 and 80: 3 CURRENT PRESENT EMISSION AND CONS
Page 81 and 82: 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
Page 97 and 98: 28 kg of hydrogen is produced {Thes
Page 99: Chapter 3 depleted brine is recircu
Page 103 and 104: Chapter 3 When measuring chlorine i
Page 105 and 106: Chapter 3 Table 3.13: Emissions of
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 and 150: Reported asbestos concentrations ar
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Chapter 3 3.7 Emissions Emission an
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{A list of techniques used on full
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3.8.3 PCDDs/PCDFs, PCBs, PCNs and P
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Chapter 3 The ‘dioxin’ pattern
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Chapter 4 4 TECHNIQUES TO CONSIDER
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Heading within the sections Cross-m
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4.1 Mercury cell plants 4.1.1 Overv
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Chapter 4 plants at comparable capa
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Chapter 4 Table 4.2: Data from the
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Chapter 4 environment can be expect
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4. Plant size Chapter 4 An increase
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Table 4.6: Comparison of reported c
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Chapter 4 Generally, conversion cos
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4.1.3 Decommissioning 4.1.3.1 Decom
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3. Emptying of the cells and handli
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Chapter 4 Table 4.7: Overview of co
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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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