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

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Table 3.29: Mercury concentrations in brine filtration sludges of chlor-alkali plants in EU-27 and EFTA countries in 2008/2009............................................................................................124 Table 3.30: Waste generation and final treatment at the AkzoNobel chlor-alkali plant in Bohus (Sweden) in 1998/1999 (chlorine capacity 100 kt/yr; production based on vacuum salt)..126 Table 3.31: Yearly waste Waste generation and final treatment at the Hydro Polymers AB chloralkali plant in Stenungsund (Sweden) (chlorine capacity 120 kt/yr; production based on vacuum salt) .......................................................................................................................127 Table 3.32: Mercury collected, recovered or disposed of with waste during decommissioning ...........130 Table 3.33: Concentrations of asbestos in air in chlor-alkali plants in the EU-27 ................................133 Table 3.34: Estimation of total number of mercury-contaminated chlor-alkali sites in EU-27 and EFTA countries and contamination levels .........................................................................137 Table 3.35: Examples of mercury-contaminated chlor-alkali sites in EU-27 and EFTA countries.......138 Table 3.36: Examples of chlor-alkali sites contaminated with PCDDs/PCDFs, PCBs, PCNs and PAHs ..................................................................................................................................140 Table 4.1: Information for each technique described in this chapter....................................................144 Table 4.2: Data from the conversion of the Borregaard chlor-alkali plant to the membrane cell technique technology..........................................................................................................151 Table 4.3: Electricity savings due to conversion to the membrane cell technique in different chloralkali plants ........................................................................................................................152 Table 4.4: Investment costs for the cell room conversion of a mercury cell plant with a final chlorine capacity of 100 kt/yr.............................................................................................155 Table 4.5: Investment costs for the conversion of a mercury cell plant with a chlorine capacity of 100 kt/yr and a design current density of 5 kA/m 2 .............................................................156 Table 4.6: Comparison of reported conversion costs ..........................................................................157 Table 4.7: Overview of contaminated solid materials arising during decommissioning and possible decontamination techniques ...............................................................................................165 Table 4.8: Techniques for monitoring of mercury in air, water and waste..........................................167 Table 4.9: Costs for decommissioning of the Borregaard plant in Sarpsborg (Norway).....................168 Table 4.10: Decommissioning costs at the Ercros mercury cell chlor-alkali plant in Sabiñánigo (Spain) in 2009...................................................................................................................169 Table 4.11: Number of cells and electrolysers as a function of current density for a bipolar membrane cell plant with a chlorine capacity of 100 kt/yr ................................................195 Table 4.12: Electricity consumption of bipolar membrane cell electrolysers using the latest technique as a function of current density..........................................................................196 Table 4.13: Typical production costs for a membrane cell chlor-alkali plant with a chlorine production capacity of 500 kt/yr ........................................................................................197 Table 4.14: Cost calculation for the replacement of an electrolysis unit...............................................199 Table 4.15: Energy consumption for brine reconcentration in membrane cell plants using solutionmined brine.........................................................................................................................207 Table 4.16: Operational data for caustic concentration of plate and shell-and-tube evaporators ..........209 Table 4.17: Monitoring techniques and frequency for pollutants of relevance in diaphragm and membrane cell chlor-alkali plants ......................................................................................213 Table 4.18: List of some preventative and corrective or emergency measures to avoid accidents at loading areas of a chlor-alkali plant ...................................................................................219 Table 4.19: List of some preventative and corrective or emergency measures to avoid accidents associated with storage of liquid chlorine ..........................................................................221 Table 4.20: Advantages and disadvantages of refrigerants frequently used in chlor-alkali plants........230 Table 4.21: Examples of operational cost savings for plants replacing brine purge or barium sulphate precipitation by nanofiltration..............................................................................235 Table 4.22: Typical operating costs for partial hypochlorite destruction using catalytic fixed-bed decomposition or chemical reduction.................................................................................241 WORKING DRAFT IN PROGRESS Table 4.23: Typical operational data from an on-site sulphuric acid reconcentration system...............252 Table 4.24: Potential techniques for the decontamination of mercury-contaminated soils ...................261 Table 6.1: Business case for a 2 MW PEMFC power plant (investment cost: EUR 5 000 000).........298 Table A.1: Installed chlorine production capacities in EU-27 and EFTA countries as of 1 January 2011....................................................................................................................................324 x December 2011 TB/EIPPCB/CAK_Draft_1
List of Figures Figure 1.1: Share per region of world chlorine production capacities in 2008 ........................................ 2 Figure 1.2: Development of chlorine production in western Europe and utilisation ratio of plant capacity in EU and EFTA countries ...................................................................................... 3 Figure 1.3: Chlor-alkali production sites in EU-27 and EFTA countries as of January 2011 Geographic distribution of chlor-alkali plants within the European Union 1999 .................. 4 Figure 1.4: Annual chlorine production capacities in EU-27 and EFTA countries in 2010 Chlorine production in western Europe in 1999................................................................................... 5 Figure 1.5: Share of cell techniques to chlorine production capacity in EU-27 and EFTA countries...... 7 Figure 1.6: Chlorine applications in EU-27 and EFTA countries in 2010 western Europe ..................... 9 Figure 1.7: Caustic soda applications in EU-27 and EFTA countries in 2010....................................... 11 Figure 1.8: Caustic potash applications in EU-27 and EFTA countries in 2009.................................... 12 Figure 2.1: Flow diagram of the three typical main chlor-alkali techniques processes.......................... 18 Figure 2.2: Simplified scheme of chlorine electrolysis cells.................................................................. 19 Figure 2.3: Schematic view of a mercury electrolysis cell with horizontal and vertical decomposer Flow diagram of mercury cell technology ........................................................................... 23 Figure 2.4: View of a mercury cell room ............................................................................................... 25 Figure 2.5: Flow diagram of the integration of the membrane or mercury and the diaphragm cell techniques ............................................................................................................................ 27 Figure 2.6: Sectional drawing of a typical monopolar diaphragm electrolysis cell ............................... 29 Figure 2.7: View of an open-air diaphragm cell room equipped with monopolar electrolysers ............ 29 Figure 2.8: Flow diagram of the integration of the membrane and mercury cell techniques ................. 32 Figure 2.9: Exploded view of a monopolar membrane electrolyser Sectional drawing of a typical bipolar membrane electrolysis cell ...................................................................................... 33 Figure 2.10: View of a membrane cell room equipped with bipolar electrolysers................................... 34 Figure 2.11: View of a membrane cell room equipped with monopolar electrolysers............................. 34 Figure 2.12: Sectional drawing of a membrane ....................................................................................... 35 Figure 2.13: Simplified scheme of monopolar and bipolar electrolysers................................................. 36 Figure 2.14: Electrolyser architecture ...................................................................................................... 36 Figure 2.15: Flow diagram of a possible layout for the brine purification system used in the membrane cell technique process ........................................................................................ 41 Figure 2.16: View of polishing filters in a secondary brine purification system...................................... 42 Figure 2.17: View of chelate resin towers in a secondary brine purification system ............................... 43 Figure 2.18: View of a chlorine absorption unit ...................................................................................... 56 Figure 2.19: View of caustic production and storage............................................................................... 59 Figure 3.1: Cell voltage and specific electrical energy consumption versus cell current density for the mercury cell technique................................................................................................... 73 Figure 3.2: Specific electrical energy consumption versus cell current density for the different chlor-alkali electrolysis techniques...................................................................................... 76 Figure 3.3: Trend of mercury emissions (weighted averages) from mercury cell chlor-alkali plants in Western Europe (OSPAR countries) as reported by Euro Chlor ................................... 109 Figure 3.4: Trend of mercury emissions (weighted averages) from mercury cell chlor-alkali plants in EU-27 and EFTA countries as reported by Euro Chlor................................................. 110 Figure 3.5: Major solid waste sources in mercury cell chlor-alkali plants Solid waste sources in the mercury process................................................................................................................. 123 Figure 3.6: Trend of the average difference to balance for chlor-alkali plants in OSPAR countries ... 128 Figure 4.1: Mercury cell plant conversion to a membrane cell plant technology ................................ 148 Figure 4.2: Deposition of an asbestos-free diaphragm on a cathode.................................................... 173 WORKING DRAFT IN PROGRESS Figure 4.3: Continuous improvement in an EMS model...................................................................... 183 Figure 4.4: Impact of technological development of the membrane cell technique on specific electricity consumption and maximum current densities................................................... 196 Figure 4.5: Choice of current density based on capital costs and electricity prices ............................. 198 Figure 4.6: Flow diagram of brine recirculation and once-through brine processes ............................ 206 Figure 4.7: Schematic Flow diagram of a catalytic decomposition reduction fixed-bed reactor process ............................................................................................................................... 240 Figure 4.8: Effect of pH value on the location of iron hydroxide precipitation in membranes............ 245 Figure 4.9: Flow diagram of acidic chlorate reduction ........................................................................ 246 Figure 4.10: Flow diagram of the on-site thermal desorption system used at a chlor-alkali site in Taipei (Taiwan) ................................................................................................................. 262 Figure 4.11: Flow diagram of a soil washing system............................................................................. 264 TB/EIPPCB/CAK_Draft_1 December 2011 xi
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: List of Tables Table 2.1: Main char
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 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
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Chapter 2 composition of the chlori
Page 69 and 70:
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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Page 107 and 108:
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 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.,
Page 323 and 324:
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
Page 341 and 342:
Euro Chlor No. Country code Company
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