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Chapter 55.4.7 Fluoride recovery and abatementDescriptionFluoride is present in most phosphate rocks at a level of 2 – 4 %, that is 20 – 40 kg/tonne rockor approximately 60 – 120 kg/tonne P 2 O 5 . Fluoride is distributed between the product acid,gypsum, vapours generated in the reactor and the acid concentration section during processing.Initially, fluoride is released in the reaction as hydrogen fluoride (HF), but in the presence ofsilica it reacts readily to form fluosilicic acid (H 2 SiF 6 ) and compounds such as MgSiF 6 andH 3 AlF 6 . The fluosilicic acid may decompose with heating to give volatile silicon tetrafluorideand hydrogen fluoride.In a dihydrate (DH) process the temperature is usually too low to cause the decomposition offluosilicic acid. The majority of fluorine compounds will be evolved with the evaporatorvapours during concentration of the weak phosphoric acid. In the hemihydrate (HH) process,most of the fluoride is released during the reaction. Fluoride leaves the reactor with the vacuumcooler condenser water or with the cooling air, depending on the cooling system used (flashcooler or air circulating cooler). To prevent fluoride emissions with condenser water, theapplication of an indirect condensation system may be considered instead of a direct contactcondenser, thus avoiding that condenser water becoming contaminated with fluoride. A typicalfluoride distribution in the dihydrate process and hemihydrate process is shown in Table 5.9.DH Process (%) HH Process (%)Acid 15 12Gypsum 43 50Reactor off-gas 5 8Flash cooler vapour 3 30Concentrator vapour 35 - xx assuming that no concentration is carried outTable 5.9: Typical fluoride distribution in DH and HH processes[31, EFMA, 2000]Fluoride can be removed by a number of different scrubbing systems (see also Section 6.4.6).Vapours from vacuum flash coolers and vacuum evaporators are usually first led through aseparator for the removal of phosphoric acid droplets that are entrained with the vapours tominimise fluosilicic acid contamination with P 2 O 5 , or something just to minimise contaminationof the scrubber effluent.If the fluorine is not recovered, the scrubber effluent will be discharged. The effluent can beneutralised with lime or limestone to precipitate fluorine as solid calcium fluoride beforedischarge (see also Section 6.4.9).Many companies recover the fluorine as fluosilicic acid (H 2 SiF 6 ), which can be used for theproduction of aluminium fluoride, and other fluorine compounds such as sodium and/orpotassium fluosilicates. In this case, a dilute solution of fluosilicic acid is used as the scrubbingliquid. The reaction to fluosilicic acid results in the formation of free silica. By carefullycontrolling the fluosilic acid strength, silica deposition is controlled. The silica is then removedby filtration. Usually, a product containing 20 – 25 % fluosilicic acid is recovered in the fluoriderecovery system.238 Large Volume Inorganic Chemicals – Ammonia, Acids and Fertilisers
Chapter 5Achieved environmental benefits• with two or more absorbers a recovery efficiency of 99 % or more can be achieved.According to [31, EFMA, 2000], achievable fluoride emission levels for new plants are5 mg/Nm 3 (40 g/tonne P 2 O 5 ). In the Netherlands, emission levels of 1 – 5 mg/Nm 3 wereachieved [29, RIZA, 2000]• recovery of fluosilicic acid (H 2 SiF 6 ) with potential for valorisation (see Section 6.4.4), forproduction of HF from fluosilicic acid, see Section 6.4.10.Cross-media effectsWater, energy and chemicals consumption for scrubbing.Operational dataNo information provided.ApplicabilityGenerally applicable. Fluosilicic acid can be valorised if there is a market available.EconomicsFor cost estimates, see Table 6.10.Driving force for implementationReduced fluoride emission levels.References to literature and example plants[29, RIZA, 2000, 31, EFMA, 2000]Large Volume Inorganic Chemicals – Ammonia, Acids and Fertilisers 239
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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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Page 224 and 225: Chapter 4EconomicsCost benefits can
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Page 228 and 229: Chapter 44.4.16 Minimisation and ab
Page 230 and 231: Chapter 44.4.17 Minimisation of NO
Page 232 and 233: Chapter 44.4.19 Tail gas scrubbing
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Page 236 and 237: Chapter 4Economics[58, TAK-S, 2003]
Page 238 and 239: Chapter 4EconomicsNo specific infor
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Page 242 and 243: Chapter 55.2 Applied processes and
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
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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 280 and 281: Chapter 5Cross-media effectsTable 5
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Page 315 and 316: Chapter 77.2.3 Direct neutralisatio
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Chapter 7Fluorine compounds origina
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Chapter7Per tonne productkWh Nm 3 k
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Chapter7Emission levelmg/Nm 3 ppm k
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Chapter7Emission levelmg/Nm 3 ppm k
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7.4 Techniques to consider in the d
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Chapter7Driving force for implement
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Chapter7Achieved environmental bene
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Chapter77.4.6 Recycling warm airDes
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Chapter77.4.7 Optimising the recycl
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Chapter7Operational dataThe volume
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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 8Driving force for implemen
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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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