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Chapter 66.2 Applied processes and techniques6.2.1 OverviewHydrogen fluoride and hydrofluoric acid are produced by the conversion of dried fluorsparusing concentrated sulphuric acid at elevated temperatures in accordance with the followingreaction:CaF 2 + H 2 SO 4 f 2HF + CaSO 4 jH R = 59 kJ/mol (1)There are secondary reactions due to impurities contained in the fluorspar. These occuralongside the main reaction, forming, e.g. silicon tetrafluoride, sulphur dioxide, hydrogensulphide, carbon dioxide, water and elementary sulphur in accordance with the followingreaction equations:SiO 2 + 2CaF 2 + 2H 2 SO 4 f SiF 4 + 2CaSO 4 + 2H 2 O (2)CaCO 3 + H 2 SO 4 f CaSO 4 + CO 2 + H 2 O (3)R 2 O 3 + 3H 2 SO 4 f R 2 (SO 4 ) 3 + 3H 2 O (R = Fe, Al) (4)CH 3 (CH 2 ) n COOH + (2n + 3)H 2 SO 4 f (n + 2)CO 2 + (3n + 5)H 2 O + (2n + 3)SO 2 (5)Fe (Reactor) + 2H 2 SO 4 f FeSO 4 + SO 2 + 2H 2 O (6)MS + H 2 SO 4 f MSO 4 + H 2 S (M = Metals) (7)2H 2 S + SO 2 f 3S + 2H 2 O (8)H 2 S formed by reaction (7) is converted to sulphur according to reaction (8). Water formed bythese reactions is removed from the reaction gases by absorption in sulphuric acid. Oleum isadded, to provide the SO 3 reacting according to equation (9) to maintain the concentration of thesulphuric acid being fed to the reactor, at a constant level.H 2 O + SO 3 f H 2 SO 4 (9)As an alternative, HF can be produced starting from H 2 SiF 6 (see Section 6.4.10).6.2.2 Fluorspar[22, CEFIC, 2000]The raw material for the production of HF is fluorspar, which is mined with a mass content ofbetween 30 and 60 % CaF 2 in the crude ore. The crude ore is ground and the CaF 2 is separatedfrom the other minerals by physical flotation at the mining site. The flotation chemicals incurrent use are mainly saturated and unsaturated vegetable fatty acids. They remain in thefluorspar, which should ideally contain at least 97 % CaF 2 for use as "acid spar".Table 6.2 shows the components in acid spar. Acid spar should not contain any fraction above0.2 mm in diameter. It is transported to the user as a bulk material with a water content ofapproximately 10 % to minimise dust generation.The fluorspar needs to be dried before it is fed to the hydrogen fluoride plant. This is usuallycarried out in directly heated flue-gas driers at approximately 120 ºC. There are also plantswithout spar drying equipment, but which purchase the spar already dried elsewhere.258 Large Volume Inorganic Chemicals – Ammonia, Acids and Fertilisers
Chapter 6Component Portion (mass content in %)Maximum acceptable valuesCaF 2 >97.0SiO 2
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EUROPEAN COMMISSIONIntegrated Pollu
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Executive SummaryEXECUTIVE SUMMARYT
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Executive SummaryII.Production and
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Executive Summarybed, using a cesiu
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Executive SummaryConversion process
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Executive SummaryBAT is to treat al
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PrefacePREFACE1. Status of this doc
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Preface5. How to understand and use
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2.2.4.2 Gasification of heavy hydro
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5.4.2 Hemihydrate process (HH) ....
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10.4.3 Fluoride recovery and abatem
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Figure 8.1: Overview of the product
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Table 4.20: Energy balance of a dou
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ScopeSCOPEThis document on Large Vo
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Chapter 197 % of nitrogen fertilise
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Chapter 11.1.2.3 High exhaust gas v
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Chapter 1the SSD of NPK does not le
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Chapter 11,8Relative production cap
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Chapter 11.2.3 Supply of steam and
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Chapter 11.3 Overview of emissions
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Chapter 1ApplicabilityGenerally app
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Chapter 11.4.3 Handling excess stea
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Chapter 11.4.5 Optimisation/mainten
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Chapter 1Operational dataNo informa
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Chapter 1ApplicabilityEspecially ap
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Chapter 11.4.9 Environmental manage
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Chapter 1(v) Documentation- establi
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Chapter 1iv. allow for comparison w
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Chapter 1A number of studies show t
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Chapter 11.5 Common BATIn understan
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Chapter 11.5.2 BAT for environmenta
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Chapter 2Location CompanyCapacity F
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Chapter 22.2.2 Output from ammonia
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Chapter 22.2.3.2 Primary reformingT
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Chapter 2Process name Solvent/reage
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Chapter 22.2.4 Partial oxidationThe
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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
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Chapter 33.4.2 Optimisation of the
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Chapter 33.4.3 Alternative oxidatio
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Chapter 33.4.4 Optimisation of the
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Chapter 3Achieved environmental ben
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Chapter 33.4.5 N 2 O decomposition
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Chapter 33.4.6 Catalytic N 2 O deco
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Chapter 3According to [89, Kuiper,
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Chapter 33.4.7 Combined NO x and N
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Chapter 3EconomicsInvestment costs.
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Chapter 3Operational dataSee descri
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Chapter 3NOx removal efficiency in
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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
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Chapter 3Operational dataNo specifi
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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
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Chapter 4Two general converter type
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Chapter 4Figure 4.6 gives an impres
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Chapter 44.2.3 Sulphur sources and
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Chapter 44.2.3.5 Non-ferrous metal
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Chapter 4Sulphur source/SO 2 produc
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Chapter 410Tail gas specific SO2 lo
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Chapter 4Capacity in tonnesof 100 %
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Chapter 4Capacity in tonnesof 100 %
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Chapter 4SO 2 sourceSpent acid and
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Chapter 4Cross-media effectsWithout
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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 (
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Chapter 44.4.6 Replacement of brick
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Chapter 4EUR/yearWaste gas volume (
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Chapter 4PlantSO 2 sourceInlet SO 2
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Chapter 44.4.10 Combination of SCR
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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
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Chapter 44.4.19 Tail gas scrubbing
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Chapter 44.4.21 Tail gas treatment:
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Page 244 and 245: Chapter 55.2.2.1 Raw materials5.2.2
Page 246 and 247: Chapter 5OriginChinaMine/regionRare
Page 248 and 249: Chapter 55.2.2.2 GrindingDepending
Page 250 and 251: Chapter 55.3 Current emission and c
Page 252 and 253: Chapter 5Emission of mg/l g/tonne P
Page 254 and 255: Chapter 55.4 Techniques to consider
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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Page 264 and 265: 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
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Page 278 and 279: Chapter 5Driving force for implemen
Page 280 and 281: Chapter 5Cross-media effectsTable 5
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Page 291 and 292: Chapter 66.3 Current emission and c
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Page 295 and 296: 6.4 Techniques to consider in the d
Page 297 and 298: Chapter 66.4.2 Energy recovery from
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Page 301 and 302: Chapter 66.4.6 Scrubbing of tail ga
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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: Chapter 77.2 Applied processes and
Page 315 and 316: Chapter 77.2.3 Direct neutralisatio
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Page 319 and 320: Chapter7Per tonne productkWh Nm 3 k
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Chapter77.4.7 Optimising the recycl
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Chapter7Operational dataThe volume
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Chapter7Achieved environmental bene
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Chapter7Achieved environmental bene
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Chapter77.4.11 Recycling of scrubbi
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Chapter77.4.12 Waste water treatmen
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Chapter7ParameterLevelmg/Nm 3Phosph
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Chapter 88.2 Applied processes and
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Chapter 88.2.1.1 Particle formation
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Chapter 8Consumption of Per tonne u
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Chapter 8Per tonne urea Unit Remark
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Chapter 8Waste water per tonne urea
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Chapter 8Pollutant Source g/tonne u
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Chapter 8Plant Emission Amount (ton
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Chapter 8Operational dataSee Table
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Chapter 8Operational dataSee Table
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Chapter 88.4.6 Redirecting fines to
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Chapter 8Existing plantCase 2Revamp
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Chapter 88.4.8 Heat integration in
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Chapter 88.4.9 Combined condensatio
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Chapter 88.4.10 Minimisation of NH
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Chapter 8Other approaches to proces
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Chapter 88.5 BAT for Urea and UANBA
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Chapter 9Country Company LocationBe
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Chapter 99.2.2 NeutralisationThe ex
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Chapter 9Scrubbing devices• packe
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Chapter 9Pollutant mg/Nm 3 g/tonne
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Chapter 99.4 Techniques to consider
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Chapter 99.4.2 Recovery of residual
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Chapter 99.4.3 Energy consideration
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Chapter 99.4.4 Steam purification a
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Chapter 99.4.5 Autothermal granulat
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Chapter 9ApplicabilityIrrigated can
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Chapter 1010 SUPERPHOSPHATES10.1 Ge
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Chapter 10Emissionto airEmissionto
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Chapter 10Input Indirect granulatio
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Chapter 10Volume5 - 10 m 3 /hourTem
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Chapter 1010.4.2 Recovery and abate
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Chapter 1010.4.4 Recycling of scrub
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Chapter 1111 CONCLUDING REMARKS11.1
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Chapter 11Production of HNO 3 : De-
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References26 Dipankar Das (1998).
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References89 Kuiper (2001). "High t
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References147 Uhde (2006). "The Uhd
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GlossaryCalculation of steam proper
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GlossaryIPCCIPPCISO 14001Intergover
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GlossaryChemical formulasAl 2 O 3Ca
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Annexes14 ANNEXES14.1 Cost calculat
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