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Fischer Tropsch
Synthesis
Rui Xu
Department of Chemical Engineering
Auburn University
Jan 29th, 2013
CHEN 4470
Process Design
Practice
XTL Technology
CHEN 4470
Process Design
Practice
Coal
Biomass
Natural Gas
Gasification
Syngas
Processing
FischerTropsch
Synthesis
Syncrude
Refining &
Upgrading
Fuel
&
Chemicals
Steam Reforming
H2/CO = 3
Endothermic
Favored for small scale operations
Partial Oxidation
CH4 + O2 CO + 2H2
H2/CO 1.70
Exothermic
Favored for large scale applications
Autothermal Reforming
Coal Gasification
CHEN 4470
Process Design
Practice
2(-CH-) + O2 2CO + H2
H/C Ratio
Ash
Impurities (Sulfur)
Biomass Gasification
CHEN 4470
Process Design
Practice
2(-CH-) + O2 2CO + H2
H/C Ratio
Ash
Moisture
Size Reduction
Syngas Processing
CHEN 4470
Process Design
Practice
CO + H2O CO2 + H2
Purification
Particulates
CHEN 4470
Process Design
Practice
Franz Fischer
Hans Tropsch
Kaiser Wilhelm
Institute, Mlheim,
Ruhr
1920s
Coal derived gases
Aim to product
hydrocarbons
Commercialized in
1930s
Germany
1923,
1934,
1938,
U.S.A
1950,
South Africa
1955, Sasol One, 3,000 BPD
1980, 1982, Sasol Two and Sasol Three, 25,000 BPD
CHEN 4470
Process Design
Practice
Fischer Tropsch
Synthesis
CO + 2H2 (CH2) + H2O
Reactions in FTS
CHEN 4470
Process Design
Practice
CHEN 4470
Process Design
Practice
Standard LTFT
product distribution
CHEN 4470
Process Design
Practice
Fischer-Tropsch
Products
Hydrocarbons Types
Olefins
High chemical value
Can be oligomerized to heavier fuels
Paraffins
High cetane index
Crack cleanly
Oxgenates
Branched compound (primarily monomethyl branching)
Aromatics (HTFT)
Fischer-Tropsch Catalysts
CHEN 4470
Process Design
Practice
Iron
oxide
K2O
MgO or
Al2O3
1500
C
Air
Molten
Magnetite
(Fe3O4)
Cooled rapidly
Crushed in a ball
mill
Fused
Iron
Fischer-Tropsch Catalysts
CHEN 4470
Process Design
Practice
Na2CO3
Co-precipitation method
Alkali promotion is also important
Cost more than fused iron catalyst
Reactor: slurry phase or fixed bed
Fe(NO3)3
pH = 7
K2CO3
Washing
Drying
Calcinati
on
Precipita
te Iron
Cat.
Fischer-Tropsch Catalysts
CHEN 4470
Process Design
Practice
Co(NO3)2
Support
Drying
Calcinati
on
Support
ed Co
Cat.
CHEN 4470
Process Design
Practice
Comparison of Co and Fe
LTFTS Catalyst
FTS Reactors
CHEN 4470
Process Design
Practice
FTS Reactors
CHEN 4470
Process Design
Practice
LTFT Reactors
CO + H2 (CH2) + H2O + 145 kJ/mol
1800 oC Adiabatic Temperature Rise
CHEN 4470
Process Design
Practice
Thermal uniformity
Excellent product extraction
Excellent economies of scale
Requires separation of wax (media) from catalyst
CHEN 4470
Process Design
Practice
Reactant adsorption
Chain initiation
Chain growth
Chain termination
Product desorption
CHEN 4470
Process Design
Practice
Chain termination
Product desorption
Readsorption and further
reaction
CHEN 4470
Process Design
Practice
FTS Mechanisms
Alkyl mechanism
Alkenyl mechanism
CO insertion
Enol mechanism
FTS Mechanisms
CHEN 4470
Process Design
Practice
FTS Mechanisms
CHEN 4470
Process Design
Practice
FTS Mechanisms
CHEN 4470
Process Design
Practice
FTS Mechanisms
CHEN 4470
Process Design
Practice
CHEN 4470
Process Design
Practice
i + i = 1 (by definition)
= Rp / (Rp + Rt)
CHEN 4470
Process Design
Practice
FTS Kinetics
CHEN 4470
Process Design
Iron
- based FT catalyst
Practice
Cobalt - based FT catalyst
Iron catalyst: at low conversion (P H2O 0 ), the reaction rate is only a
function of hydrogen partial pressure.
The kinetic equations imply that water inhibits iron but not cobalt.
For cobalt catalyst, when the CO partial pressure is very high, (1+bP CO)
2
H2
PCO .
FTS Economics
CHEN 4470
Process Design
Practice
Overall Cost
Capital Cost
50% to 65% of total production cost is due to capital cost
$10 per BBL for Natural Gas feedstock, $20 per BBL for Coal or Biomass feedstock
Operating Cost
$5 per BBL for Natural Gas, $10 per BBL for Coal or Biomass
Cost Distribution
NTL case 1: 25% for the gas, 25% for the operations and 50% for the capital
NTL case 2: 15% for the gas, 21% for the operations and 64% for the capital
(28% reforming, 24% FTS system, 23% oxygen plant, 13% product
enhancement and 12% power recovery)
BTL capital (21% for biomass treatment, 18% for gasifier, 18% for syngas
cleaning, 15% for oxygen plant, 1% for water-gas-shift (WGS, CO + H 2O
CO2 + H2) reaction, 6% for FTS system, 7% for gas turbine, 11% for heat
recovery / steam generation, 4% for other)
Syncrude Upgrading
CHEN 4470
Process Design
Practice
Hydrocracking
Oligomerization
Other Reactions
Polymerization
Hydrogenation
Reference
CHEN 4470
Process Design
Practice
www.fischer-tropsch.org
Book: Fischer Tropsch Technology
Review Articles:
CHEN 4470
Process Design
Practice