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GasificationGasification
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Low temperature (200-240°C) and mid pressure (20-30 bar) to promote F-T over methanation reaction
Active catalyst based on IRON or COBALT
Production of high molecular weight linear waxes for further hydroprocessing step to optimize the overall liquid production, because it is impossible to produce directly a well defined range of products (i.e. middle distillates)
Fischer-Tropsch Reaction
nCO + 2nH2 n(-CH2-) + n H2O ΔH=-167 kJ/mole
CO + 3 H2 CH4 + H2O Methanation (ΔH=-206 kJ/mole)CO + H2O CO2 + H2 Water Gas Shift (ΔH=-41 kJ/mole)2CO C + CO2 Boudouard reaction (ΔH=-172 kJ/mole)H2 + CO C + H2O Coke formation (ΔH=-133 kJ/mole)
MainMain featuresfeatures of of modernmodern GTLGTL--FT:FT:
LiquidFuels
Product
upgradingNG
F-T
synthesis
Syngas
Production
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Fischer-Tropsch
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Fischer-Tropsch
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Gas-to-Liquids (FT) Process
ProductProductUpgradeUpgrade
LPG
Kero/Diesel
NaphthaSyngasSyngas
GenerationGenerationH2
COFischerFischer--TropschTropsch
(CH2)
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Technology –FT Process
ProductProductUpgradeUpgrade
LPG
Kero/Diesel
NaphthaSyngasSyngas
GenerationGenerationH2
COFischerFischer--TropschTropsch
(CH2)
•Catalyst•Heat removal•Reactor design•Scale-up
Technical challenges
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The Sasol Slurry Bed Reactor
The largest commercialThe largest commercial--sized FT reactor sized FT reactor -- SASOL SASOL Pictures Courtesy of Sasol
Technical challenges
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Technology – Product Upgrade
ProductProductUpgradeUpgrade
LPG
Kero/Diesel
NaphthaSyngasSyngas
GenerationGenerationH2
COFischerFischer--TropschTropsch
(CH2)
•Catalyst•Capacity
Technical challenges
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History
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History
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Novocherkassk
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Novocherkassk
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History
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FT Reactor CapacitiesFT Reactor CapacitiesHistorical overviewHistorical overview
0
2000
4000
6000
8000
10000
12000
14000
16000
1910 1930 1950 1970 1990 2010 2030
Bar
rel /
day
Prof. Franz Fischer Dr. Hans TropschProf. Franz FischerProf. Franz Fischer Dr. Hans TropschDr. Hans Tropsch
Sasol CFBR
Sasol FFBR
Shell SMDSFBR
RuhrchemieFBR
Oryx GTL SBCR
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Mechanism
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Mechanism
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Mechanism: chain growth
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Mechanism
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Products
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Kinetics
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Catalysts
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Catalysts
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Fe
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Co
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Co catalysts
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Co catalysts
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SummarySummary: FT : FT CatalystCatalystActive Phase: Active Phase: CobaltCobalt, , IronIron
PromoterPromoterStructural: Structural: increase metal dispersion (Re, Zr, Hf, Ce) Reduction: Reduction: increase extent of reduction (Ru, Pd, Pt, Cu)Activity: Activity: prevent coke deposition (Noble Metals)Selectivity: Selectivity: alter the product distribution (Na, K, Cs)
Carrier: SiOCarrier: SiO22, Al, Al22OO33, TiO, TiO22, mix, mixStructural promoter itselfInfluence selectivity due to secondary reaction (i.e. acid sites)
Co Co basedbased catalystcatalystExpensiveHigh selectivity to long chainparaffinsLow selectivity to olefins and oxygenatesresistant to deactivationlimited WGS activity
Fe Fe basedbased catalystcatalystEconomicLow selectivity to long chainparaffinsHigh selectivity to olefins and oxygenatesWGS catalystFast deactivation (coke)
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Catalysts
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Reactors
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Catalyst d> 1mm; Effectiveness factor below unity
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Reactors
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Fluidized beds
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Slurry
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Slurry
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Operation
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Reactor comparison
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Technologies
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Plants
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Sasol Synfuels, Secunda, South Africa, (2008)
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SASOL II
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Products from GTL-FT process
LPG 3%
Naphtha
Gasoline
Middle Distillates
Fuel Oil 20%
40%
27%
10%
Lubes/Waxes
Middle Distillates
LPG/Naphtha
0 - 30%
20 - 35%
50 - 75%
Refinery Barrel Yield(Brent, vol)
GTL Barrel(vol)
Typical FT product composition after upgrading is: 25% Virgin Naphtha, 25% Jet Fuel and 50% Diesel
and minor amounts of LPG and bottom hydrocracking. The heavier fraction can be usedfor the production of lubricating bases or chemicals.
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-1
- 11
55
22
4.5
835
180-360
Blu Blu DieselDieselAgipAgip
0
- 15
> 51
30
50
820 – 845
180-360
ConventionConventionalal DieselDiesel
-15 n.d.Cloud point (°C)
- 20 - 12CFPP* (°C)
> 70 56 Cetane number (CN)
< 0.13Aromatics (% vol)
< 1 6Sulfur (ppm vol)
780805Density @ 15°C (kg/m3 )
150-360180-275Boiling range (°C)
FT FT ––DieselDiesel
##
SWCL1SWCL1QualityQuality
* Cold Filter Plug Point;
ConventionalConventional vs. vs. GtLGtL DieselDieselGtLGtL Technology: Technology: HydrocrakingHydrocraking
# Diesel from waxes produced on pilot runs
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G.Olah : Beyond Oil and Gas: The Methanol Economy
- storing energy in the form of methanol
– excellent fuel; easily stored, transported and used
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Methanol
CO+2H2 CH3OH, ΔH=-90.8 kJ/mol
CO2+3H2 CH3OH+H2O, ΔH=-49.6 kJ/mol
CO+H2O CO2+H2, ΔH=-41 kJ/mol
T lowBy-products: higher alcohols and hydrocarbons from COPhase: gasCatalyst: selective CuZn/Al2O3
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Methanol
Catalyst: sintering possible, thus t< 200-270oCdeactivation by S, C⇒(purification)
Operation policy : pressure increase with deactivation (not T)
Gas composition: 74% H2, 15% CO, 8% CO2, 3% CH4p=50-100 bar, conversion 15-30% in adiabatic reactor
Recycle of gases : recycle/make-up = 3-7 (range to avoid build up of CH4 and Ar)Products : distillationImprovements: 1) remove heat to keep reaction T as low as possible2)removal of methanol to shift equilibrium3) more active catalyst
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Methanol
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Methanol synthesis
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Catalysts
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Catalyst Activity
Operation policy: increase pressure, not T
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Crude methanol analysis from a modern converter
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Reactor: adiabatic
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Tandem
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Prices
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