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3.4.6 Catalytic N 2 O decomposition in the oxidation reactor .................................................1233.4.7 Combined NO x and N 2 O abatement in tail gases..........................................................1273.4.8 Non-selective catalytic reduction of NO x and N 2 O in tail gases...................................1303.4.9 Selective catalytic reduction of NO x (SCR) .................................................................1323.4.10 Addition of H 2 O 2 to the last absorption stage...............................................................1353.4.11 NO X reduction during startup/shutdown.......................................................................1373.5 BAT for nitric acid..................................................................................................................1403.6 Emerging techniques for nitric acid........................................................................................1423.6.1 Combined NO x and N 2 O abatement with addition of hydrocarbons ............................1424 SULPHURIC ACID .......................................................................................................................1454.1 General information................................................................................................................1454.2 Applied processes and techniques ..........................................................................................1514.2.1 Overview ......................................................................................................................1514.2.2 Catalysts .......................................................................................................................1554.2.3 Sulphur sources and SO 2 production ............................................................................1564.2.3.1 Sulphur combustion..............................................................................................1564.2.3.2 Regeneration of spent acids ..................................................................................1564.2.3.3 Pyrite roasting.......................................................................................................1574.2.3.4 Spent acid from TiO 2 production and roasting of metal sulphates .......................1574.2.3.5 Non-ferrous metal production...............................................................................1584.2.3.6 Other raw gas sources...........................................................................................1594.2.4 Product H 2 SO 4 treatment ..............................................................................................1614.3 Current emission and consumption levels ..............................................................................1624.4 Techniques to consider in the determination of BAT .............................................................1714.4.1 Single contact/single absorption process ......................................................................1714.4.2 Double contact/double absorption process ...................................................................1734.4.3 Addition of a 5 th bed to a double contact process .........................................................1764.4.4 Application of a Cs-promoted catalyst .........................................................................1784.4.5 Change over from single to double absorption.............................................................1814.4.6 Replacement of brick-arch converters ..........................................................................1824.4.7 Increasing the O 2 /SO 2 ratio of the inlet gas ..................................................................1834.4.8 Wet catalysis process....................................................................................................1854.4.9 Combined wet/dry catalysis processes .........................................................................1874.4.10 Combination of SCR and wet catalysis ........................................................................1884.4.11 Raw gas purification.....................................................................................................1894.4.12 Prevention of catalyst activity loss ...............................................................................1914.4.13 Maintaining heat exchanger efficiency.........................................................................1934.4.14 Monitoring of SO 2 levels..............................................................................................1944.4.15 Energy recovery and export..........................................................................................1954.4.16 Minimisation and abatement of SO 3 emissions ............................................................2004.4.17 Minimisation of NO x emissions....................................................................................2024.4.18 Treatment of waste waters............................................................................................2034.4.19 Tail gas scrubbing with NH 3 .........................................................................................2044.4.20 Tail gas scrubbing with ZnO ........................................................................................2054.4.21 Tail gas treatment: Sulfazide process ...........................................................................2064.4.22 Tail gas scrubbing with H 2 O 2 .......................................................................................2074.4.23 Removal of Hg from process gases ..............................................................................2094.5 BAT for sulphuric acid ...........................................................................................................2115 PHOSPHORIC ACID....................................................................................................................2135.1 General information................................................................................................................2135.2 Applied processes and techniques ..........................................................................................2145.2.1 Overview ......................................................................................................................2145.2.2 Wet process ..................................................................................................................2145.2.2.1 Raw materials .......................................................................................................2165.2.2.2 Grinding................................................................................................................2205.2.2.3 Recrystallisation ...................................................................................................2205.2.2.4 Evaporation...........................................................................................................2205.2.2.5 Co-product phosphogypsum.................................................................................2215.2.2.6 Co-product fluosilicic acid....................................................................................2215.3 Current emission and consumption levels ..............................................................................2225.4 Techniques to consider in the determination of BAT .............................................................2265.4.1 Dihydrate process (DH)................................................................................................226xviLarge Volume Inorganic Chemicals – Ammonia, Acids and Fertilisers
5.4.2 Hemihydrate process (HH) .......................................................................................... 2285.4.3 Hemi-dihydrate recrystallisation process, single-stage filtration ................................. 2305.4.4 Hemi-dihydrate recrystallisation process, double-stage filtration................................ 2325.4.5 Di-hemihydrate recrystallisation process, double-stage filtration................................ 2345.4.6 Repulping..................................................................................................................... 2365.4.7 Fluoride recovery and abatement ................................................................................. 2385.4.8 Recovery and abatement of dust from rock grinding ................................................... 2405.4.9 Phosphate rock selection (1) ........................................................................................ 2415.4.10 Phosphate rock selection (2) ........................................................................................ 2435.4.11 Decadmation of H 3 PO 4 by reactive extraction ............................................................. 2445.4.12 Use of entrainment separators...................................................................................... 2465.4.13 Disposal and valorisation options for phosphogypsum................................................ 2475.4.14 Upgrading of phosphogypsum ..................................................................................... 2495.4.15 Thermal process ........................................................................................................... 2515.5 BAT for phosphoric acid........................................................................................................ 2556 HYDROFLUORIC ACID............................................................................................................. 2576.1 General information ............................................................................................................... 2576.2 Applied processes and techniques.......................................................................................... 2586.2.1 Overview...................................................................................................................... 2586.2.2 Fluorspar ...................................................................................................................... 2586.2.3 Reaction stage and options for increasing the capacity................................................ 2596.2.4 Process gas treatment ................................................................................................... 2616.2.5 Tail gas treatment......................................................................................................... 2626.2.6 Co-product anhydrite ................................................................................................... 2626.2.7 Product storage and handling....................................................................................... 2626.3 Current emission and consumption levels.............................................................................. 2636.3.1 Consumption levels...................................................................................................... 2636.3.2 Emission levels to air ................................................................................................... 2646.3.3 Liquid effluents and solid wastes................................................................................. 2666.4 Techniques to consider in the determination of BAT............................................................. 2676.4.1 Heat transfer design ..................................................................................................... 2676.4.2 Energy recovery from kiln heating .............................................................................. 2696.4.3 Valorisation of anhydrite ............................................................................................. 2706.4.4 Valorisation of fluosilicic acid ..................................................................................... 2716.4.5 Spar calcination............................................................................................................ 2726.4.6 Scrubbing of tail gases: fluorides................................................................................. 2736.4.7 Scrubbing of tail gases: fluorides along with SO 2 and CO 2 ......................................... 2756.4.8 Abatement of dust emissions from drying, transfer and storage .................................. 2776.4.9 Waste water treatment.................................................................................................. 2796.4.10 Fluosilicic acid process ................................................................................................ 2806.5 BAT for hydrofluoric acid...................................................................................................... 2827 NPK AND CN ................................................................................................................................ 2837.1 General information ............................................................................................................... 2837.2 Applied processes and techniques.......................................................................................... 2857.2.1 Overview...................................................................................................................... 2857.2.2 Phosphate rock digestion ............................................................................................. 2867.2.2.1 Nitrophosphate route............................................................................................ 2867.2.3 Direct neutralisation (pipe reactor) .............................................................................. 2877.2.4 Pre-neutralisation ......................................................................................................... 2877.2.5 Drum granulation with ammoniation ........................................................................... 2877.2.6 Particle formation and conditioning............................................................................. 2877.2.7 Conversion of Ca(NO 3 ) 2 . 4 H 2 O into AN and lime ..................................................... 2887.2.8 Ammonium phosphates production ............................................................................. 2887.2.9 Emission sources into air and exhaust gas treatment ................................................... 2887.3 Current emission and consumption levels.............................................................................. 2907.4 Techniques to consider in the determination of BAT............................................................. 2977.4.1 Minimisation of NO x formation ................................................................................... 2977.4.2 Particle formation (1): spherodiser............................................................................... 2987.4.3 Particle formation (2): drum granulation ..................................................................... 3007.4.4 Particle formation (3): prill tower ................................................................................ 3027.4.5 Plate bank product cooler............................................................................................. 3047.4.6 Recycling warm air ...................................................................................................... 307Large Volume Inorganic Chemicals – Ammonia, Acids and Fertilisersxvii
Page 1 and 2: EUROPEAN COMMISSIONIntegrated Pollu
Page 3 and 4: Executive SummaryEXECUTIVE SUMMARYT
Page 5 and 6: Executive SummaryII.Production and
Page 7 and 8: Executive Summarybed, using a cesiu
Page 9 and 10: Executive SummaryConversion process
Page 11 and 12: Executive SummaryBAT is to treat al
Page 13 and 14: PrefacePREFACE1. Status of this doc
Page 15 and 16: Preface5. How to understand and use
Page 17: 2.2.4.2 Gasification of heavy hydro
Page 21 and 22: 10.4.3 Fluoride recovery and abatem
Page 23 and 24: Figure 8.1: Overview of the product
Page 25 and 26: Table 4.20: Energy balance of a dou
Page 27: ScopeSCOPEThis document on Large Vo
Page 30 and 31: Chapter 197 % of nitrogen fertilise
Page 32 and 33: Chapter 11.1.2.3 High exhaust gas v
Page 34 and 35: Chapter 1the SSD of NPK does not le
Page 36 and 37: Chapter 11,8Relative production cap
Page 38 and 39: Chapter 11.2.3 Supply of steam and
Page 40 and 41: Chapter 11.3 Overview of emissions
Page 42 and 43: Chapter 1ApplicabilityGenerally app
Page 44 and 45: Chapter 11.4.3 Handling excess stea
Page 46 and 47: Chapter 11.4.5 Optimisation/mainten
Page 48 and 49: Chapter 1Operational dataNo informa
Page 50 and 51: Chapter 1ApplicabilityEspecially ap
Page 52 and 53: Chapter 11.4.9 Environmental manage
Page 54 and 55: Chapter 1(v) Documentation- establi
Page 56 and 57: Chapter 1iv. allow for comparison w
Page 58 and 59: Chapter 1A number of studies show t
Page 60 and 61: Chapter 11.5 Common BATIn understan
Page 62 and 63: Chapter 11.5.2 BAT for environmenta
Page 64 and 65: Chapter 2Location CompanyCapacity F
Page 66 and 67: Chapter 22.2.2 Output from ammonia
Page 68 and 69:
Chapter 22.2.3.2 Primary reformingT
Page 70 and 71:
Chapter 2Process name Solvent/reage
Page 72 and 73:
Chapter 22.2.4 Partial oxidationThe
Page 74 and 75:
Chapter 2In the moving bed process,
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Chapter 22.2.6 Storage and transfer
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Chapter 2Production process Feedsto
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Chapter 22.3.2 NO x emissionsTable
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Chapter 22.3.3 Other consumption le
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Chapter 2ParameterProcessEmission l
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Chapter 22.4 Techniques to consider
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Chapter 22.4.2 Processes with reduc
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Chapter 22.4.3 Heat exchange autoth
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Chapter 22.4.4 Revamp: increase cap
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Chapter 22.4.5 Pre-reformingDescrip
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Chapter 2ApplicabilityGenerally app
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Chapter 22.4.7 Advanced process con
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Chapter 22.4.9 Combined Claus unit
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Chapter 2Operational dataSee Descri
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Chapter 22.4.12 Preheating of combu
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Chapter 22.4.14 Isothermal shift co
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Chapter 22.4.16 Stripping and recyc
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Chapter 22.4.18 Use of sulphur resi
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Chapter 22.4.20 Indirect cooling of
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Chapter 22.4.22 Ammonia removal fro
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Chapter 22.4.24 Metal recovery and
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Chapter 2Driving force for implemen
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Chapter 22.5 BAT for ammoniaBAT is
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Chapter 33 NITRIC ACID3.1 General i
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Chapter 3Pressure in bar Temperatur
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Chapter 33.2.5 Tail gas properties
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Chapter 33.3 Current emission and c
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Chapter 3N 2 O emission levelProces
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Chapter 3N 2 O emission levelProces
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Chapter 3Process typeNO x emission
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Chapter 3Process typeNO x emission
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Chapter 3140120Generation factor %1
Page 141 and 142:
Chapter 33.4.2 Optimisation of the
Page 143 and 144:
Chapter 33.4.3 Alternative oxidatio
Page 145 and 146:
Chapter 33.4.4 Optimisation of the
Page 147 and 148:
Chapter 3Achieved environmental ben
Page 149 and 150:
Chapter 33.4.5 N 2 O decomposition
Page 151 and 152:
Chapter 33.4.6 Catalytic N 2 O deco
Page 153 and 154:
Chapter 3According to [89, Kuiper,
Page 155 and 156:
Chapter 33.4.7 Combined NO x and N
Page 157 and 158:
Chapter 3EconomicsInvestment costs.
Page 159 and 160:
Chapter 3Operational dataSee descri
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Chapter 3NOx removal efficiency in
Page 163 and 164:
Chapter 33.4.10 Addition of H 2 O 2
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Chapter 33.4.11 NO X reduction duri
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Chapter 3Installing a low temperatu
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Chapter 3NO x emission level as NO
Page 171:
Chapter 3Operational dataNo specifi
Page 174 and 175:
Chapter 4Country Company Location C
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Chapter 4Country Company Location C
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Chapter 4Figure 4.2 gives an overvi
Page 180 and 181:
Chapter 4Two general converter type
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Chapter 4Figure 4.6 gives an impres
Page 184 and 185:
Chapter 44.2.3 Sulphur sources and
Page 186 and 187:
Chapter 44.2.3.5 Non-ferrous metal
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Chapter 4Sulphur source/SO 2 produc
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Page 192 and 193:
Chapter 410Tail gas specific SO2 lo
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Chapter 4Capacity in tonnesof 100 %
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Chapter 4Capacity in tonnesof 100 %
Page 198 and 199:
Chapter 4SO 2 sourceSpent acid and
Page 200 and 201:
Chapter 4Cross-media effectsWithout
Page 202 and 203:
Page 204 and 205:
Chapter 44.4.3 Addition of a 5 th b
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Chapter 44.4.4 Application of a Cs-
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Chapter 4EUR/yearWaste gas volume (
Page 210 and 211:
Chapter 44.4.6 Replacement of brick
Page 212 and 213:
Chapter 4EUR/yearWaste gas volume (
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Chapter 4PlantSO 2 sourceInlet SO 2
Page 216 and 217:
Chapter 44.4.10 Combination of SCR
Page 218 and 219:
Page 220 and 221:
Page 222 and 223:
Chapter 44.4.14 Monitoring of SO 2
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Chapter 4EconomicsCost benefits can
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Chapter 4Energy inputRecovery and l
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Chapter 44.4.16 Minimisation and ab
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Chapter 44.4.17 Minimisation of NO
Page 232 and 233:
Chapter 44.4.19 Tail gas scrubbing
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Chapter 44.4.21 Tail gas treatment:
Page 236 and 237:
Chapter 4Economics[58, TAK-S, 2003]
Page 238 and 239:
Chapter 4EconomicsNo specific infor
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Chapter 4BAT is to minimise and red
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Chapter 55.2 Applied processes and
Page 244 and 245:
Chapter 55.2.2.1 Raw materials5.2.2
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Chapter 5OriginChinaMine/regionRare
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Chapter 55.2.2.2 GrindingDepending
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Page 252 and 253:
Chapter 5Emission of mg/l g/tonne P
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Page 256 and 257:
Chapter 55.4.2 Hemihydrate process
Page 258 and 259:
Chapter 55.4.3 Hemi-dihydrate recry
Page 260 and 261:
Chapter 55.4.4 Hemi-dihydrate recry
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Chapter 55.4.5 Di-hemihydrate recry
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Chapter 55.4.6 RepulpingDescription
Page 266 and 267:
Chapter 55.4.7 Fluoride recovery an
Page 268 and 269:
Chapter 55.4.8 Recovery and abateme
Page 270 and 271:
Chapter 5Operational dataNo informa
Page 272 and 273:
Chapter 55.4.11 Decadmation of H 3
Page 274 and 275:
Chapter 55.4.12 Use of entrainment
Page 276 and 277:
Chapter 5Cross-media effects• dis
Page 278 and 279:
Page 280 and 281:
Chapter 5Cross-media effectsTable 5
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Chapter 5ApplicabilityAt present, o
Page 285 and 286:
Chapter 66 HYDROFLUORIC ACID6.1 Gen
Page 287 and 288:
Chapter 6Component Portion (mass co
Page 289 and 290:
Chapter 66.2.4 Process gas treatmen
Page 291 and 292:
Page 293 and 294:
Chapter 6Emission of kg/tonne HF Re
Page 295 and 296:
6.4 Techniques to consider in the d
Page 297 and 298:
Chapter 66.4.2 Energy recovery from
Page 299 and 300:
Chapter 66.4.4 Valorisation of fluo
Page 301 and 302:
Chapter 66.4.6 Scrubbing of tail ga
Page 303 and 304:
6.4.7 Scrubbing of tail gases: fluo
Page 305 and 306:
Chapter 66.4.8 Abatement of dust em
Page 307 and 308:
Chapter 66.4.9 Waste water treatmen
Page 309 and 310:
Chapter 6Cross-media effects• 5 -
Page 311 and 312:
Chapter 77 NPK AND CN7.1 General in
Page 313 and 314:
Page 315 and 316:
Chapter 77.2.3 Direct neutralisatio
Page 317 and 318:
Chapter 7Fluorine compounds origina
Page 319 and 320:
Chapter7Per tonne productkWh Nm 3 k
Page 321 and 322:
Chapter7Emission levelmg/Nm 3 ppm k
Page 323 and 324:
Chapter7Emission levelmg/Nm 3 ppm k
Page 325 and 326:
7.4 Techniques to consider in the d
Page 327 and 328:
Chapter7Driving force for implement
Page 329 and 330:
Page 331 and 332:
Page 333 and 334:
Chapter7Achieved environmental bene
Page 335 and 336:
Chapter77.4.6 Recycling warm airDes
Page 337 and 338:
Chapter77.4.7 Optimising the recycl
Page 339 and 340:
Chapter7Operational dataThe volume
Page 341 and 342:
Page 343 and 344:
Page 345 and 346:
Chapter77.4.11 Recycling of scrubbi
Page 347 and 348:
Chapter77.4.12 Waste water treatmen
Page 349:
Chapter7ParameterLevelmg/Nm 3Phosph
Page 352 and 353:
Page 354 and 355:
Chapter 88.2.1.1 Particle formation
Page 356 and 357:
Chapter 8Consumption of Per tonne u
Page 358 and 359:
Chapter 8Per tonne urea Unit Remark
Page 360 and 361:
Chapter 8Waste water per tonne urea
Page 362 and 363:
Chapter 8Pollutant Source g/tonne u
Page 364 and 365:
Chapter 8Plant Emission Amount (ton
Page 366 and 367:
Page 368 and 369:
Chapter 8Operational dataSee Table
Page 370 and 371:
Chapter 8Operational dataSee Table
Page 372 and 373:
Page 374 and 375:
Chapter 88.4.6 Redirecting fines to
Page 376 and 377:
Chapter 8Existing plantCase 2Revamp
Page 378 and 379:
Chapter 88.4.8 Heat integration in
Page 380 and 381:
Chapter 88.4.9 Combined condensatio
Page 382 and 383:
Chapter 88.4.10 Minimisation of NH
Page 384 and 385:
Page 386 and 387:
Chapter 8Other approaches to proces
Page 388 and 389:
Page 390 and 391:
Chapter 88.5 BAT for Urea and UANBA
Page 392 and 393:
Chapter 9Country Company LocationBe
Page 394 and 395:
Chapter 99.2.2 NeutralisationThe ex
Page 396 and 397:
Chapter 9Scrubbing devices• packe
Page 398 and 399:
Page 400 and 401:
Chapter 9Pollutant mg/Nm 3 g/tonne
Page 402 and 403:
Page 404 and 405:
Chapter 99.4.2 Recovery of residual
Page 406 and 407:
Chapter 99.4.3 Energy consideration
Page 408 and 409:
Chapter 99.4.4 Steam purification a
Page 410 and 411:
Chapter 99.4.5 Autothermal granulat
Page 412 and 413:
Chapter 9ApplicabilityIrrigated can
Page 415 and 416:
Chapter 1010 SUPERPHOSPHATES10.1 Ge
Page 417 and 418:
Chapter 10Emissionto airEmissionto
Page 419 and 420:
Chapter 10Input Indirect granulatio
Page 421 and 422:
Chapter 10Volume5 - 10 m 3 /hourTem
Page 423 and 424:
Chapter 1010.4.2 Recovery and abate
Page 425 and 426:
Chapter 1010.4.4 Recycling of scrub
Page 427 and 428:
Chapter 1111 CONCLUDING REMARKS11.1
Page 429:
Chapter 11Production of HNO 3 : De-
Page 432 and 433:
References26 Dipankar Das (1998).
Page 434 and 435:
References89 Kuiper (2001). "High t
Page 436 and 437:
References147 Uhde (2006). "The Uhd
Page 438 and 439:
GlossaryCalculation of steam proper
Page 440 and 441:
GlossaryIPCCIPPCISO 14001Intergover
Page 442 and 443:
GlossaryChemical formulasAl 2 O 3Ca
Page 445 and 446:
Annexes14 ANNEXES14.1 Cost calculat
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