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

More documents

Recommendations

Info

Chapter 4 Reference literature [ 69, Regierungspräsidium Dessau 1999 ], [ 192, Euro Chlor 2011 ] [Dutch report, 1998], [Gest 76/52, 1986], [Gest 87/130, 1996], [Gest 92/169, 1994], [Le Chlore, 1996], [Schubert], [Wunderlich] 4.3.5.2 Scrubbing with hydrogen peroxide to reduce emissions of chlorine dioxide Description This technique consists in reducing emissions of chlorine dioxide to air from the chlorine absorption unit by using hydrogen peroxide. This can be achieved in a separate scrubber or by adding peroxide dosing equipment to the chlorine absorption unit. Technical description Small amounts of chlorine dioxide can be emitted to air from the chlorine absorption unit. Chlorine dioxide is formed because of a side reaction of chlorine or hypochlorous acid with chlorite (chlorite originates from the disproportionation of hypochlorite, see Section 2.6.12.2) [ 185, Infomil 2011 ], [ 191, Lassche 2011 ], [ 193, Jia et al. 2000 ], [ 194, Gordon and Tachiyashiki 1991 ]: 2 ClO2 - + Cl2 V 2 ClO2 + 2 Cl - 2 ClO2 - + HOCl V 2 ClO2 + H + + 2 Cl - The formation of chlorine dioxide via this reaction is favoured by higher temperatures. It is also favoured by pH values below 7 where dissolved molecular chlorine or hypochlorous acid dominate over hypochlorite. These pH values can be caused by an insufficient surplus of sodium hydroxide to absorb chlorine, often due to local concentration gradients. Moreover, higher concentrations of non-condensable gases such as oxygen and nitrogen in the waste gas lead to increased stripping [ 185, Infomil 2011 ], [ 191, Lassche 2011 ], [ 194, Gordon and Tachiyashiki 1991 ]. Solvay reported that chlorine dioxide can also be formed by a side reaction of the acidic chlorate reduction (see Section 4.3.6.4.3) [ 34, Solvay 2010 ]: 5 ClO3 - + Cl - + 6 H + V 6 ClO2 + 3 H2O The waste gas from the reactor is therefore treated before entering the chlorine absorption unit [ 34, Solvay 2010 ]. However, AkzoNobel reported that chlorine dioxide is not formed when chlorate is destroyed with hydrochloric acid (or another reducing agent) [ 191, Lassche 2011 ]. Chlorine dioxide hardly dissolves in the produced bleach and is therefore continuously stripped out with the waste gas. The monitoring equipment usually measures both chlorine and chlorine dioxide (see Section 4.3.4.4). Chlorine dioxide can be destroyed with hydrogen peroxide to produce chlorite, the latter remaining in the bleach [ 185, Infomil 2011 ], [ 191, Lassche 2011 ]: WORKING DRAFT IN PROGRESS 2 ClO2 + H2O2 + 2 OH - V 2 ClO2 - + O2 + 2 H2O At the AkzoNobel plant in Rotterdam (Netherlands), a separate hydrogen peroxide scrubber was installed while at the AkzoNobel plants in Delfzijl (Netherlands) and Ibbenbüren (Germany), peroxide dosing equipment was added to the chlorine absorption unit. In the latter case, the dosage of hydrogen peroxide is controlled by an analyser in the off gas which starts when the chlorine dioxide concentration exceeds 0.7 mg/m 3 . The hydrogen peroxide is stored in an intermediate bulk container which is placed on a liquid impermeable floor. The hydrogen peroxide has a concentration of approximately 35 wt-%. The inflow takes place automatically via a pump and a flexible pipeline which is connected to the circulation flow of the secondary 226 December 2011 TB/EIPPCB/CAK_Draft_1
Chapter 4 chlorine scrubber, immediately after the cooler. A check valve prevents backflow. The pump is indirectly controlled by the signal from the chlorine analyser, resulting in a pulse dose. A continuous dosage is not possible because the chlorine dioxide concentration is not constant and the hydrogen peroxide concentration in the bleach needs to be as low as possible to increase the lifetime of the cooler and to maintain the quality of the produced bleach [ 68, AkzoNobel 2007 ], [ 185, Infomil 2011 ]. Achieved environmental benefits The achieved environmental benefit of this technique is a reduction of chlorine dioxide emissions to air. Environmental performance and operational data At the AkzoNobel plant in Delfzijl (Netherlands), hydrogen peroxide is added to the chlorine destruction unit. This reduces the chlorine dioxide concentration from 9 – 22 mg/m 3 in untreated vent gas (corresponding to loads of 2.3 – 5.5 g/h and emission factors of 0.18 – 0.44 g/t annual chlorine capacity) to less than 0.4 mg/m 3 (corresponding to loads of 0.1 g/h and emission factors of 8 mg/t annual chlorine capacity) at a flow rate of approximately 250 m 3 /h [ 68, AkzoNobel 2007 ], [ 185, Infomil 2011 ]. {Please TWG provide more information.} Cross-media effects Some raw materials and energy are consumed for the installation and operation of the scrubber or dosing equipment. In particular, the technique requires hydrogen peroxide that, depending on the concentration, can be oxidising and irritant/corrosive. The estimated consumption of 35 wt-% H2O2 at the AkzoNobel plant in Delfzijl (Netherlands) is approximately 2 m 3 per month. In the case of a separate scrubber, waste in the form of a chlorite/chlorate containing hydrogen peroxide solution is generated [ 68, AkzoNobel 2007 ], [ 185, Infomil 2011 ]. Technical considerations relevant to applicability Generally, there are no technical restrictions to the applicability of this technique. The peroxide dosing equipment has the advantage that only a small modification of the system is needed compared to a separate scrubber [ 68, AkzoNobel 2007 ], [ 185, Infomil 2011 ]. Economics The installation of peroxide dosing equipment requires lower investment costs than a separate scrubber [ 68, AkzoNobel 2007 ], [ 185, Infomil 2011 ]. {Please TWG provide more information.} Driving force for implementation The driving force for implementation of this technique is environmental legislation. Example plants AkzoNobel in Delfzijl (Netherlands), chlorine capacity 109 kt/yr; AkzoNobel in Ibbenbüren (Germany), chlorine capacity 125 kt/yr; AkzoNobel in Rotterdam-Botlek (Netherlands), chlorine capacity 633 kt/yr. WORKING DRAFT IN PROGRESS Reference literature [ 34, Solvay 2010 ], [ 68, AkzoNobel 2007 ], [ 185, Infomil 2011 ], [ 191, Lassche 2011 ], [ 193, Jia et al. 2000 ], [ 194, Gordon and Tachiyashiki 1991 ] TB/EIPPCB/CAK_Draft_1 December 2011 227
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 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 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
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 105 and 106:
Page 107 and 108:
Page 109 and 110:
Chapter 3 concentrations of organic
Page 111 and 112:
Chapter 3 3.4.3 Emissions and waste
Page 113 and 114:
Chapter 3 {Please TWG provide infor
Page 115 and 116:
Chapter 3 in process and waste wate
Page 117 and 118:
Chapter 3 produced per year has bee
Page 119 and 120:
Page 121 and 122:
Chapter 3 of chlorine capacity. The
Page 123 and 124:
Table 3.23: Mercury emissions from
Page 125 and 126:
Mercury emissions in g Hg/t Cl capa
Page 127 and 128:
Chapter 3 Table 3.24: Mercury emiss
Page 129 and 130:
Page 131 and 132:
Chapter 3 KCl are higher than from
Page 133 and 134:
Chapter 3 When concentrated solid c
Page 135 and 136:
Chapter 3 Generally, storage of con
Page 137 and 138:
Chapter 3 recycled brine systems si
Page 139 and 140:
Process Maintenance To solid treatm
Page 141 and 142:
3.5.9.5 Graphite and activated Acti
Page 143 and 144:
Chapter 3 Table 3.31: Yearly waste
Page 145 and 146:
Chapter 3 The fact that the differe
Page 147 and 148:
Chapter 3 3.6 Emissions Emission an
Page 149 and 150:
Reported asbestos concentrations ar
Page 151 and 152:
Chapter 3 3.7 Emissions Emission an
Page 153 and 154:
{A list of techniques used on full
Page 155 and 156:
3.8.3 PCDDs/PCDFs, PCBs, PCNs and P
Page 157 and 158:
Chapter 3 The ‘dioxin’ pattern
Page 159 and 160:
Chapter 4 4 TECHNIQUES TO CONSIDER
Page 161 and 162:
Heading within the sections Cross-m
Page 163 and 164:
4.1 Mercury cell plants 4.1.1 Overv
Page 165 and 166:
Chapter 4 plants at comparable capa
Page 167 and 168:
Chapter 4 Table 4.2: Data from the
Page 169 and 170:
Chapter 4 environment can be expect
Page 171 and 172:
4. Plant size Chapter 4 An increase
Page 173 and 174:
Table 4.6: Comparison of reported c
Page 175 and 176:
Chapter 4 Generally, conversion cos
Page 177 and 178:
4.1.3 Decommissioning 4.1.3.1 Decom
Page 179 and 180:
3. Emptying of the cells and handli
Page 181 and 182:
Chapter 4 Table 4.7: Overview of co
Page 183 and 184:
Table 4.8: Techniques for monitorin
Page 185 and 186:
Chapter 4 Table 4.10: Decommissioni
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
Page 195 and 196: Chapter 4 4.2.3 Conversion of asbes
Page 197 and 198: Chapter 4 directly from the cells.
Page 199 and 200: 4.3 All Diaphragm and membrane cell
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 and 228: Chapter 4 Technical description The
Page 229 and 230: Chapter 4 Table 4.17: Monitoring te
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
Page 237 and 238: Chapter 4 Good pipework design to m
Page 239 and 240: Chapter 4 was the solution at that
Page 241: differential pressure at inlet and
Page 245 and 246: Chapter 4 Achieved environmental be
Page 247 and 248: {Please TWG provide more informatio
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
Page 255 and 256: 4.3.6.3.4 Catalytic decomposition r
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
Page 271 and 272: Chapter 4 b) closing of doors and w
Page 273 and 274: 4.4 Membrane cell plants 4.4.1 High
Page 275 and 276: 4.5.3 Containment Chapter 4 Descrip
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
Page 281 and 282: Chapter 4 However, the soil washing
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 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 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
show all

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

Create successful ePaper yourself

Delete template?

Save as template?