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

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Chapter 3 environment are included in Annex II to the Industrial Emissions Directive [ 77, Directive 2010/75/EU 2010 ]. 3.4.2.3.5 Chlorate and bromate The main sources of chlorate and bromate are the purge from brine purification and sometimes also water streams that have been treated to decompose free oxidants into the less reactive chlorate and bromate. Chlorate (ClO3 - ) and (to a much lesser extent) bromate (BrO3 - ) are formed as by-products during electrolysis, particularly when using the diaphragm or membrane cell technique (see Section 2.1 and Table 2.1). Bromate is present in small quantities, as bromine is only present as a contaminant of the salt. Chlorine may react with hydroxyl anions (OH - ) to produce chlorate while bromine may react with hydroxyl anions (OH - ) to produce bromate. Due to the recycling of the brine, these components build up. Chlorate and bromate are unwanted compounds in the process as their presence will reduces the solubility of incoming salt and, in the case of the membrane cell technique, may negatively affect the caustic soda quality, the ion-exchange resins used for brine purification and the membranes. Measures are usually taken to keep the level of chlorate low (usually below 10 g/l in the feed brine). To maintain this level, there is a need to purge an appropriate volume of the brine, which can be carried out along with operating under acidic conditions in the anolyte (approx. pH 2, see Sections 2.5.3.2 and 4.3.6.4.2) or along with using a chlorate decomposer (see Sections 2.5.5, 4.3.6.4.3 and 4.3.6.4.4). The purge can also be used as raw material in a plant which produces sodium chlorate (see Section 4.3.6.4.5). In the case of diaphragm cell plants, any bromate or chlorate formed in the anolyte compartment migrates through the diaphragm and may be reduced by nascent hydrogen at the cathode (see Section 4.3.6.3.6). The residual levels remain in the caustic liquor which leaves the cell. To maintain this level, there is a need to operate under acid conditions (approx. pH 2) in the anolyte. If this is not the option chosen for the process (higher pH), a chlorate decomposer may be necessary to remove chlorate before purging. The reported concentration is between 5 to 10 g/l if no chlorate decomposer is installed and around 1 to 2 g/l after decomposition [Bayer Uerdingen, 1998]. Specific emissions are between 0.14 and 1 kg per tonne of chlorine produced. Chlorate is less reactive than chlorine and has a lower toxicity for aquatic biota. Bromate, on the contrary, is a reactive compound. Nevertheless, it is present in small quantities, as bromine is only present as a contaminant of the salt. Bromate releases are typically 10 – 100 times lower than the chlorate figures. Reported emission concentrations and factors are summarised in Table 3.13 and Table 3.14. WORKING DRAFT IN PROGRESS 88 December 2011 TB/EIPPCB/CAK_Draft_1
Chapter 3 Table 3.13: Emissions of chlorate to water from chlor-alkali plants in EU-27 and EFTA countries in 2008/2009 Chlorate emission concentrations in g/l ( 1 ) ( 2 ) ( 3 ) Value reported ( 4 ) Min. 10th percentile 25th percentile Median 75th percentile 90th percentile Max. Min. ( 5 ) 0.00020 0.0010 0.0090 0.22 0.77 3.0 5.0 Max. ( 6 ) 0.0070 0.051 0.46 1.4 5.0 5.7 14 Chlorate emission factors in g per tonne of annual chlorine capacity ( 1 ) ( 3 ) Value reported ( 4 10th 25th Min. ) percentile percentile Median 75th 90th Max. percentile percentile Min. ( 7 ) 24 ND 64 120 510 ND 670 Max. ( 8 ) 1.8 ( 9 ) ND 720 1400 3300 ND 5000 Average ( 10 ) 100 ND 160 200 340 ND 500 ( 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 ) All of the reporting plants perform periodic measurements (mostly semi-monthly and monthly). Averaging periods reported were mostly daily. ( 4 ) Some plants reported ranges with minimum and maximum values, some reported average values and some reported both. ( 5 ) 11 data from 11 plants. In addition, 3 plants reported values below the detection limit. ( 6 ) 14 data from 14 plants. ( 7 ) 6 data from 6 plants. In addition, 2 plants reported values below the detection limit and 1 plant a value of < 6 g/t. ( 8 ) 9 data from 9 plants. ( 9 ) This plant uses catalytic chlorate reduction with hydrogen. The corresponding minimum values reported were below the detection limit. ( 10 ) 7 data from 7 plants. NB: ND = not enough data. Source: [ 57, EIPPCB 2011 ] Table 3.14: Emissions of bromate to water from chlor-alkali plants in EU-27 and EFTA countries in 2008/2009 Bromate emission concentrations in mg/l ( 1 ) ( 2 ) ( 3 ) Value reported ( 4 ) Min. Median Max. Min. ( 5 ) 0.30 and 2.0 Max. ( 6 ) 0.50 10 990 Bromate emission factors in g per tonne of annual chlorine capacity ( 1 ) ( 3 ) Value reported ( 4 ) Min. Median Max. Min. ( 7 ) 0.26 and 3.2 Max. ( 8 ) 0.51 and 63 and 850 Average ( 9 ) 0.050 and 0.30 ( 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 ) All of the reporting plants perform periodic measurements (daily, weekly, monthly). Averaging periods reported were daily, monthly, semi-yearly and yearly. ( 4 ) Some plants reported ranges with minimum and maximum values and some reported average values. ( 5 ) 2 data from 2 plants. In addition, 3 plants reported values below the detection limit, 1 plant a value of < 1.2 mg/l, 1 plant a value of < 3 mg/l and 1 plant a value of < 5 mg/l. ( 6 ) 5 data from 5 plants. In addition, 1 plant reported a value of < 1.2 mg/l, 1 plant a value of < 3 mg/l and 1 plant a value of < 5 mg/l. ( 7 ) 2 data from 2 plants. In addition, 1 plant reported a value below the detection limit, 1 plant a value of < 0.5 g/t and 1 plant a value of < 6 g/t. ( 8 ) 3 data from 3 plants. In addition, 1 plant reported a value of < 0.5 g/t and 1 plant a value of < 6 g/t. ( 9 ) 2 data from 2 plants. Source: [ 57, EIPPCB 2011 ] WORKING DRAFT IN PROGRESS TB/EIPPCB/CAK_Draft_1 December 2011 89
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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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Page 55 and 56: 2.5 Brine supply 2.5.1 Sources, qua
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 and 100: Chapter 3 depleted brine is recircu
Page 101 and 102: Chapter 3 Table 3.10: Emissions of
Page 103: 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 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
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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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