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

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Chapter 1 1.5 Environmental relevance of the chlor-alkali industry The chlor-alkali industry is an energy-intensive industry and consumes large amounts of electricity during the electrolysis process. Additional energy in the form of steam or electricity is necessary for auxiliary processes, which depend on the cell technique used. In 2008, the total electricity consumption of the chlor-alkali sector in EU-27 and EFTA countries amounted to 36 TWh [ 13, Euro Chlor 2008 ]. This was equivalent to 17 % of the total final energy consumption in the form of electricity of the chemical industry and to approximately 3 % of all industry sectors in this region [ 14, Eurostat 2010 ]. Inputs and pollutant outputs from the chlor-alkali industry are quite specific to the cell technology used, the purity of the incoming salt and the specifications of the products. Because of the huge amount of electricity needed in the process, energy can be considered as a raw material. The chlor-alkali process is one of the largest consumers of electrical energy. All three cell techniques (mercury, diaphragm and membrane cell technique) may give rise to emissions of chlorine to air through leakages during production, handling and storage, as well as to channelled emissions from the chlorine absorption unit. The substances emitted through waste water include free oxidants, chlorate, bromate, chloride, sulphate and halogenated organic compounds. For many years, the mercury cell technique has been a significant source of environmental pollution, because some mercury is lost from the process to air, water, products and wastes. Inorganic mercury can be metabolised to form highly toxic methyl mercury by anaerobic bacteria, and this organic mercury is bio-accumulated 1 in the food chain. Most of the mercury which leaves an installation is disposed of with waste. Releases to the environment from the installation mostly occur to the atmosphere as diffuse emissions from the cell room. Significant emissions may also occur during decommissioning of the installation. It is recognised that the main part of the mercury losses is in the different wastes from the process. Considerable emissions of mercury can also occur with run-off water. The soil at many sites is contaminated with mercury due to deposition of diffuse emissions and/or historical disposal of mercury contaminated wastes. The mercury leaks from the soil and ends up in the run-off water. Another big entry is the ‘Difference to Balance’. The annual mercury balance for a site is never zero. This is because mercury accumulates in plant equipment and structures during the life of the plant. Data on mercury emissions for EU-27 and EFTA countries can be found in the technical background report to the global atmospheric mercury assessment from AMAP/UNEP for the reference year 2005 [ 15, AMAP/UNEP 2008 ]. Based on these data, the total annual mercury emissions of the chlor-alkali industry for EU-27 and EFTA countries amounted to 5.98 t, equivalent to 5.2 % of the total anthropogenic emissions in this region. The greatest emissions of mercury originate from stationary combustion (45.4 %), metal production (15.1 %) and cement production (13.6 %). There is, however, some uncertainty about mercury emissions from mercury cell chlor-alkali plants due to methodological difficulties in quantifying the diffuse emissions and in setting up a mercury input-output balance. WORKING DRAFT IN PROGRESS The chlor-alkali industry was the largest domestic user of mercury in the years 1989 to 1990 in the US and this could be expected to be the same in Europe [J. Ind. Ecology, 1997]. Based on the European Atmospheric Emission Inventory of Heavy Metals and Persistent Organic Pollutants [UBA (D)-TNO report, 1997] in the 15 EU countries, the highest emitters of mercury to air in 1990 include: coal burning electric utilities (highest figure of 90.5 tonnes), municipal 1 In the 1950s a chemical plant producing acetaldehyde discharged a spent catalyst containing organic mercury into Minimata Bay, Japan. A number of people (mostly fishermen) became seriously ill and some were disabled. This event was at the origin of environmental regulations in Japan and caused changes into mercury free technologies in some industrial sectors. {Minamata is mentioned with less details in 2.4.1}. 14 December 2011 TB/EIPPCB/CAK_Draft _1
Chapter 1 and hazardous waste incinerators and cement industry (37.7 tonnes). Chlor-alkali emissions to air are reported to be 28.4 tonnes. A USEPA report, dated 1998, identifies the same sources of emissions: municipal waste incinerators, medical waste incinerators, hazardous waste incinerators and industrial boilers. In addition, certain manufacturing processes, most notably chlor-alkali and cement plants, are listed although their emissions are substantially lower than those of incineration sources. According to Euro Chlor, the total mercury emission to air, water and products from chlor-alkali plants in western Europe the EU-27 was 9.5 tonnes in 1998, ranging between 0.2-3.0 g Hg/tonne of chlorine capacity at the individual plants. Several policy initiatives and regulations on a European and international level since the 1990s have aimed at reducing mercury emissions to the environment, starting with the PARCOM decision 90/3. This decision recommended that existing mercury cell chlor-alkali plants should be phased out as soon as practicable, with the objective of a complete phase-out by 2010. Moreover, the EU mercury strategy was adopted in 2005, the EU mercury export ban took effect in 2011 and negotiations under the auspices of UNEP to develop a global, legally-binding instrument on mercury started in 2010. Decision 90/3 of 14 June 1990 of the Commission for the Protection of the Marine Environment of the North-East Atlantic (PARCOM 2 ) recommends that existing mercury cell chlor-alkali plants should be phased out as soon as practicable. The objective was that they should be phased out completely by 2010. Emissions of asbestos are of concern for some diaphragm cell plants. Regulation EC/1907/2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH), generally prohibit the use of asbestos fibres, but EU Member States can grant an exemption for the use of asbestos-containing diaphragms in existing electrolysis installations until they reach the end of their service life, or until suitable asbestos-free substitutes become available, whichever is the sooner. The use of asbestos diaphragms has been prohibited in France and the state of São Paulo (Brasil). As regards the diaphragm cell technique, due to the potential exposure of employees to asbestos and releases to the environment, the use of good practices is needed and some efforts are being made to replace the asbestos with other diaphragm material. At some sites, historical mercury and PCDD/PCDF contamination of land and waterways from mercury and diaphragm cell chlor-alkali plants is a big major environmental problem. at some sites. Accident prevention and minimising their consequences to the environment is also of major importance for chlor-alkali installations which in most cases fall under the scope of the Seveso II Directive (96/82/EC). With the inputs/outputs of the chlor-alkali sector, it is also relevant to point out the special importance of safety aspects related to production, handling, transport and storage of chlorine. WORKING DRAFT IN PROGRESS 2 Since 1992 OSPARCOM. Publications can be found at http://www.ospar.org TB/EIPPCB/CAK_Draft_1 December 2011 15
Page 1 and 2: EUROPEAN COMMISSION JOINT RESEARCH
Page 3 and 4: PREFACE 1. Status of this document
Page 5 and 6: Reference Document on Best Availabl
Page 7 and 8: 3.4.7 Emissions of noise ..........
Page 9 and 10: 4.3.6.3.3 Chemical reduction ......
Page 11 and 12: List of Tables Table 2.1: Main char
Page 13 and 14: List of Figures Figure 1.1: Share p
Page 15 and 16: SCOPE WORKING DRAFT IN PROGRESS Sco
Page 17 and 18: 1 GENERAL INFORMATION 1.1 Industria
Page 19 and 20: Chlorine production in Mt/yr 12 11
Page 21 and 22: Chapter 1 Figure 1.4 shows the annu
Page 23 and 24: Share of total capacity in % 70 70%
Page 25 and 26: 1.4 Chlor-alkali products and their
Page 27 and 28: Total consumption: 9 801 kt Miscell
Page 29: 1.4.5 Consumption of hydrogen Chapt
Page 33 and 34: 2 APPLIED PROCESSES AND TECHNIQUES
Page 35 and 36: Chapter 2 WORKING DRAFT IN PROGRESS
Page 37 and 38: Chapter 2 The main characteristics
Page 39 and 40: 2.2 The mercury cell technique proc
Page 41 and 42: Chapter 2 Characteristics of the ca
Page 43 and 44: 2.3 The diaphragm cell technique pr
Page 45 and 46: Source: [ 2, Le Chlore 2002 ] [USEP
Page 47 and 48: 2.4 The membrane cell technique pro
Page 49 and 50: Chapter 2 (carcinogenic) [ 76, Regu
Page 51 and 52: Chapter 2 The membranes used in the
Page 53 and 54: Table 2.2: Typical configurations o
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
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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
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3.5.9.5 Graphite and activated Acti
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Chapter 3 Table 3.31: Yearly waste
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Chapter 3 The fact that the differe
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Chapter 3 3.6 Emissions Emission an
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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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