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

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Chapter 4 efficiency. When the cell is put back into operation, the iron oxides are reduced to iron and become points for the evolution of hydrogen leading to increased hydrogen levels in chlorine [ 216, O'Brien et al. 2005, Section 4.6.6 ]. Techniques to refresh plugged diaphragms and to remove iron are available (e. g. by washing with hydrochloric acid) [ 216, O'Brien et al. 2005, Section 4.7.6 ]. , since an accumulation of corrosion products over several years may result in high levels of hydrogen in chlorine before the end of the useful diaphragm life. Patented procedures to overcome the plugging of a diaphragm with brine impurities are available (for example from OxyTech). A plugged diaphragm is frequently the cause of low cell efficiency. Removing iron from the diaphragm is also important, as iron also can be a source of elevated hydrogen levels in chlorine. However, the preferred method of operation is to avoid these problems by using pure and in particular filtered brine, especially if vacuum salt from a caustic evaporator is used. Techniques to protect the cathode during shutdown include the injection of reducing agents and a polarisation rectifier [ 31, Euro Chlor 2010 ]. General Electric in Mount Vernon (USA), was fully converted to PMX ® diaphragms at one time but problems with iron in the brine forced General Electric GE to switch back to PMA diaphragms. The brine contained high levels of iron and gluconate originating from the recycling of waste water from a polycarbonate production unit. The impurities plugged the diaphragms within 9 – 15 months while the gluconate prevented any acid washing. The asbestos-free diaphragms were therefore not economical [ 221, Florkiewicz 1998 ]. Problems with iron impurities were also reported by the Zachem plant in Bydgosczc (Poland) during test runs with asbestos-free diaphragms in 1999/2000. The plant recycles salt-containing waste water from other production units back into the brine system (see Section 4.3.2.1.3). Zachem reports that the use of asbestos-free diaphragms would therefore require major changes of the brine treatment system [ 220, Polish Ministry 2011 ]. Economics Economic benefits of using non-asbestos diaphragms come from [ 31, Euro Chlor 2010 ]: reduced operating costs due to lower cell voltage; the reduction of reduced cell renewal labour costs due to the longer lifetimes of the diaphragms and steel cathodes (fewer shutdowns lead to less corrosion); and the reduction of the reduced waste handling and disposal costs due to asbestos-free materials. Despite the higher purchase costs (up to 20 times the costs of a PMA diaphragm), the interest of using asbestos-free diaphragms has been proven industrially in several plants [ 31, Euro Chlor 2010 ]. However, this needs to be offset against the substantially higher purchase costs (up to 20 times the cost of a PMA diaphragm) and the costs due to the need for closer control and monitoring. According to [Florkiewicz, 1997] a 3 year life of the PMX diaphragm is the minimum required to achieve breakeven. On-site capital requirements for a conversion remain highly site-specific and the configuration of the cells (cells with large active area, linked to the chlorine production per m 2 of diaphragm) may greatly influence the cost of a conversion. The additional equipment required for WORKING DRAFT IN PROGRESS conversion may include a diaphragm preparation facility, a reducing agent injection system and a polarisation rectifier to protect the cathodes against corrosion as well as additional brine purification equipment [ 31, Euro Chlor 2010 ]. The total cost (everything included) for converting a diaphragm cell plant with a chlorine capacity of 160 kt/yr an annual capacity of 160 kt Cl2 to PMX ® diaphragms is was reported to be EUR 1.4 – 2 million in 1999 [ 75, COM 2001 ] euros. A new diaphragm preparation plant will be built to supply two sites with PMX diaphragms in France. ChlorAlp in Pont de Claix (France) has estimated the costs for the modification of existing equipment at 0.4-0.8 million euros (costs of raw materials not included). 176 December 2011 TB/EIPPCB/CAK_Draft_1
Driving force for implementation The driving forces for implementation of this technique include: environmental as well as occupational health and safety legislation; reduction of costs related to energy consumption; reduction of costs related to cell maintenance. Chapter 4 Environmental occupational health regulations (asbestos ban, tighter asbestos regulations) are the key driving forces leading to the following benefits: no emissions of asbestos less generation of wastes because the renewal of the diaphragm is less frequent generated waste is non-hazardous Example plants Approximately ten plants worldwide use asbestos-free diaphragms [ 215, German Ministry 2011 ]. Example plants include: Arkema in Fos-sur-mer (France), chlorine capacity of diaphragm cell unit 150 kt/yr, cells: MDC-55, conversion to PMX ® diaphragms in 2000 – 2002 [ 31, Euro Chlor 2010 ]; Arkema in Lavera (France), chlorine capacity of diaphragm cell unit 175 kt/yr, cells: HC-4B, conversion to PMX ® diaphragms in 2000 – 2002 [ 31, Euro Chlor 2010 ]; Carbochloro in Cubatão/São Paulo (Brazil), chlorine capacity of diaphragm cell unit 140 kt/yr, cells: MDC-55, conversion announced for 2008 – 2009 [ 31, Euro Chlor 2010 ], [ 219, Carbocloro 2008 ]; Hüls in Rheinfelden (Germany), full conversion to PMX ® diaphragms in 1991, plant was shut down 1993 [ 221, Florkiewicz 1998 ]; Mexichem in Coatzacoalcos/Vera Cruz (Mexico); chlorine capacity of diaphragm cell unit 264 kt/yr, cells: Glanor [ 31, Euro Chlor 2010 ]; OxyChem (formerly Vulcan Chemicals) in Geismar/Louisiana (US), chlorine capacity of diaphragm cell unit 273 kt/yr, cells: MDC-55; full conversion to PMX ® diaphragms since 1993; Perstorp in Le Pont de Claix (France), chlorine capacity 170 kt/yr (only diaphragm cells), cells: H-4, HC-3B, conversion to PMX ® diaphragms in 1999 – 2003 [ 31, Euro Chlor 2010 ]; PPG in Lake Charles/Louisiana (US), chlorine capacity of diaphragm cell unit ~ 1 100 kt/yr, cells: Glanor V-1161 and V-1244; full conversion of V-1244 cells (chlorine capacity ~ 680 kt/yr) to Tephram ® diaphragms since 2003; full plant conversion to Tephram ® diaphragms finalised in 2010 [ 217, PPG 2010 ], [ 218, Ahmed and Foller 2003 ]; PPG in Natrium/West Virginia (US), chlorine capacity of diaphragm cell unit 297 kt/yr, cells: MDC-55, N-3 and N-6; full conversion of N-6 cells (chlorine capacity 58 kt/yr) to Tephram ® diaphragms since 1992; full plant conversion to Tephram ® diaphragms nearly completed in 2010 [ 214, Dilmore and DuBois 1995 ], [ 217, PPG 2010 ], [ 218, Ahmed and Foller 2003 ]; Sasol in Sasolburg (South Africa), chlorine capacity of diaphragm cell unit 92 kt/yr, cells: MDC-55 [ 31, Euro Chlor 2010 ]; Solvay in Rheinberg (Germany), chlorine capacity of diaphragm cell unit 110 kt/yr, cells: DAT/DBT-43, conversion to PMX ® diaphragms in 2011 – 2012 [ 118, Solvay 2011 ]. WORKING DRAFT IN PROGRESS OxyTech’s Polyramix (PMX) Diaphragm Vulcan Chemicals, Geismar, Louisiana, USA, has been fully converted to PMX diaphragms since 1993. This plant uses OxyTech MDC-55 cells at 150 kA. All of the 152 cells are equipped TB/EIPPCB/CAK_Draft_1 December 2011 177
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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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Chapter 3 current) and the efficien
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Chapter 3 distance means a higher f
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3.3.4.3.6 Production of caustic pot
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Chapter 3 hydrogen at low pressure
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28 kg of hydrogen is produced {Thes
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Chapter 3 depleted brine is recircu
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Chapter 3 Table 3.10: Emissions of
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Chapter 3 When measuring chlorine i
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Chapter 3 concentrations of organic
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Chapter 3 3.4.3 Emissions and waste
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Chapter 3 {Please TWG provide infor
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Chapter 3 in process and waste wate
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Chapter 3 produced per year has bee
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Chapter 3 of chlorine capacity. The
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Table 3.23: Mercury emissions from
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Mercury emissions in g Hg/t Cl capa
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Chapter 3 Table 3.24: Mercury emiss
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Chapter 3 KCl are higher than from
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Chapter 3 When concentrated solid c
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Chapter 3 Generally, storage of con
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Chapter 3 recycled brine systems si
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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
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
Page 191: Chapter 4 diaphragms [ 31, Euro Chl
Page 195 and 196: Chapter 4 4.2.3 Conversion of asbes
Page 197 and 198: Chapter 4 directly from the cells.
Page 199 and 200: 4.3 All Diaphragm and membrane cell
Page 201 and 202: Chapter 4 non-standardised) will be
Page 203 and 204: Chapter 4 removal of conductive com
Page 205 and 206: Chapter 4 Cross-media effects Plant
Page 207 and 208: Environmental performance and opera
Page 209 and 210: Example plants Dow, Stade (Germany)
Page 211 and 212: Chapter 4 current density resulting
Page 213 and 214: Chapter 4 modifications to auxiliar
Page 215 and 216: Table 4.14: Cost calculation for th
Page 217 and 218: Chapter 4 membrane lifetimes range
Page 219 and 220: Chapter 4 Cross-media effects Some
Page 221 and 222: Chapter 4 The drawback of using fer
Page 223 and 224: Chapter 4 evaporation unit integrat
Page 225 and 226: Chapter 4 Environmental performance
Page 227 and 228: Chapter 4 Technical description The
Page 229 and 230: Chapter 4 Table 4.17: Monitoring te
Page 231 and 232: Chapter 4 Environmental performance
Page 233 and 234: Environmental performance and opera
Page 235 and 236: Chapter 4 Prevention of chlorine re
Page 237 and 238: Chapter 4 Good pipework design to m
Page 239 and 240: Chapter 4 was the solution at that
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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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