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

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Chapter 3 sent to a deposit. In some cases the filter cakes are dissolved to be pumped to the waste water treatment unit and the sludge therefrom is distilled at the plant, temporarily stored or sent to a deposit [ 3, Euro Chlor 2011 ]. Reported mercury concentrations in brine filtration sludges are summarised in Table 3.29. Table 3.29: Mercury concentrations in brine filtration sludges of chlor-alkali plants in EU-27 and EFTA countries in 2008/2009 Mercury concentrations in brine filtration sludges in g/t waste ( 1 ) ( 2 ) Value reported ( 3 10th 25th Min. ) percentile percentile Median 75th 90th Max. percentile percentile Min. ( 4 ) 1.0 ND 10 68 200 ND 1000 Max. ( 5 ) 3.0 ND 130 210 730 ND 18 000 Average ( 6 ) 25 25 29 95 250 1600 2000 ( 1 ) 9 plants out of a total of 22 reported solids contents in the brine sludge which ranged from 35 wt-% to 100 wt-%. ( 2 ) In addition, 2 plants reported mercury concentrations in brine softening sludges of 0.031 and 136 g/t waste. ( 3 ) Some plants reported ranges with minimum and maximum values, some reported average values and 1 plant reported both. ( 4 ) 9 data from 9 plants. In addition 1 plant reported a value below the detection limit and 1 plant a value of < 200 g/t waste. ( 5 ) 10 data from 10 plants. In addition 1 plant reported a value of < 200 g/t waste. ( 6 ) 12 data from 12 plants. NB: ND = not enough data. Source: [ 57, EIPPCB 2011 ] The quantity of mercury contained in sludges from brine filters is variable: A plant using vacuum salt reported a mercury amount of 1.8 kg in 21.3 tonnes of sludges produced from the brine filters for 1997 and 1.8 kg in 18 tonnes of sludges for 1998 (chlorine production capacity is about 120000 tonnes). Another plant, also using vacuum salt, reports figures of 12 tonnes of sludges from brine filtration, but an amount of mercury of 60 kg a year (chlorine production capacity of 110000 tonnes). 3.5.9.3 Solids from caustic filtration: (See Section 4.2.1.3) The sludge from caustic filtration consists of carbon pre-coat contaminated with significant amounts of mercury. It is dewatered and in some cases led to a mercury recovery retort (see Section 3.5.9.7). The residual solid waste is subsequently disposed of. In other cases, the sludge is disposed of without mercury recovery [ 3, Euro Chlor 2011 ]. 3.5.9.4 Solids from waste water treatment The different treatment techniques for mercury-contaminated waste water (see Section 4.1.3.1) result in different types of solid waste. Ion-exchange resins can usually be regenerated with hydrochloric acid. Otherwise the resins can be treated as solid waste, retorted or sent to underground storage. Precipitated mercury sulphide filtered from the waste water may be dissolved and fed back into the brine system, treated in the mercury distillation unit or disposed of as stabilised mercury sulphide. Activated carbon contaminated with mercury resulting from adsorptive treatment is usually treated by distillation [ 94, Euro Chlor 2009 ]. WORKING DRAFT IN PROGRESS 124 December 2011 TB/EIPPCB/CAK_Draft_1
3.5.9.5 Graphite and activated Activated carbon from the treatment of gaseous streams: (See Section 4.2.1.1) Chapter 3 Solid waste results when process exhausts or hydrogen is treated with iodised or sulphurised activated carbon or with metals on a carrier. Mercury adsorbed on activated carbon or metals may be recovered by distillation or disposed of [ 3, Euro Chlor 2011 ], [ 87, Euro Chlor 2006 ]. 3.5.9.6 Graphite from decomposer packing The packing within the decomposers (the reactors where the mercury/sodium amalgam is converted to caustic soda and hydrogen) is usually composed of graphite balls or granules. In During normal use, there is an attrition of the graphite and approximately every 10 years decomposers will need repacking. The graphite, typically containing 1 – 10 wt-% mercury, can be retorted. The quantity of graphite is approximately 1 – 2 g/t annual chlorine capacity [ 75, COM 2001 ]. tonnes for each 100 000 tonnes of Cl2 capacity. 3.5.9.7 Residues from retorts The retorting or distillation process can be applied to most materials containing metallic mercury, such as caustic filter media and decomposer graphite, stock tank sludges, etc. The distilled mercury is recovered. However, not all contaminated wastes can be retorted because some produce volatile mercury compounds which are difficult to remove from the process exhaust. The solid residue is landfilled or stored underground (mines) [ 87, Euro Chlor 2006 ], [ 94, Euro Chlor 2009 ]. The residue typically contains from < 10 – 200 mg Hg/kg waste. The final solids typically contain from less than 10 up to 200 mg mercury/kg waste. In some cases, particularly concerning materials having very fine pore sizes, this may increase to approximately about 1000 mg Hgmercury/kg waste. Under normal circumstances, the quantity of retort residues will be determined by the volume of caustic filtration solids and is typically about 5 g/t annual chlorine capacity. , say 5 tonnes per 100 000 tonnes of Cl2 capacity. However, retorts are frequently worked in campaigns and the quantity may be highly augmented by special activities such as stock tank recoveries or sump cleaning [ 75, COM 2001 ]. 3.5.9.8 Wastes from maintenance and renewal and demolition By their nature, both the quantity and character of these wastes is highly variable. Materials include personal protective equipment, process equipment and construction materials. Materials can range from protective gloves to thousands of tonnes of bricks from demolished cell rooms. 3.5.9.9 Reported waste Waste generation levels Most of the mercury which leaves an installation is contained in waste. In 2010, mercury in waste disposed of by chlor-alkali plants in EU-27 and EFTA countries ranged from WORKING DRAFT IN PROGRESS 0 – 98 g/t annual chlorine capacity, the median being 5.0 g/t annual chlorine capacity (Table 3.23). In general, the amount of waste disposed of varies considerably from one year to the next depending on the type of maintenance work which is done and other factors, such as the time during which waste is temporarily stored on site. Table 3.30 and Table 3.31 provide examples of waste types, amounts, applied treatments and mercury contents from two mercury cell chlor-alkali plants in Sweden. To give an idea of what types and amounts of waste that are generated, Table 3.4 and Table 3.5 presents the yearly waste generation and treatment for AkzoNobel in Bohus and Hydro Polymers AB in Stenungsund (both plants in Sweden). The production is based on vacuum salt TB/EIPPCB/CAK_Draft_1 December 2011 125
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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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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 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: Process Maintenance To solid treatm
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
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
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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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