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Chapter 1010.2 Applied processes and techniques10.2.1 OverviewFor an overview, see Figure 10.1.SSP and TSP are manufactured as follows: phosphate rock is ground very finely and mixed withacid (SSP: 65 – 75 % H 2 SO 4 ; TSP: a H 3 PO 4 with a P 2 O 5 content of 50 – 55 %), giving thefollowing overall reactions:(SSP)(TSP)Ca 10 F 2 (PO 4 ) 6 + 7 H 2 SO 4 + H 2 O f 3 Ca(H 2 PO 4 ) 2·H 2 O + 7 CaSO 4 + 2 HFCa 10 F 2 (PO 4 ) 6 + 14 H 3 PO 4 + 10 H 2 O f 10 Ca(H 2 PO 4 ) 2·H 2 O + 2 HFIn the SSP process, H 3 PO 4 is formed only as an intermediate. The reactions are rapid (more than96 % yield) but can continue for several days as the remaining free acid continues reacting withthe excess phosphate rock. The SSP process retains the calcium sulphate (CaSO 4 ) in the productunlike the similar reaction producing phosphoric acid.Ground phosphate rock and acid are mixed in a reaction vessel. The reaction begins in thereactor, and is exothermic, reaching temperatures of 90 – 100 ºC. The slurry is fed on to a slowmoving conveyor belt (the so-called “den”) or to a holding vessel and held for a period from 10to up to 40 minutes. The superphosphate is crushed and afterwards fed to a granulation line(direct granulation) or to storage (pile) for “curing” from one to up to six weeks. Thesuperphosphate can be fed to the granulation line (indirect granulation) or sold without furtherprocessing from the storage facility.As well as SSP or TSP, partially acidulated phosphate rock (PAPR) can also be produced.PAPR is a mixture of superphosphate and phosphate rock. This product can be made in an SSPor TSP plant using a lower proportion of H 2 SO 4 or H 3 PO 4 to phosphate rock.From the storage pile, the cured superphosphate is ground and granulated. Steam, water or acidmay be added to help granulation. Direct granulation has some advantages in comparison togranulation after storage (pile) for curing; production costs are usually lower and the granulesare denser and stronger [52, infoMil, 2001]. Some disadvantages of direct granulation are theneed to use reactive phosphate rock and the possibility of greater losses of soluble P 2 O 5 due tothe incomplete reactions.Phosphate rock can contain small amounts of organic compounds. During the reaction with theacid, these organic compounds are released. Compounds, such as mercaptanes can cause odournuisance. For phosphate rock selection, see also Section 5.4.9.10.2.2 Raw materialsAn important factor in the production of SSP and TSP is the amount of aluminium (as Al 2 O 3 ),iron (as Fe 2 O 3 ) and magnesium compounds in the phosphate rock; the presence of theseelements reduces the water solubility of the phosphate. Two sources of H 2 SO 4 used insuperphosphate production are virgin acid and spent acid of sufficient quality. Virgin acid isproduced from SO 2 derived from burning elemental sulphur (sulphur-H 2 SO 4 ), pyrite (pyriteacid) or as a by-product acid from non-ferrous metal smelters processing sulphide ores (fatalacid). Spent acid is recycled from various industries (e.g. non-ferrous metal smelters) that uselarge quantities of H 2 SO 4 . For more information on phosphate rock and sulphuric acid, seeSections 5.2.2.1.1 and 5.2.2.1.2.388 Large Volume Inorganic Chemicals – Ammonia, Acids and Fertilisers
Chapter 10Emissionto airEmissionto airH 2 OH 2 OPhosphaterockFabricfilterScrubbingsystemScrubbingsystemScrubbingsystemRockgrindingWastewaterCycloneGround rawphosphateMixer?Waste watertreatmentGranulationDryingH 2 SO 4H 2 OH 3 PO 4Enclosed conveyor“den” and crushingCuringbuildingScreeningCoolingEmissionto water“run of the pile”productDirectly orindirectlygranulated productFigure 10.1: Overview of the production of superphosphates including an example for an exhaust gas abatement systemThis figure is based on [9, Austrian UBA, 2002, 52, infoMil, 2001, 53, German UBA, 2002]Large Volume Inorganic Chemicals – Ammonia, Acids and Fertilisers 389
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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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Chapter 4BAT is to minimise and red
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Chapter 55.2 Applied processes and
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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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Chapter 5Emission of mg/l g/tonne P
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Chapter 55.4 Techniques to consider
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Chapter 55.4.2 Hemihydrate process
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Chapter 55.4.3 Hemi-dihydrate recry
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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
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Chapter 55.4.7 Fluoride recovery an
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Chapter 55.4.8 Recovery and abateme
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Chapter 5Operational dataNo informa
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Chapter 55.4.11 Decadmation of H 3
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Chapter 55.4.12 Use of entrainment
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Chapter 5Cross-media effects• dis
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Chapter 5Cross-media effectsTable 5
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Chapter 5ApplicabilityAt present, o
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Chapter 66 HYDROFLUORIC ACID6.1 Gen
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Chapter 6Component Portion (mass co
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Chapter 66.2.4 Process gas treatmen
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Chapter 6Emission of kg/tonne HF Re
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6.4 Techniques to consider in the d
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Chapter 66.4.2 Energy recovery from
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Chapter 66.4.4 Valorisation of fluo
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Chapter 66.4.6 Scrubbing of tail ga
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6.4.7 Scrubbing of tail gases: fluo
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Chapter 66.4.8 Abatement of dust em
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Chapter 66.4.9 Waste water treatmen
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Chapter 6Cross-media effects• 5 -
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Chapter 77 NPK AND CN7.1 General in
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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 88.2.1.1 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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Page 372 and 373: Chapter 8Driving force for implemen
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Page 376 and 377: Chapter 8Existing plantCase 2Revamp
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Page 380 and 381: Chapter 88.4.9 Combined condensatio
Page 382 and 383: Chapter 88.4.10 Minimisation of NH
Page 386 and 387: Chapter 8Other approaches to proces
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: Chapter 99.3 Current emission and c
Page 400 and 401: Chapter 9Pollutant mg/Nm 3 g/tonne
Page 402 and 403: Chapter 99.4 Techniques to consider
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: Chapter 1010 SUPERPHOSPHATES10.1 Ge
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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