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

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Chapter 4 4.3.3 Metal anodes {All chlor-alkali installations in the world use metal anodes. It is therefore proposed to delete this section. An update can be found in the section on high-performance electrodes and coatings (Section 4.3.2.3.4).} 4.3.4 Techniques for monitoring of emissions 4.3.4.1 Overview Generic issues of monitoring are described in the Reference Document on General Principles of Monitoring [ 70, COM 2003 ]. This section deals with specific issues of monitoring of emissions which are of relevance for the chlor-alkali manufacturing industry. This includes the monitoring frequency and the available analytical methods. Some analytical methods are described in detail either because their use in the sector shows some peculiarities or because there are different methods used which lead to different results. The monitoring of process parameters which are not linked to emissions is not covered in this section. 4.3.4.2 Common issues of all monitoring techniques In order to avoid repetitions in the following sections, common issues for all monitoring techniques are described here. Achieved environmental benefits The achieved environmental benefit of monitoring is an improvement of environmental performance by helping to maintain a proper operation of the plant, including its pollution prevention and control systems. Monitoring is a prerequisite for corrective actions. Cross-media effects Some equipment, ancillary materials and energy are required for the monitoring. Technical considerations relevant to applicability Generally, there are no technical restrictions to the applicability of monitoring techniques. Driving force for implementation The driving forces for implementation of this technique include: environmental legislation; process control. 4.3.4.3 Monitoring techniques and frequency Description Monitoring techniques and frequency used vary considerably in chlor-alkali plants in EU-27 and WORKING DRAFT IN PROGRESS EFTA countries. The monitoring frequency is usually determined using a risk-based approach which takes into account both the likelihood of exceeding an emission limit value and the resulting consequences [ 70, COM 2003 ]. Technical description Table 4.17 provides an overview of monitoring techniques and frequency. 212 December 2011 TB/EIPPCB/CAK_Draft_1
Chapter 4 Table 4.17: Monitoring techniques and frequency for pollutants of relevance in diaphragm and membrane cell chlor-alkali plants Environmental Medium Substance Technique used Standard/Analytical method Measurement frequency ( 1 ) Chlorine See Section 4.3.4.4 C, SM, Q, SY Air Chlorine dioxide See Section 4.3.4.4 NRM Bromate {Please TWG provide information.} D, W, M ( 3 ) Chlorate Titration Ion chromatography [ 169, Ijspeerd et al. 1977 ] [ 170, Desai et al. 1999 ], [ 171, Metrohm 2011 ] SM, M Ion chromatography EN ISO 10304-1 [ 172, CEN 2009 ] Chloride Flow analysis EN ISO 15682 [ 173, CEN 2001 ] D, W, SM, M Silver nitrate titration (Mohr's method) ISO 9297 [ 174, ISO 1989 ] Free oxidants See Section 4.3.4.5 C, D, M Halogenated organic compounds See Section 4.3.4.6 SM, M, Q, SY ( 2 Water ) Sulphate Ion chromatography Continuous flow EN ISO 10304-1 [ 172, CEN 2009 ] ISO 22743 [ 176, ISO D, W, SM, M analysis 2006 ] ( 1 ) Information taken from [ 57, EIPPCB 2011 ]. See also Chapter 3. ( 2 ) Data from less than 10 plants. NB: C = continuous, D = daily; M = monthly; NRM = not routinely measured; Q = quarterly; SM = semi-monthly; SY = semi-yearly; W = weekly. Letters in bold indicate measurement frequencies which are mostly used. Environmental performance and operational data {Please TWG provide information.} Economics {Please TWG provide information.} Example plants Most of the parameters listed in Table 4.17 are frequently measured by diaphragm and membrane cell chlor-alkali plants in EU-27 and EFTA countries. Chlorine dioxide in air as well as bromate and halogenated organic compounds in water are less frequently measured. Reference literature [ 57, EIPPCB 2011 ], [ 70, COM 2003 ], [ 169, Ijspeerd et al. 1977 ], [ 170, Desai et al. 1999 ], [ 171, Metrohm 2011 ], [ 172, CEN 2009 ], [ 173, CEN 2001 ], [ 174, ISO 1989 ], [ 176, ISO 2006 ] WORKING DRAFT IN PROGRESS 4.3.4.4 Monitoring of chlorine and chlorine dioxide in air Issues of general relevance for all monitoring techniques are described in Section 4.3.4.2. Description Two categories of monitoring techniques for chlorine in air are generally used. The first is based on absorption of chlorine in a liquid with subsequent wet chemical analysis while the second is based on direct measurements in the gas phase with electrochemical cells. Other oxidising TB/EIPPCB/CAK_Draft_1 December 2011 213
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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
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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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Page 179 and 180: 3. Emptying of the cells and handli
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Page 187 and 188: 4.2 Diaphragm cell plants 4.2.1 Aba
Page 189 and 190: Source: [ 146, Arkema 2009 ] Figure
Page 191 and 192: Chapter 4 diaphragms [ 31, Euro Chl
Page 193 and 194: Driving force for implementation Th
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Page 197 and 198: Chapter 4 directly from the cells.
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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: Chapter 4 Technical description The
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
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Page 239 and 240: Chapter 4 was the solution at that
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Page 243 and 244: Chapter 4 chlorine scrubber, immedi
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Page 249 and 250: environmental legislation; generati
Page 251 and 252: Chapter 4 Table 4.21: Examples of o
Page 253 and 254: Chapter 4 Driving force for impleme
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Page 257 and 258: Chapter 4 In both cases, the spent
Page 259 and 260: Chapter 4 Example plants Thermal de
Page 261 and 262: Chapter 4 migration of hydroxide io
Page 263 and 264: eduction of chlorate emissions; red
Page 265 and 266: Example plants Solvin in Antwerp-Li
Page 267 and 268: eduction of costs related to equipm
Page 269 and 270: Chapter 4 Off-site reconcentration
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Page 273 and 274: 4.4 Membrane cell plants 4.4.1 High
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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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