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

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Chapter 3 3.2 Overall Overview of emission and consumption levels of all cell plants Emission and consumption levels Inputs and pollutant outputs of the chlor-alkali industry are quite specific to the cell technique technology used but also depend on the specifications of the products (O2 or CO2 content, for example), the purity of the incoming salt and the geographical location of the plant. The inputs are primarily salt and water as feedstock, acids and chemical precipitants used to remove impurities in the input brine or output chlorine/caustic soda, as well as refrigerants cooling agents (CFCs, HCFCs, HFCs, ammonia, etc.) for liquefying and purifying the chlorine gas produced. The chlor-alkali process needs huge amounts of electricity and electrical energy is a major input. The main pollutant outputs which are common to all three electrolytic processes are emissions of chlorine and refrigerants to air, emissions of noise, emissions of free oxidants, chlorate, bromate, chloride, sulphate and halogenated organic compounds to water as well as the generation of spent acids from chlorine drying and sludges from brine purification. chlorine gas emissions, spent acids, cooling agents, impurities removed from the input salt or brine. The major pollutant in terms of environmental impact, originating from the mercury cell technique amalgam technology, is mercury. Due to the process characteristics, mercury can be released emitted from the process to through air, water, wastes and in the products. The diaphragm cell and membrane cell techniques are more concerned with spent materials generation, such as asbestos waste in the case of asbestos diaphragms. because of the replacement of the cell materials needed for the process. In the diaphragm process, deterioration of the asbestos-based diaphragms is the main reason for cell renewal. In view of the potential exposure of employees to asbestos and releases into the environment, special care must be taken. In addition, the improvement in cell component materials such as metal anodes and modified diaphragms, which are more stable, has helped to reduce the formation of undesirable and polluted by-products. {This information is too detailed for an introducing section.} Mercury outputs have decreased in the last twenty years as amalgam cell plant operators have been more active in reducing mercury emissions, although the attention paid to this may vary from one country to another. According to Euro Chlor, mercury emissions to air and water per tonne chlorine capacity in western Europe were 27 g in 1977, 8 g in 1987 and around 2 g in 1997. Furthermore, the industry moved away in the 1990s from the mercury process to the more efficient (in terms of material and energy inputs and outputs) membrane cell process (first European membrane plant in 1983 at Akzo in Rotterdam). {The information was updated and moved to Section 3.5.5.} Table 3.1 gives an overview of the main emission and consumption levels inputs and outputs of the three chlor-alkali techniques technologies, using a brine recirculation process. The information is collected from available sources and is not complete. Chlorine liquefaction is not included, nor are emissions from cooling systems. This table represents a summary of Chapter 3. WORKING DRAFT IN PROGRESS 64 December 2011 TB/EIPPCB/CAK_Draft_1
Chapter 3 Table 3.1: Overview of emission and consumption levels inputs and outputs of the three chlor-alkali manufacturing techniques processes {The column order was modified.} INPUTS Consumption, per tonne of chlorine produced Mercury Amalgam Diaphragm Membrane Comments Raw materials Depends on impurities; in Salt (NaCl) 1650 – 2340 1750 kg theory 1650 1660 kg (with no losses) Salt (KCl) 2100 – 2200 kg Depends on impurities; theory 2100 kg (no losses) in Water 1 – 2.8 m 3 {Please TWG provide updated data.} Only process water {Please TWG provide updated data.} Steam for caustic concentration NA 2.7 – 5.3 t 610 kWh 0.5 – 1.7 t 180 kWh AC, typical use For 50 wt-% caustic Electricity for electrolysis Auxiliaries 3000 – 4400 AC kWh 3560 kWh 2.6 – 10.9 g 2600 – 3100 AC kWh 2970 kWh 2300 – 3000 AC kWh 2790 kWh AC, typical use, Depends on the current density; chlorine liquefaction/evaporation excluded Mercury {Please TWG provide updated data.} NA NA Asbestos NA 0.1 – 0.3 kg NA Only if asbestos diaphragms are used Emissions, per tonne of annual chlorine capacity produced Mercury Amalgam Diaphragm Membrane Comments To air Hydrogen < 0.3 – 14 kg 100 – 1000 g < 1 % to emitted > 50 % hydrogen Chlorine 0.000050 – 13 g 0 – 16 g Refers to channelled emissions CO2 1.2 – 5 kg Mercury 0.09 – 1.47 g 0.2 – 2.1 g NA 0.04 mg NA western Europe 1998 Asbestos To water NA {Please TWG provide updated data.} NA Only if asbestos diaphragms are used higher figure if remains from Free oxidants 0.0003 – 300 g 0.001 – 1.5 kg bleach discharged destruction are Chlorate < 0.0018 – 5 kg 0.14 – 4 kg Depends on whether a chlorate decomposer is installed or not; higher figure if thermal bleach destruction is applied Bromate 0.050 – 850 g 0.22 – 550 g higher figure if thermal bleach destruction is applied Chloride Halogenated organic 0.043 – 200 kg 4 – 25 kg compounds Chlorinated hydrocarbons 0.015 – 7 g 0.03 – 1.16 g Measured as AOX or EOX WORKING DRAFT IN PROGRESS TB/EIPPCB/CAK_Draft_1 December 2011 65
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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
Page 29 and 30: 1.4.5 Consumption of hydrogen Chapt
Page 31 and 32: Chapter 1 and hazardous waste incin
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: 3 CURRENT PRESENT EMISSION AND CONS
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 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
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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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