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

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Chapter 6 Achieved environmental benefits The achieved environmental benefit of this technique is a reduction of energy consumption. Environmental performance and operational data At the AkzoNobel chlor-alkali plant in Delfzijl (Netherlands), a 70 kW PEMFC power plant was put into operation in 2007. The rated electrical peak power of the unit is 120 kW, but to extend the lifetime and to attain a high conversion efficiency, the unit operates at partial load. At a load of 50 kW, a total of 12 stacks comprising a total of 900 cells (cell area of 200 cm 2 ) are connected in series, generating 630 V direct current at 80 A. An inverter converts the direct current to 400 V alternating current which is fed into the local electricity grid. Although the chlor-alkali plant uses direct power, it was more economical to feed to the grid than to feed to the electrolysers. The conversion efficiency of the fuel cells is 55 %, but the balance of the plant including the inverters reduces the overall efficiency to 45 % (on the basis of the lower heating value of hydrogen). The PEMFC system was reported to be very reliable. In April 2011 it had been 20 000 h on the grid and the stack lifetime in real life was reported to be higher than 8000 h with an average cell voltage loss of 3 ZV/h. However, a drawback of the design with the serial connection of the stacks is that the whole unit stops when the voltage of a single cell falls below a threshold [ 109, Verhage et al. 2010 ], [ 110, Verhage 2011 ]. At the Solvin chlor-alkali plant in Antwerp-Lillo (Belgium), a 1 MW PEMFC power plant is expected to be put into operation in 2011. It will be the world's largest PEMFC power plant. At 1 MW, it is expected that the balance-of-plant can be reduced so as to raise the overall conversion efficiency to 50 % (on the basis of the lower heating value of hydrogen). The problem of non-availability of a PEMFC power plant due to cell failure is expected to be solved by switching 12 power modules of 85 kW in parallel. Failure of a cell in a module will trip one module but the other 11 will compensate for the loss by automatically raising the current. Stack replacement is designed to be rapid and restoration of the original situation should occur within 1 h [ 109, Verhage et al. 2010 ], [ 110, Verhage 2011 ]. In the United States, the company K2 expects to put into operation a new bleach production plant by 2012 in Pittsburg, California. The co-produced hydrogen will be converted to electricity in a 163 kW fuel cell generator [ 111, Ballard 2010 ]. PEMFCs can also be used for the hydrogen generated during the electrolytic production of sodium chlorate. A 120 kW pilot plant ran unattended for approximately 2500 h at the Caffaro chlorate plant in Brescia (Italy) from September to December 2006 [ 112, Santorelli et al. 2007 ]. Cross-media effects Some raw materials and energy are consumed for the manufacture of the fuel cells. One equipment provider reports that all materials used in their fuel cells are easy to recycle and allow for the reuse of the major components. The scarce and valuable platinum can be recycled to an extent of approximately 98 % [ 108, Nedstack 2011 ]. Technical considerations relevant to applicability If the fuel cell power plant is run with purified hydrogen and feeds alternating current to the WORKING DRAFT IN PROGRESS grid, there are generally no technical restrictions to its use in new or existing chlor-alkali installations. In 2011, however, there is only one fuel cell plant to be put into operation with a rated power equal to or greater than 1 MW and practical experience with this plant size needs yet be gained. In addition, if the fuel cell system is to be completely embedded in the electrolysis process, installed inside or close to the cell room, more information is needed, such as on performance in the presence of specific contaminants and on durability under the typical operating conditions of a chlor-alkali plant [ 114, Delfrate and Schmitt 2010 ]. Economics From an economic point of view, it is ideal to use fuel cells for hydrogen which is otherwise emitted. The hydrogen used as a chemical will never be accessible for other uses, while the 296 December 2011 TB/EIPPCB/CAK_Draft_1
Chapter 6 hydrogen that is burnt to produce steam may become available to fuel cells if the overall system price allowed for interesting paybacks. The payback time depends on the end use (e.g. use of direct current in electrolysis cells to reduce electricity consumption or to increase production capacity, conversion to alternating current and feeding to the grid) and associated costs (e.g. hydrogen value, grid electricity price, value of extra production) [ 114, Delfrate and Schmitt 2010 ]. A business case provided by one equipment provider for a 2 MW PEMFC power plant with estimated investment costs of EUR 5 000 000 is presented in Table 6.1. Based on these figures, a payback time of approximately six years can be calculated. Another equipment provider estimates a payback time of approximately five years if the electricity price is approximately 100 EUR/MWth [ 111, Ballard 2010 ]. However, if an electricity price of 60 EUR/MWh is assumed, it can be derived from Table 6.1 that the technique is not economically viable, which is in line with a previous study [ 113, Moussallem et al. 2009 ]. WORKING DRAFT IN PROGRESS TB/EIPPCB/CAK_Draft_1 December 2011 297
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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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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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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
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Page 293 and 294: Chapter 5 6. In order to reduce ene
Page 295 and 296: 5.6 Monitoring of emissions Chapter
Page 297 and 298: [This BAT conclusion is based on in
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: 6.3 Use of fuel cells in chlor-alka
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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