GTL-Case nov 10 Lovraj Workshop-1
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Transcript of GTL-Case nov 10 Lovraj Workshop-1
24/11/2010Slide Number- 1 of 38
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GTL: A CASE STUDY FORGTL: A CASE STUDY FOR6000 BPD GTL PLANT6000 BPD GTL PLANT
R. N. MAITIR. N. MAITI, AJAY N. DESHPANDE, AJAY N. DESHPANDE
R&D DIVISIONR&D DIVISION
24 - 2524 - 25thth November, 2010 November, 2010
LOVRAJ KUMAR MEMORIAL TRUST ANNUAL WORKSHOPLOVRAJ KUMAR MEMORIAL TRUST ANNUAL WORKSHOP
NEW DELHINEW DELHI
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OVERVIEWOVERVIEW
IntroductionIntroduction
Key technical components in GTL plant with FT routeKey technical components in GTL plant with FT route
Design Configuration of 6000 BPD GTL PlantDesign Configuration of 6000 BPD GTL Plant
Conversions & Thermal efficienciesConversions & Thermal efficiencies
Broad specifications of key equipmentsBroad specifications of key equipments
ConclusionsConclusions
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GTL IN GAS ECONOMYGTL IN GAS ECONOMY
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GTLGTL
GTL technology converts C1 fraction of natural gas to GTL technology converts C1 fraction of natural gas to hydrocarbon liquids hydrocarbon liquids
CH4 is chemically very stable components and requires CH4 is chemically very stable components and requires significant amount of energy and sophisticated catalyst systemssignificant amount of energy and sophisticated catalyst systems
GTL is residue free, sulphur freeGTL is residue free, sulphur free Products of GTLProducts of GTL
Naphtha; Diesel; High value Wax; High quality lube base Naphtha; Diesel; High value Wax; High quality lube base oilsoils
Not as substitute for piped natural gas/LNG/crudeNot as substitute for piped natural gas/LNG/crude
But as a unique feedstock for high quality fuels and lubesBut as a unique feedstock for high quality fuels and lubes
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Basic Gas to Liquids Process
Base Oil / LubricantsSolvents ( n –parrafins)
Methane (+Ethane)
Ethane
Jet / Kerosene
Specialty Waxes
Optional Products
Sulfur
Synthetic
Crude
O2
NaphthaDiesel
GasProcessing
SynthesisGas
FischerTropsch
ProductRefining
AirSeparation
Utilities =Water, Steam & Power
Offsites =Flares, Controls, Bldgs.
Natural GasAir
LPGs – Propane/Butane
CO
H2
LPG
Condensate – C5+
Steam & Water
Steam
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THREE STEP PROCESSTHREE STEP PROCESS
Syn Gas Generation: Steam Methane Reforming/partial Syn Gas Generation: Steam Methane Reforming/partial oxidation to produce syn gas (a mixture of hydrogen and CO oxidation to produce syn gas (a mixture of hydrogen and CO in the ratio of 2:1 molar)in the ratio of 2:1 molar)
Fischer Tropsch Synthesis: Syn gas synthesis to produce Fischer Tropsch Synthesis: Syn gas synthesis to produce liquid hydrocarbonsliquid hydrocarbons
Downstream processing (Tail gas treatment, Hydrocracking Downstream processing (Tail gas treatment, Hydrocracking of liquid products)of liquid products)
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Step 1- Synthesis Gas GenerationStep 1- Synthesis Gas Generation
Synthesis Gas Generation- Steam Methane Reforming (SMR)- Partial Oxidation (POX)- Autothermal Reforming (ATR)
Natural Gas
SMR : CH4 + H2O
POX : CH4 + 1/2O2
Synthesis Gas
CO + 3H2, endothermic 206 kJ/mol
CO + 2H2, exothermic 38 kJ/mol
xH2 + yCO
Available Technology
800oCCatalytic
900-1400oCNon-catalyticATR : Same as POX but catalytic & uses air instead of oxygen
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REACTIONS OCCURRING IN SYN GAS REACTORREACTIONS OCCURRING IN SYN GAS REACTOR
Reaction Mechanism
Reaction chemistry Hydrogen to CO ratio, Molar
Heat of Reaction, KJ/mol (20)
Steam Reforming CH4 + H2O CO + 3 H2 3 -206.1
Partial Oxidation 2CH4 + O2 2CO + 4 H2 2 38.0
Water Gas Shift reaction
CO + H2O CO2 + H2 - 41.15
CO2 Reforming CH4 + CO2 2CO + 2 H2 1 -247.3
Carbon Deposition CH4 2H2 + C -74.82Carbon Conversion C + H2O CO + H2 1 -131.3
Carbon Deposition 2CO CO2 + C - 173.3
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SYN GAS REACTORSSYN GAS REACTORS
Processes Typical H2/CO ratio, molar
Oxygen Requirement
(Kg/Kg of NG)
Steam Methane Reforming (SMR)
>2.5 Nil
Partial Oxidation (POX) 1.5 - 2.0 1.0 - 1.2
Autothermal
(SMR + POX)
1.5 - 2.7 0.3 – 0.5
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STEP 2 : F-T SYNTHESIS CONVERSIONSTEP 2 : F-T SYNTHESIS CONVERSION
F-T Reactor
Available Technology - Fixed bed - Fluidized bed (Circulating / Fixed) - Slurry bed
Synthesis Gas
Catalysts - Cobalt - Iron
CO hydrogenation nCO + 2nH2
Water gas shift CO + H2O
Methanation CO + 3H2
Syncrude (Long chain aliphatic HC,mainly n-paraffins)
(-CH2-)n + nH2O-152 kJ/molH2 + CO2 -41 kJ/molH2O + CH4 -206 kJ/mol
xH2+yCO (-CH2-)n
180-350oC20-35 bar
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PRODUCT DISTRIBUTIONPRODUCT DISTRIBUTION
For further distribution of heavy cuts (CFor further distribution of heavy cuts (C55++) into gasoline ) into gasoline
(C(C5 5 - C- C1111), diesel (C), diesel (C11 11 - C- C1818), wax (C), wax (C1919++) Shultz-Flory ) Shultz-Flory
theory was used as given belowtheory was used as given below
Where WWhere Wr+r+ is weight of product with carbon number is weight of product with carbon number
greater than r-1, x = 5 and α is the probability of chain greater than r-1, x = 5 and α is the probability of chain growth.growth.
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SALIENT FEATURES OF F-T SYNTHESIS SALIENT FEATURES OF F-T SYNTHESIS Composition is a function of chain growth mechanismComposition is a function of chain growth mechanism
Product is a mixture of light & heavy hydrocarbonsProduct is a mixture of light & heavy hydrocarbons
Composition depends on reaction temperature Composition depends on reaction temperature
-- 180-250 deg C : Predominantly diesel & waxes180-250 deg C : Predominantly diesel & waxes
-- 330-350 deg C : Predominantly gasoline & olefins330-350 deg C : Predominantly gasoline & olefins
Heat removal and control of temperature extremely critical. Heat Heat removal and control of temperature extremely critical. Heat typically recovered by boiling water in reactor tubes. typically recovered by boiling water in reactor tubes.
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F-T CATALYSTS F-T CATALYSTS Focused on achieving highest chain growth (>0.95) Focused on achieving highest chain growth (>0.95)
towards heavy waxestowards heavy waxes Comprise of primary metal (Co or Fe), secondary metal Comprise of primary metal (Co or Fe), secondary metal
(Ru-Noble metal) & oxide promoter on alumina / silica (Ru-Noble metal) & oxide promoter on alumina / silica supportsupport
Co CatalystCo Catalyst Fe CatalystFe CatalystLifeLife Long Long Short Short
CostCost ExpensiveExpensive Low cost Low costSyngas H2/COSyngas H2/CO 2.0 2.0 0.7 to 2.0 0.7 to 2.0ProductsProducts Lower MW Lower MW High MW High MWBy productsBy products H2OH2O H2O/CO2 H2O/CO2
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F-T REACTORSF-T REACTORS
Fixed Bed Reactor (FB)Fixed Bed Reactor (FB) Multitubular design with catalyst packed in tubesMultitubular design with catalyst packed in tubes Diameter limited by slow heat removalDiameter limited by slow heat removal Good for heavy liquid & waxesGood for heavy liquid & waxes
Fluidised Bed ReactorFluidised Bed Reactor Two typesTwo types : Circulating Fluidised Bed (CFB) : Circulating Fluidised Bed (CFB)
Fixed Fluidised Bed (FFB)Fixed Fluidised Bed (FFB) Improved heat removal by circulating gasImproved heat removal by circulating gas Suitable for gasoline ; Unsuitable for heavy waxesSuitable for gasoline ; Unsuitable for heavy waxes Reduced catalyst consumption in FFBReduced catalyst consumption in FFB
Slurry Reactor (MPSR)Slurry Reactor (MPSR) Very high heat transfer rateVery high heat transfer rate High conversion per pass avoids recycle costHigh conversion per pass avoids recycle cost Higher catalyst activity with better selectivity as no hot spotsHigher catalyst activity with better selectivity as no hot spots Catalyst regeneration by continuous purge and feedCatalyst regeneration by continuous purge and feed
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STEP 3 : PRODUCT REFININGSTEP 3 : PRODUCT REFINING
ProductRefining
Long chain waxy HC Naphtha,Kero, Diesel,Waxes
(-CH2-)n
• Hydroprocessing Section - Hydroisomerisation / hydrocracking of n-paraffins to iso-paraffins of
desired length & boiling range- Mild hydrocracking at 300-350 deg C & 30-50 bar- Reactivity increases with increasing number of paraffins - Maximum yield of middle distillates
- Minimum yield of C4 & lighters• Distillation Section
Conventional distillation for product fractionation• Gas Processing & Wax Finishing as necessary
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TAIL GASTAIL GAS
Efficient utilization of tail gas is must to improve economicsEfficient utilization of tail gas is must to improve economics
Fuel Gas CombustionFuel Gas Combustion
LPG Recovery followed by Gas CombustionLPG Recovery followed by Gas Combustion
CO2 recovery followed by gas combustionCO2 recovery followed by gas combustion
CO2 recovery followed by adsorption for H2CO2 recovery followed by adsorption for H2
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GTL Block Flow DiagramGTL Block Flow Diagram
Tail gas
GTL ProductsSMR+ATR
Air sep unit
NG feed
CO2 Recycle
O2
Steam GenerationExport Steam
H2
N2
CO2
Amine treating
FT synthesis
Water treatment
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CONCEPT STUDIESCONCEPT STUDIES
BASISBASIS
Tripura Gas composition is taken as the basisTripura Gas composition is taken as the basis
SMR+ATR simulations were carried out using SMR+ATR simulations were carried out using
FEM of Gibbs Energy algorithm in Aspen PLUSFEM of Gibbs Energy algorithm in Aspen PLUS
Fixed bed FT reactor ( Reactor Model; in-house)Fixed bed FT reactor ( Reactor Model; in-house)
Utilization of tail gas Utilization of tail gas
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GAS COMPOSITIONSGAS COMPOSITIONS
Composition Mol% H2
CH4 97.53C2H6 1.97C3H8 0.12
C4H10 0.02N2 0O2 0CO 0
CO2 0.36H2O 0CO2 0
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SYN GAS GENERATIONSYN GAS GENERATION
FEM studies (using ASPEN RGIBBS reactor module) show that FEM studies (using ASPEN RGIBBS reactor module) show that POX, Steam Reforming, and ATR reactors operate close to POX, Steam Reforming, and ATR reactors operate close to thermodynamic equilibrium.thermodynamic equilibrium.
The model is used to determine steam and oxygen feed rates, and The model is used to determine steam and oxygen feed rates, and operating temperature and pressure required for obtaining syngas operating temperature and pressure required for obtaining syngas of required composition.of required composition.
Part of the Natural gas is reformed at high steam to carbon ratio Part of the Natural gas is reformed at high steam to carbon ratio with heat derived from hot syn gas from POXwith heat derived from hot syn gas from POX
Partially reformed syn gas along with balance natural gas and Partially reformed syn gas along with balance natural gas and oxygen is oxidised in second reactor at substoichiometric conditionoxygen is oxidised in second reactor at substoichiometric condition
Syn gas from second reactor provides heat for reforming in first Syn gas from second reactor provides heat for reforming in first reactorreactor
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FT REACTORFT REACTOR
Multi tubular fixed bed reactor modelMulti tubular fixed bed reactor model Kinetics based on FE catalystKinetics based on FE catalyst Once through typeOnce through type Intermittent removal of WaterIntermittent removal of Water Optimum Tube diameter for better heat Optimum Tube diameter for better heat
removalremoval
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FLOW SCHEMEFLOW SCHEME
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FLOW SCHEMEFLOW SCHEME
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OVERALL MATERIAL BALANCEOVERALL MATERIAL BALANCE
H/C 1046 TPD
Water 1394 TPD
SMR +ATR
ASU/PSA
PSA
Three Phase Flash
NG 1947 TPD(1612+336)
SG 7452 TPD
CO2 Recyl 840 TPD
O2 (95%) 362 TPD
Power Plant
Amine
Treating
CO2 Purge450 TPD
FT I/II/III
TG454 TPD
Water3071TPD
H2191 TPD
Steam 4639 TPD
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CONVERSIONSCONVERSIONS
Conversion calculations
NG Feed Basis
Feed 67155 Kg/h
Product 43583 Kg/h
Conversion 64.9 %
Total NG Basis
NG to Feed 67155 Kg/h
NG to fuel header 13981 Kg/h
Product 43583 Kg/h
Conversion 53.7 %
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OVER ALL ENTHALPY BALANCEOVER ALL ENTHALPY BALANCE
Overall Enthalpy Balance
Feed Q, mmkcal/hTo Unit 725To SMR 151
ProductsH/C Liquid 436Hydrogen 228Tail gas 111Loss with Flue Gas 38Loss with Syn gas Cooler 45 Thermal Conversion 60.1%
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OVERALL GTL CHEMISTRYOVERALL GTL CHEMISTRY
(12+x) CH4 + (5.5 +2 x) O2 (12+x) CH4 + (5.5 +2 x) O2
n C12 H26 + (11+2x) H2O + x CO2n C12 H26 + (11+2x) H2O + x CO2
With x = 0With x = 0 Max theoretical energy efficiency : 78%Max theoretical energy efficiency : 78% Carbon conversion efficiency : 100%Carbon conversion efficiency : 100%
With x = 2.4 - 3.6With x = 2.4 - 3.6 Thermal efficiency up to 60-65%Thermal efficiency up to 60-65% Carbon conversion efficiency up to 77-83 %Carbon conversion efficiency up to 77-83 %
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CARBON BALANCE THROUGH CARBON BALANCE THROUGH REACTORSREACTORS
Carbon Balance
Feed 4183 kmol/h
Product
Liquid Products 3072 kmol/h
Tail Gas 682 kmol/h
CO2 vent 427 kmol/h
Total 4180
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CARBON DISTRIBUTIONCARBON DISTRIBUTION
H/C 73.5
Water
SMR +ATR
ASU/PSA
PSA
Three Phase Flash
NG 120
SG100
CO2 Recyl
O2 (95%)
Power Plant
Amine
Treating
CO2 Purge10.2
FT I/II/III
TG16.3
Water
H2
Steam
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ENTHALPYENTHALPY
H/C 60.1
Water
SMR +ATR
ASU/PSA
PSA
Three Phase Flash
NG 100+20
SG
CO2 Recyl
O2 (95%)
Power Plant
Amine
Treating
CO2 Purge
FT I/II/III
TG
Water
H231.5
Steam
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UTILITY: HP STEAM DRIVEN COMPRESSORSUTILITY: HP STEAM DRIVEN COMPRESSORS
Compressors
K-01 ng compressor 2109 KW
K-02syn gas compressor 17900 KW
K-03 O2 compressor 1160 KW
K-04 CO2 compressor 4240 KW
K-05 air compressor 660 KW
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UTILITIES: STEAM GENERATION/CONSUMPTIONUTILITIES: STEAM GENERATION/CONSUMPTION
HP Steam Consumption Press (Kg/cm2.g)
Temp (Deg C)
Reformer193276 kg/hr 42 258
Compressors K-01 to K-05192056 kg/hr 42 450
Excess Steam for power generation 97944 kg/hr 42 450
MP steam Amine Absorber
FT Feed Heaters
Generation
HP Steam Flue Gas + ATR o/I200000 kg/hr 42 258
Flue Gas + ATR o/I290000 kg/hr 42 450
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BROAD SPECIFICATION OF FT REACTORSBROAD SPECIFICATION OF FT REACTORS
FT Reactors
40 mm ID tube, 12 m
R-04 A/B/C
FT Reactor-1 63 MMKcal/h, 12000 tubes, 4000 tubes/reactor
R-5 A/B FT Reactor-231 MMKcal/h, 5800 tubes, 2900/reactor
R-06 FT Reactor-317 MMKcal/h, 4000 tubes
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BROAD SPECIFICATION OF COMPRESSORSBROAD SPECIFICATION OF COMPRESSORS
Power, KW Turbine type
HP steam driven (steam @ 42 kg/cm2 g, 450 deg C)
K-01 NG compressor 2109 Back Press
K-02 syn gas compressor 17900 Condensing
K-03 O2 compressor 1160 Back Press
K-04 CO2 compressor 4240 Back Press
K-05 Air compressor 6600 Back Press
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BROAD SPECIFICATION OF EXCHANGERSBROAD SPECIFICATION OF EXCHANGERS
Exchangers Q, mmKcal/h
E-01 RG Boiler 147
E-02 Economiser 45
E-03A DM water Heater 24
E-03B Syn gas Cooler 54
E-04 Feed to Reactor FT-1 10.57
E-05 FT-1 o/I and syn gas exchanger 4.45
E-06 FT-1 product cooler 25.6
E-07 FT-2 feed heater 4.42
E-08 FT-2 O/I and syn gas exchanger 3.16
E-09 FT-2 Product cooler 13.6
E-10 FT-3 feed heater 3.02
E-11 FT-3 product cooler 10.5
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CONCLUSIONSCONCLUSIONS
The various technical components of GTL plant through The various technical components of GTL plant through FT route for natural gas utilization are presentedFT route for natural gas utilization are presented
Conceptual design configuration of 6000 BPD GTL plant Conceptual design configuration of 6000 BPD GTL plant providedprovided
Recycle of CO2 and utilization of Tail gas scheme Recycle of CO2 and utilization of Tail gas scheme incorporated for better economyincorporated for better economy
Mass conversion is found to be 64.9%Mass conversion is found to be 64.9% Thermal conversion was found to be 60.1% for H/C liquids Thermal conversion was found to be 60.1% for H/C liquids
and 75.8% considering H2 productionand 75.8% considering H2 production
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CONCLUSIONSCONCLUSIONS
HP steam(@450 0C, 42 ata) and excess H2 is for export or HP steam(@450 0C, 42 ata) and excess H2 is for export or integration with refinery.integration with refinery.
GTL is very expensive process. An attempt is made to provide GTL is very expensive process. An attempt is made to provide the Facts and Figures of a semi-commercial size GTL plant. the Facts and Figures of a semi-commercial size GTL plant.
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Economics for a 7100 BPD GTL Plant at NumaligarhEconomics for a 7100 BPD GTL Plant at Numaligarh
Case Natural Gas @ Rs 0.6/SCM*
Natural Gas @ Rs 1.7/SCM
Natural Gas @ Rs 3.0/SCM
Installed Cost 350 350 350
Annual Expenditure
Feed Stock 13.2 37.5 66.2
Others 15.9 19.8 24.3
Annual Revenue 131.2 131.2 131.2
Internal Rate of Return, % 23 17 8
In Million US Dollars* ~ 0.5 US $/Million BTU
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Product distributionProduct distribution
C5-12=28%C5-12=28%
C13-18=22.6%C13-18=22.6%
C18+=49.6%C18+=49.6%
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Free Energy Minimization StudiesFree Energy Minimization Studies
ASPEN Plus RGIBBS reactor model usedASPEN Plus RGIBBS reactor model used Chemical and phase equilibrium composition can be Chemical and phase equilibrium composition can be
calculated calculated Approach used is Gibbs free energy minimization Approach used is Gibbs free energy minimization
(FEM) of the system subject to atom balance (FEM) of the system subject to atom balance constraints constraints
Reaction stoichiometry need not be specifiedReaction stoichiometry need not be specified However, with reaction stoichiometry defined, approach However, with reaction stoichiometry defined, approach
to equilibrium can be specifiedto equilibrium can be specified
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Conclusions from FEM StudiesConclusions from FEM Studies POX, Steam Reforming, and ATR reactors operate POX, Steam Reforming, and ATR reactors operate
close to thermodynamic equilibriumclose to thermodynamic equilibrium.. ASPEN RGIBBS reactor module can be used for ASPEN RGIBBS reactor module can be used for
predicting the equilibrium outlet composition for predicting the equilibrium outlet composition for SMR, POX and ATR.SMR, POX and ATR.
The model can be used to determine steam and The model can be used to determine steam and oxygen feed rates, and operating temperature and oxygen feed rates, and operating temperature and pressure required for obtaining syngas of required pressure required for obtaining syngas of required composition.composition.
Design of individual systems such as burner, Design of individual systems such as burner, reactor size, feed distributor, catalyst bed etc is to reactor size, feed distributor, catalyst bed etc is to be decided by specialized groupbe decided by specialized group
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SYN gas generationSYN gas generation
ASPEN RGIBBS reactor module can be used for ASPEN RGIBBS reactor module can be used for predicting the equilibrium outlet composition for SMR, predicting the equilibrium outlet composition for SMR, POX and ATRPOX and ATR
POX, Steam Reforming, and ATR reactors operate POX, Steam Reforming, and ATR reactors operate close close to thermodynamic equilibriumto thermodynamic equilibrium..
Part of the Natural gas is reformed at high steam to Part of the Natural gas is reformed at high steam to carbon ratio with heat derived from hot syn gas from POXcarbon ratio with heat derived from hot syn gas from POX
Partially reformed syn gas along with balance natural gas Partially reformed syn gas along with balance natural gas and oxygen is oxidised in second reactor at and oxygen is oxidised in second reactor at substoichiometric conditionsubstoichiometric condition
Syn gas from second reactor provides heat for reforming Syn gas from second reactor provides heat for reforming in first reactorin first reactor
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Studies with actual caseStudies with actual case
Part of the Natural gas is reformed at high steam to Part of the Natural gas is reformed at high steam to carbon ratio with heat derived from hot syn gas from carbon ratio with heat derived from hot syn gas from POXPOX
Partially reformed syn gas along with balance natural Partially reformed syn gas along with balance natural gas and oxygen is oxidised in second reactor at gas and oxygen is oxidised in second reactor at substoichiometric conditionsubstoichiometric condition
Syn gas from second reactor provides heat for Syn gas from second reactor provides heat for reforming in first reactorreforming in first reactor
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Methane Autothermal reformingMethane Autothermal reforming
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Performance IndicesPerformance Indices
Conversion (H2+CO):-Conversion (H2+CO):- 94%94% Conversion H2:-Conversion H2:- 96.1%96.1% Conversion CO:-Conversion CO:- 89.9%89.9%
C5+ g/NM3 of (H2+CO) converted:- 190C5+ g/NM3 of (H2+CO) converted:- 190 C5+ conversion based on NG= 61%C5+ conversion based on NG= 61% Recycle compressor eliminated for FT reactorRecycle compressor eliminated for FT reactor
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Procedure Validation (POX)Procedure Validation (POX)
Simulation of Shell Gasification Process (SGP) Data for Natural Gas Feedstock
Parameter Case-1 Case-2 Case-3
Steam/C 0.176 0.176 0.655
O2/C 0.638 0.642 0.684
CO2/C 0.35 Nil Nil
Shell Aspen Shell Aspen Shell Aspen
H2/CO
H2 mol% dry
CO “
CO2 “
CH4 “
1.6
57.46
35.83
5.45
1.0
1.64
58.8
35.8
4.6
0.64
1.83
61.88
33.75
3.1
1.0
1.93
63.6
33.0
2.8
0.4
2.0
61.71
30.85
6.16
1.0
2.17
63.7
29.4
6.28
0.37
GTL: A case study for 6000BPD GTL Plant24/11/2010
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Procedure Validation (Primary/Secondary Procedure Validation (Primary/Secondary Reformer)Reformer)
Parameter Case1(P=9.5bar) Case2 (P=16.0bar) Case3 (POX)
Steam/C 2.226 4.0 Nil
O2/C 0.2923 0.239 0.665
Kellogg Aspen Kellogg Aspen Texaco Aspen
% Conv 99.12 99.73 99.04 99.75 >99.9 >99.9
H2/CO 3.564 3.57 4.86 4.72 1.745 1.659
GTL: A case study for 6000BPD GTL Plant24/11/2010
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Procedure Validation (ATR)Procedure Validation (ATR)
Simulation of Haldor Topsoe (HT) Data
Parameter Case-A Case-B Case-C Case-D
Steam/C 0.6 0.36 0.21 0.51
O2/C 0.58 0.57 0.59 0.62
CO2/C 0.01 0.01 0.01 0.19
HT Aspen HT Aspen HT Aspen HT Aspen
Temp, C 1000 1020 1021 1022 1065 1100 1031 1025
H2/CO
H2+CO*
CH4+CO2*
2.34 2.3 2.16
93.4
6.5
2.15
93.6
6.2
2.02
95.7
4.2
1.96
95.4
4.4
1.83
91.3
8.6
1.8
91.5
8.3
* Mol % dry
GTL: A case study for 6000BPD GTL Plant24/11/2010
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REACTOR MODEL: FT ReactionREACTOR MODEL: FT Reaction
molkJH
OHCHOHCO
R /152298
120
222
molkJH
HCOOHCO
R /41298
30
222
molkJH
OHCHHCO
R /206298
230
242
GTL: A case study for 6000BPD GTL Plant24/11/2010
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REACTOR MODEL: Rate equationREACTOR MODEL: Rate equation
OHSoHSSCO
HMoHMMCO
HFToFTCO
SCOMCOFTCOiCOmn
cekcTkr
cekcTkr
cekr
rrrr
RTMAE
RTMAE
COcOHc
RTFTAE
cat
CO
2,2,
2,2,
6.11
12,,
,,,,
,
,
2
,
conversion CO of rate Total
GTL: A case study for 6000BPD GTL Plant24/11/2010
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REACTOR MODEL: Mass, Momentum and energy REACTOR MODEL: Mass, Momentum and energy balancebalance
40
COforequationContinuty
, zru iCOBZC
SCO
50
equation BalanceEnergy 4
,
coolDU
RiCOBZT
ptS TTHizrCCu
mht
DoDi
hohiU 111
where
75.1
6
equationbalance Momentum
Re150
100133.11
2
163
2
p
pf
p
p
r
Gf
ZP
f
GTL: A case study for 6000BPD GTL Plant24/11/2010
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Process Integration IssuesProcess Integration Issues
Large energy streams for syn gas generation and syn Large energy streams for syn gas generation and syn gas synthesisgas synthesis
The process can be configured to maximize on The process can be configured to maximize on power/hydrogen/Steam for exportpower/hydrogen/Steam for export
Efficient utilisation of tail gas is must to improve Efficient utilisation of tail gas is must to improve economicseconomics Four options were studiedFour options were studied
GTL: A case study for 6000BPD GTL Plant24/11/2010
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Utilisation of Fuel GasUtilisation of Fuel Gas(Option-1 Fuel Gas Combustion)(Option-1 Fuel Gas Combustion)
Gas Combustion
Power/Steam
CO2 to vent
Fuel Gas 2407 TPD
Air
CO2 2560 TPD
•Gas to combustion has very low calorific value (1930 Kcal/kg)
•May require a support fuel
CO 169 TPD
CO2 1923
H2 89
N2 74
H/C 144
H2O 8
GTL: A case study for 6000BPD GTL Plant24/11/2010
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Utilisation of Fuel GasUtilisation of Fuel Gas(Option-II LPG Recovery followed by Gas Combustion)(Option-II LPG Recovery followed by Gas Combustion)
LPG Recovery
LPG 78 TPD
Gas Combustion
Power/Steam
CO2 to vent
Fuel Gas 2407 TPD
Air
CO2 2200 TPD
CO 6% Mol
CO2 43.6%
H2 44.4%
N2 2.6%
H/C 2.9%
H2O 0.5%
•Gas to combustion has very low calorific value (1600 Kcal/kg) may require a support fuel
•Additional recovery of LPG
CO 169 TPD
CO2 1923
H2 89
N2 74
H/C 144
H2O 8
GTL: A case study for 6000BPD GTL Plant24/11/2010
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Utilisation of Fuel GasUtilisation of Fuel Gas(Option-III CO2 recovery followed by gas (Option-III CO2 recovery followed by gas
combustion)combustion)
CO2 Recovery by DEA
CO2 1923 TPD
Gas Combustion
Power/Steam
CO2
Fuel Gas 2407 TPD
Air
CO 9.8% Mol
H2 72.6%
N2 4.3%
H/C 12.6%
H2O 0.7%
•Gas to combustion has high calorific value (9600 Kcal/kg)
•Size of gas turbine is drastically reduced
GTL: A case study for 6000BPD GTL Plant24/11/2010
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Utilisation of Fuel GasUtilisation of Fuel Gas(Option-IV CO2 recovery followed by Adsorption)(Option-IV CO2 recovery followed by Adsorption)
CO2 Recovery
CO2 1923 TPD to vent
Low Pressure Gas to CO boiler/ Flare
Fuel Gas 2407 TPD
CO 9.8% Mol
H2 72.6%
N2 4.3%
H/C 12.6%
H2O 0.7%•Additional hydrogen is recovered; reduces steam injection to POX
•CO2 vented out separately
PSA
H2 to Export
GTL: A case study for 6000BPD GTL Plant24/11/2010
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EIL NEW DELHI INDIA
Partial OxidationPartial Oxidation
•CH4 + 1/2 O2 CO + 2 H2
•Combustion chamber at high temperature (1200- 1500°C); no catalyst
•Three process sections:
• Burner section where combustion occurs (with oxygen to avoid presence of nitrogen—nitrogen is desirable only when making ammonia)
• Heat recovery section
• Carbon black removal section: first by water scrubbing, Then, extraction by naphtha from the sludge
GTL: A case study for 6000BPD GTL Plant24/11/2010
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EIL NEW DELHI INDIA
Steam Methane ReformingSteam Methane Reforming CH4 + H2O CH4 + H2O CO + 3 H2 CO + 3 H2 Carried out in the presence of catalyst—usually nickel Carried out in the presence of catalyst—usually nickel
dispersed ondispersed onalumina supportalumina support
Operating conditions: 850 - 940°C, 30 Kg/cm2Operating conditions: 850 - 940°C, 30 Kg/cm2 Tubular, packed reactors with heat recovery from flue Tubular, packed reactors with heat recovery from flue
gases using feed preheating or steam production in gases using feed preheating or steam production in waste heat boilerswaste heat boilers
Combination of steam reforming with partial oxidationCombination of steam reforming with partial oxidation—uses the heat produced from partial oxidation to —uses the heat produced from partial oxidation to provide heat for steam reforming; resulting provide heat for steam reforming; resulting combination is autothermalcombination is autothermal– Gases from partial oxidation burner are mixed with – Gases from partial oxidation burner are mixed with steam and sent to the steam reformersteam and sent to the steam reformer