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

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Chapter 5 5.7 Emissions to air 10. In order to reduce channelled emissions of chlorine and chlorine dioxide to air from the processing of chlorine, BAT is to use a chlorine absorption unit. Description The chlorine absorption unit consists of a wet scrubber with caustic solution as scrubbing liquid which can make use of packed columns or ejectors. Hydrogen peroxide dosing equipment or a separate wet scrubber with hydrogen peroxide is used to reduce emissions of chlorine dioxide. The BAT-associated emission level for chlorine and chlorine dioxide (expressed as Cl2) is < 0.10 – 1.0 mg/m 3 as hourly average value at the outlet of the chlorine absorption unit based on absorption of the waste gas in sulphamic acid solution and determination of total chlorine according to EN ISO 7393–1 or –2 (see BAT 9). The lower end of the range is close to the typical limit of detection of the monitoring method. [This BAT conclusion is based on information given in Sections 4.3.5.1.2 and 4.3.5.2.] 11. In order to reduce channelled emissions of chlorine during incidents and accidents including power failure, BAT is to use a chlorine absorption unit that absorbs the full cell room production for a sufficient duration until the plant is shut down. Description See BAT 10. [This BAT conclusion is based on information given in Section 4.3.5.1.2.] 12. The use of carbon tetrachloride for the elimination of nitrogen trichloride or the recovery of chlorine from tail gas is not BAT. In order to prevent emissions of carbon tetrachloride to air, BAT is to avoid the use of carbon tetrachloride by using a combination of the techniques given below. Technique Description Applicability a Direct use of chlorine Chlorine is compressed and used directly without liquefaction, in order to prevent the potential accumulation of nitrogen trichloride in liquid chlorine. Applicable to sites which can directly use the chlorine of this quality. b Reduction of nitrogen intake The nitrogen intake via the raw materials (salt, water, ancillary materials) is reduced, in order to reduce the formation of nitrogen trichloride. Generally applicable. c Removal of ammonia from the brine Ammonia is removed from the brine at alkaline pH by stripping or by breakpoint chlorination, in order to reduce the formation of nitrogen trichloride. Techniques to destroy NCl3 include: Generally applicable. Destruction of reaction with sodium hydroxide or d nitrogen hydrochloric acid; Generally applicable. trichloride decomposition using heat, irradiation or activated carbon. e Absorption of chlorine in caustic solution Absorption leads to the recovery of chlorine from the tail gas to produce bleach which can be sold, recycled to the brine system or destroyed. Generally applicable. f Production of other substances The residual chlorine in the tail gas is used to produce other substances such as hydrochloric acid, iron(III) chloride and ethylene dichloride. Applicable to sites with a demand or market for the produced substances. WORKING DRAFT IN PROGRESS 280 December 2011 TB/EIPPCB/CAK_Draft_1
[This BAT conclusion is based on information given in Section 4.3.5.3.] Chapter 5 13. In order to prevent emissions of ozone-depleting substances and of substances with high global warming potential such as HCFCs and HFCs to air from the chlorine liquefaction process, BAT is to use refrigerants without ozone depletion potential and with a global warming potential below 10. Description Suitable refrigerants include ammonia, carbon dioxide, chlorine, and water. [This BAT conclusion is based on information given in Section 4.3.5.4.] 5.8 Emissions to water 14. In order to reduce emissions of chloride to water from the brine purge and the chlorine absorption unit, BAT is to use a combination of the techniques given in BAT 4. The BAT-associated emission level of chloride (Cl - ) is {tbd} kg/t of chlorine produced as yearly average value. {NB: {tbd} = to be determined after further data collection.} 15. In order to reduce emissions of free oxidants to water from the brine purge and the chlorine absorption unit, BAT is to use one or a combination of the techniques given below. Technique Description a Chemical reduction b Catalytic decomposition c Thermal decomposition d Acidic decomposition The free oxidants are destroyed by reaction with reducing agents such as sulphite and hydrogen peroxide in stirred tanks. The free oxidants are decomposed to chloride and oxygen in catalytic fixed-bed reactors. The catalyst used can be a nickel oxide promoted with iron on an alumina support. The free oxidants are converted to chloride and chlorate by thermal decomposition at approximately 70 °C. The resulting effluent requires further treatment to reduce emissions of chlorate and bromate (see BAT 16). The free oxidants are decomposed by acidification with release and recovery of chlorine. Acidic decomposition can be carried out in a separate reactor or by recycling of the waste water to the brine system. The degree of recycling of waste water to the brine circuit is restricted by the water balance of the plant. [Section on which BAT conclusion is based] [4.3.6.3.3] [4.3.6.3.4] [4.3.6.3.5] [4.3.6.3.6] The BAT-associated emission level for the sum of free oxidants (expressed as Cl2) is < 0.10 – 0.50 mg/l in spot samples based on measuring total chlorine according to EN ISO 7393–1 or –2 (see BAT 9). The lower end of the range is close to the typical limit of detection of the monitoring method and is achieved by plants using chemical reduction. WORKING DRAFT IN PROGRESS TB/EIPPCB/CAK_Draft_1 December 2011 281
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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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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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Page 249 and 250: environmental legislation; generati
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Page 263 and 264: eduction of chlorate emissions; red
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Page 277 and 278: Chapter 4 Sections 4.5.4.2 and 4.5.
Page 279 and 280: Chapter 4 At this site, mercury con
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Page 283 and 284: 5 BEST AVAILABLE TECHNIQUES Scope
Page 285 and 286: General considerations In these BAT
Page 287 and 288: 5.2 Decommissioning of mercury cell
Page 289 and 290: 5.3 Environmental management system
Page 291 and 292: Chapter 5 The BAT-associated enviro
Page 293 and 294: Chapter 5 6. In order to reduce ene
Page 295: 5.6 Monitoring of emissions Chapter
Page 299 and 300: 5.9 Generation of waste Chapter 5 1
Page 301 and 302: 5.11 Site remediation Chapter 5 20.
Page 303 and 304: Chapter 5 inorganic chloramines, di
Page 305 and 306: 6 EMERGING TECHNIQUES 6.1 Introduct
Page 307 and 308: Chapter 6 cooperation with the Japa
Page 309 and 310: Chapter 6 In December 1998 a test w
Page 311 and 312: 6.3 Use of fuel cells in chlor-alka
Page 313 and 314: Chapter 6 hydrogen that is burnt to
Page 315 and 316: Chapter 7 7 CONCLUDING REMARKS AND
Page 317 and 318: REFERENCES References [1] Ullmann's
Page 319 and 320: References [63] Euro Chlor, Euro Ch
Page 321 and 322: References [112] Santorelli et al.,
Page 323 and 324: References [161] Germany, 'Verordnu
Page 325 and 326: [212] Florkiewicz, Long life diaphr
Page 327 and 328: References [259] Rappe et al., 'Lev
Page 329 and 330: GLOSSARY OF TERMS AND ABBREVIATIONS
Page 331 and 332: V. Units · VI. Chemical elements T
Page 333 and 334: VIII. Acronyms and definitions AC A
Page 335 and 336: EOX Extractable Organically-bound H
Page 337 and 338: Glossary Technique Ensemble of both
Page 339 and 340: ANNEX Annex {The CAK plant capaciti
Page 341 and 342: Euro Chlor No. Country code Company
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