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

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Chapter 3 Table 3.17: Generation of brine filtration sludges in chlor-alkali plants in EU-27 and EFTA countries in 2008/2009 Generation of brine filtration sludges in kg per tonne of annual chlorine capacity Plants using NaCl and KCl from all salt sources ( 1 ) Value reported ( 2 ) Min. percentile percentile Median 75th percentile 90th percentile Max. Min. ( 3 ) 0 0.040 0.50 4.1 18 24 72 Max. ( 3 ) 0.080 0.72 1.9 14 27 50 120 Average ( 4 ) 0.015 0.054 0.11 1.5 14 26 33 10 th 25 th Plants using exclusively NaCl vacuum salt Value reported ( 2 ) Min. percentile percentile Median 75th percentile 90th percentile Max. Min. ( 5 ) 0.070 ND 0.22 0.50 0.50 ND 0.60 Max. ( 5 ) 0.24 ND 0.48 1.0 1.0 ND 1.7 Average ( 6 ) 0.020 ND 0.070 0.11 0.12 ND 0.40 10 th 25 th Plants using exclusively NaCl rock salt Value reported ( 2 ) Min. percentile percentile Median 75th percentile 90th percentile Max. Min. ( 7 ) 10 ND ND 20 ND ND 29 Max. ( 7 ) 15 ND ND 29 ND ND 45 Average ( 6 ) 3.7 ND 6.0 18 27 ND 33 10 th 25 th Plants using 90 % NaCl solution-mined brine Value reported ( 2 10 Min. ) th 25 percentile th percentile Median 75th 90th Max. percentile percentile Min. ( 7 ) 0.14 ND ND 10 ND ND 45 Max. ( 7 ) 1.2 ND ND 27 ND ND 68 Average ( 7 ) 0.020 ND ND 17 ND ND 28 Value reported ( 2 Plants using exclusively NaCl solar salt ) Range ( 8 ) 4.1 – 6.5 and 10 – 50 Value reported ( 2 Plants using exclusively NaCl salt from potash mining wastes ) Ranges, Average ( 7 10 – 50 and 13 – 20 and 18 – 22 and 22 ) ( 1 ) 15 plants out of a total of 48 reported solids content in the brine sludge which ranged from 30 wt-% to 100 wt-%. ( 2 ) Some plants reported ranges with minimum and maximum values, some reported average values and 1 plant reported both. ( 3 ) 27 data from 26 plants. 1 of these plants provided separate data for different electrolysis units. 4 of the 26 plants included brine-softening sludges and pre-coat filter in the reported values. ( 4 ) 23 data from 23 plants. 1 of the 23 plants included brine-softening sludges and pre-coat filter in the reported value. ( 5 ) 6 data from 6 plants. 1 of the 6 plants included brine-softening sludges and pre-coat filter in the reported value. ( 6 ) 5 data from 5 plants. ( 7 ) 4 data from 4 plants. ( 8 ) 2 data from 2 plants. NB: ND = not enough data. Source: [ 57, EIPPCB 2011 ] WORKING DRAFT IN PROGRESS Table 3.17 shows that rock salt, solution-mined brine and salt from potash mining wastes usually generate much higher amounts of brine filtration sludges than vacuum salt. As regards the membrane process, the technology In addition, the membrane cell technique requires more rigorous purification of the brine, and sludge disposal from the filters is thus more significant. 94 December 2011 TB/EIPPCB/CAK_Draft_1
Chapter 3 3.4.3 Emissions and waste generation from chlorine processing, gas production, cooling, drying, liquefaction and storage and handling 3.4.3.1 Overview Air emissions consist of fugitive emissions of carbon dioxide and chlorine from the processing steps, from storage and handling of chlorine as well as of channelled emissions from, the chlorine destruction unit and the handling/storage of chlorine. The process of purifying and liquefying impure chlorine gas involves the use of carbon tetrachloride at a few installations in Europe, which is recovered to a large extent or incinerated. Small amounts of chlorine dioxide could also be emitted from the chlorine destruction unit as well as small amounts of refrigerants from the chlorine liquefaction system. The condensed water formed after cooling is usually recycled as brine make-up although some facilities combine this waste stream with other waste water streams prior to treatment. The remaining water vapour is removed by scrubbing the chlorine gas with concentrated sulphuric acid. The spent sulphuric acid waste is either used for other purposes, sent back to the vendor, is recycled or released sent to the site's waste water system. 3.4.3.2 Emissions to air Air emissions 3.4.3.2.1 Carbon dioxide Small amounts of carbon dioxide are released from the anode compartment and are collected and treated together with the chlorine. During chlorine liquefaction, carbon dioxide and other gases (and N2, O2, H2) remain in the gas phase and are finally purged from the system, together with a small amount of chlorine. This waste gas stream is usually processed in the chlorine destruction unit. The part of the Carbon dioxide that is not absorbed by the chlorine destruction unit is emitted into the atmosphere. 3.4.3.2.2 Chlorine Because chlorine is a hazardous gas, extreme precaution is taken to avoid prevent emissions of chlorine from the process and from handling and storage. Therefore, emissions of chlorine gas into the atmosphere are generally low and the sources of significant potential emissions are normally connected with the chlorine destruction unit. When measuring chlorine in the gas phase, other oxidising species are included due to the analytical method employed. This holds true for both categories of measurement techniques. The first is based on absorption of a gas stream in a liquid with subsequent wet chemical analysis while the second is based on direct measurements in the gas phase with electrochemical cells (see Section 4.3.4.4) [ 67, Euro Chlor 2010 ]. Other oxidising species are usually unlikely to be present in relevant concentrations with the exception of chlorine dioxide (see Section 3.4.3.2.3). WORKING DRAFT IN PROGRESS Emissions from non-condensable gases remaining from liquefaction Chlorine is liquefied in several steps of cooling and compressing. Gases (H2, O2, N2, CO2) in the process stream tend to concentrate in the gas phase. Therefore, chlorine gas liquefaction has an outlet for non-condensable gases. The chlorine content of these non-condensable gases ranges from 1-8% of the raw chlorine gas produced. The non-condensable gases are directed to a system which is able to handle chlorine such as a chlorine absorption/destruction unit or the manufacture of HCl, FeCl3 or ethylene dichloride, thus avoiding emissions into the atmosphere. TB/EIPPCB/CAK_Draft_1 December 2011 95
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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
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 and 104: Chapter 3 When measuring chlorine i
Page 109: Chapter 3 concentrations of organic
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
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
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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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