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Chapter 6low boilers leaving the column are gathered with the residual gases from the condensers andpassed through a final H 2 SO 4 scrubber, where most of the HF is recovered. Thereafter residualgases pass through the SiF 4 absorber, where H 2 SiF 6 is produced as an aqueous solution. Inplants without a final H 2 SO 4 scrubber, H 2 SiF 6 acid with a relatively high HF content isproduced.Cold H 2 SO 4 from the final H 2 SO 4 scrubber, which contains dissolved HF, passes to the firstH 2 SO 4 scrubber (pre-purification column), where it is heated in contact with the process gasesof the kiln. Acid from the scrubber is mixed in a vessel with fresh H 2 SO 4 and oleum to yield thefeed H 2 SO 4 for the reaction process.Depending on the quality of the HF after the low boilers distillation and on the end-use, asecond distillation may be required to remove any high boilers, mainly H 2 O and H 2 SO 4 . As allthe HF has to be evaporated, this distillation requires a significant amount of energy, estimatedat 350 kg steam per tonne of HF (0.6 GJ/tonne HF). The corresponding amount of refrigerationenergy required to condense the HF also needs to be taken into account. The liquid HF leavingthe head condenser is pure HF. Part of the HF is mixed with water to produce HF of varyingconcentrations: 85, 73, 60 and 40 %. Mixing is strongly exothermic and sufficient coolingsystems are necessary to avoid HF losses by evaporation. The production of high purityelectronic grade HF out of technical grade HF requires special plants and sophisticatedanalytical techniques.6.2.5 Tail gas treatmentThe quantity of tail gases needing treatment depends on the composition of the fluorspar. Awater and/or caustic absorption treatment of tail gases produces a neutralised aqueous effluentcontaining sulphates and fluorides, e.g. silica impurities in the fluorspar will be contained in theanhydrite or released as SiF 4 in the tail gases. In order to reduce SO 4 2- and F - concentrations,precipitation with calcium compounds and solid/liquid separation techniques are applied. Thisresults in a solid waste (CaSO 4 , CaF 2 ) which may be combined with the main flow of anhydriteco-product. The water absorption of the SiF 4 produces aqueous H 2 SiF 6 , which in some casesmay be sold or used as a feed material for the manufacture of fluorides or silicofluorides. H 2 SiF 6can also be chemically combined to produce CaF 2 and silica.6.2.6 Co-product anhydriteThe process generates anhydrite, CaSO 4 . This can, after further treatment of varying complexityand cross-media effects (i.e. after neutralisation), be further used as a market product in cementindustries or as binders for floor screed. This reduces the amount of waste for disposal [6,German UBA, 2000]. If not marketable, anhydrite is disposed of.6.2.7 Product storage and handlingAnhydrous HF is a liquid, which boils at 19.5 °C. It is possible to keep liquid HF at a lowtemperature, preferably below 15 °C, by cooling or by the installation of condensers in thestorage vent pipelines which condenses the evaporating HF. Liquid HF is normally stored atatmospheric pressure in carbon steel tanks. A thin protective layer of FeF 2 is quickly formedwhich prevents further corrosion. Liquid velocity in the pipelines should be below 1 m/s toavoid erosion of the FeF 2 layer.HF acid with a concentration of at least 70 % is stored in carbon steel tanks. Acid withconcentrations of less than 70 % is stored in lined steel tanks or alternatively in polyethylenetanks.262 Large Volume Inorganic Chemicals – Ammonia, Acids and Fertilisers
Chapter 66.3 Current emission and consumption levels6.3.1 Consumption levelsTable 6.4 shows the reported consumption levels for the production of HF.Raw materialsConsumption of per tonne HF Remark ReferenceFluorspar (CaF 2 ) 2100 – 2200 kg Of CaF 2H 2 SO 4 2600 – 2700 kg Of equivalent 100 % H 2 SO 4AuxiliaryNaOHFor alkaline scrubbingchemicals Ca(OH) 2 , CaO For neutralisationUtilitiesSteam150 – 800 kgProcess water 0.5 – 25 m 3Cooling water 30 – 100 m 3Electric power150 – 300 kWhRefrigeration2 – 3 GJFor distillation, kiln heating,cooling/condensation of HF.Concerning the fuel consumption, a dataset gathered in 1999 from 11 companiesshows:- 7 plants with levels between 4.5 and6.5 GJ/tonne HF[22, CEFIC, 2000]Fuel4 – 10 GJ- 2 plants with levels 7 GJ/tonne HFTable 6.4: Reported consumption levels for the production of HFLarge Volume Inorganic Chemicals – Ammonia, Acids and Fertilisers 263
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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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Chapter 4Economics[58, TAK-S, 2003]
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Chapter 4EconomicsNo specific infor
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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
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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
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Page 264 and 265: Chapter 55.4.6 RepulpingDescription
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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 315 and 316: Chapter 77.2.3 Direct neutralisatio
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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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