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Chapter 22.4.3 Heat exchange autothermal reformingDescriptionFrom a thermodynamic point of view, it is wasteful to use the high level heat of the secondaryreformer outlet gas and the primary reformer flue-gas, both at temperatures of around 1000 °C,just to raise steam. Recent developments aim to recycle this heat to the process itself, by usingthe heat content of the secondary reformer gas in a newly developed primary reformer (gasheated reformer, heat exchange reformer), thus eliminating the need for a fired reformerfurnace. Surplus air or oxygen-enriched air is required in the secondary reformer to meet theheat balance in this autothermal design.Heat for the reform reaction is supplied to the reforming tubes by hot process gas from thesecondary reformer. In a heat exchange primary reformer, excess air has to be supplied to thesecondary reformer to ensure a heat balance between these two steps, and this results in anoverstoichiometric amount of nitrogen in the gas. The high temperature shift reactor and the lowtemperature shift reactor are, in this technique, also replaced by a single isothermal mediumtemperature shift reactor using heat from the shift conversion for the saturation of process gaswith steam and recycling process condensates. A “pressure swing adsorption” (PSA) system isused to remove carbon dioxide and residual carbon monoxide and methane, to produce apurified synthesis gas. A cryogenic purification system may need to be incorporated in theprocess to remove the surplus nitrogen. A modified synthesis converter using an improvedcatalyst with a total resulting in a lower overall synthesis pressure further simplifies the process.Other configurations of the heat exchange primary reformer concept use alternative steps for theshift reaction and synthesis gas purification and ammonia synthesis compared to the above. Inone of these alternatives, only one third of the feed passes through the exchanger reformer withthe residual amount being sent directly to the secondary (autothermal) reformer, which usesenriched air (30 % O 2 ) instead of excess air. The ammonia synthesis uses a new rutheniumbasedcatalyst.Achieved environmental benefits• emissions to the air are reduced significantly by eliminating the flue-gas from the primaryreformer• NO x emissions may be reduced by 50 % or more, depending on the extent of auxiliarycombustion in the plant compared to conventional steam reforming.For achievable emission and consumption levels, see:• Table 2.6 for energy consumption• Table 2.7 for NO x emissions• and Table 2.8 and Table 2.9 for other levels.Cross-media effects• energy may need to be imported to drive mechanical equipment• higher total energy consumption in comparison with other steam reforming concepts.Operational dataNo specific information provided.62 Large Volume Inorganic Chemicals – Ammonia, Acids and Fertilisers
Chapter 2ApplicabilityApplicable for new plants.EconomicsNo specific information provided.Driving force for implementationThis plant concept allows the building of a plant which can be started up quickly.References to literature and example plants[1, EFMA, 2000, 3, European Commission, 1997], so far seven installations of capacities from350 to 1070 tonnes per day have been built and operated.Large Volume Inorganic Chemicals – Ammonia, Acids and Fertilisers 63
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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
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
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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,
Page 76 and 77: Chapter 22.2.6 Storage and transfer
Page 78 and 79: Chapter 2Production process Feedsto
Page 80 and 81: Chapter 22.3.2 NO x emissionsTable
Page 82 and 83: Chapter 22.3.3 Other consumption le
Page 84 and 85: Chapter 2ParameterProcessEmission l
Page 86 and 87: Chapter 22.4 Techniques to consider
Page 88 and 89: Chapter 22.4.2 Processes with reduc
Page 92 and 93: Chapter 22.4.4 Revamp: increase cap
Page 94 and 95: Chapter 22.4.5 Pre-reformingDescrip
Page 96 and 97: Chapter 2ApplicabilityGenerally app
Page 98 and 99: Chapter 22.4.7 Advanced process con
Page 100 and 101: Chapter 22.4.9 Combined Claus unit
Page 102 and 103: Chapter 2Operational dataSee Descri
Page 104 and 105: Chapter 22.4.12 Preheating of combu
Page 106 and 107: Chapter 22.4.14 Isothermal shift co
Page 108 and 109: Chapter 22.4.16 Stripping and recyc
Page 110 and 111: Chapter 22.4.18 Use of sulphur resi
Page 112 and 113: Chapter 22.4.20 Indirect cooling of
Page 114 and 115: Chapter 22.4.22 Ammonia removal fro
Page 116 and 117: Chapter 22.4.24 Metal recovery and
Page 118 and 119: Chapter 2Driving force for implemen
Page 120 and 121: Chapter 22.5 BAT for ammoniaBAT is
Page 123 and 124: Chapter 33 NITRIC ACID3.1 General i
Page 125 and 126: Chapter 3Pressure in bar Temperatur
Page 127 and 128: Chapter 33.2.5 Tail gas properties
Page 129 and 130: Chapter 33.3 Current emission and c
Page 131 and 132: Chapter 3N 2 O emission levelProces
Page 133 and 134: Chapter 3N 2 O emission levelProces
Page 135 and 136: Chapter 3Process typeNO x emission
Page 137 and 138: Chapter 3Process typeNO x emission
Page 139 and 140: 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 44.3 Current emission and c
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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 4Driving force for implemen
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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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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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