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

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Chapter 2 Table 2.4: Typical impurities with sources and effects on the membrane cell technique as well as typical brine specifications Example of brine specifications for the membrane process operating at a current density up to 4 kA/m 2 Impurity Source Ca 2+ + Mg 2+ Sr 2+ Ba 2+ Al 3+ Fe 3+ Hg 2+ Ni 2+ ClO3 - I (e.g. H2IO6 3- ) Iodine F - SO4 2- Salt 20 ppb Salt Upper limit of brine specification 0.1 – 4 ppm 0.04 ppm Effects Influence Ca: CE Mg: V CE, V Salt 0.05 – 0.5 ppm CE, V Salt 0.1 ppm CE, V Salt, pipework, tank material, anti-caking agent Parallel operation of mercury cell plant 0.05 – 0.1 ppm ( 1 ) 1 ppm 0.2 ppm heavy metals 10 ppm V Mechanism Remarks Ca: Precipitation with various anions near cathode side of membrane, precipitation with silica and iodine in the membrane Mg: Fine precipitation with OH - near anode side of membrane, precipitation with silica in the membrane Precipitation with hydroxide on cathode side of membrane, precipitation with silica and iodine in the membrane Sr and SiO2 seem to be co-precipitated within the membrane. (synergistic effect) 0.04 ppm in Sr content in purified brine is easily kept under normal operation of Chelating Resin Tower. If SiO2 content is kept less than 1 ppm, then Sr is allowable up to 0.1 ppm. Very fine precipitation with iodine in the membrane, precipitation with silica in the membrane Ba and Iodine seem to be co-precipitated within the membrane. (synergetic effect) When SO4 content is kept 6 g/l, Ba content should be 0.05ppm or less. Precipitation with silica in the membrane, precipitation of calcium/strontium aluminosilicates near cathode side of membrane Deposition on cathode, precipitation with hydroxide on anode side of membrane or in the membrane (depending on pH of the brine) V Deposition on cathode Mainly due to caustic user needs and risk of cathode damage Salt, pipework, 0.2 ppm heavy tank material, metals V Deposition on cathode, absorption in membrane cathode 0.01 ppm Process side reactions 10 g/l (as NaClO3) 20 g/l O Chlorination of ion-exchange resin Salt 0.5 ppm 0.1 – 0.2 ppm CE, V Very fine precipitation with calcium, strontium or barium in the membrane, precipitation with sodium on cathode side of membrane Iodine originates from underground salt and water. If solar salt and ordinary surface water are used, Iodine content should be 0.1 ppm or less. Salt 0.5 ppm V Destruction of anode coating Salt, dechlorination with NaHSO3 < 4 – 8 g/l (as Na2SO4) 6 g/l CE Precipitation with sodium near cathode side of membrane, anode coating with barium We are evaluating to raise the upper limit to 8 g/l. WORKING DRAFT IN PROGRESS 44 December 2011 TB/EIPPCB/CAK_Draft_1
Impurity Source Upper limit of brine specification Effects Influence SiO2 (e.g. SiO3 2- ) Salt 10 ppm CE Mechanism Remarks WORKING DRAFT IN PROGRESS Chapter 2 Silica itself is harmless, but in presence of magnesium, calcium, strontium, barium or aluminium, silicates can be formed (see above) Suspended solids SS Salt 0.5 – 1 ppm V Precipitation on anode side of membrane Suspended Solid Total organic carbon TOC Salt 1 – 10 ppm V Increased foaming, overplating Total Organic Carbon Heavy Metals 0.1 ppm Mn 0.1 ppm The limit is 0.05 ppm in some plants due to caustic user needs. Cr 1 ppm Mainly due to caustic user needs Cu 0.01 ppm Mainly due to caustic user needs ( 1 ) Higher iron concentrations could be permissible in cases of non-acidified feed brine. NB: CE = current efficiency decreases; O = other effects; V = cell voltage increases. Source: [ 1, Ullmann's 2006 ], [ 23, BASF 2010 ], [ 72, Nishio 2011 ], [ 136, Asahi Kasei 2008 ], [ 146, Arkema 2009 ] (Source: Asahi Glass Co) {The table was updated and restructured (order of rows: earth alkali metals, other cations, anions, other impurities; column on source of impurity was added; columns on upper limit and unit were merged; information in the column on condition was moved to the mechanism column).} CE: Current Efficiency should decrease V: Cell Voltage should increase TB/EIPPCB/CAK_Draft 1 December 2011 45
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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 ..........
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 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: Source: [ 29, Asahi Glass 1998 ] (p
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 and 110: 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 Table 3.21: Emissions of
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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 Table 3.25: Emissions of
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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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