1. Fischer-Tropsch Synthesis
Biomass
Syn Gas
Liquid Fuels
Fischer-Tropsch Synthesis 8
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2. Historical development
Fischer-Tropsch Synthesis
Historical development
1902 Sabatier and Sendersen report that methane is formed from CO and hydrogen over Ni and Co catalysts.
1908 Orlov finds ethene from synthesis gas over NiPd catalysts.
1913 BASF patent for "Preparation of a liquid oil from synthesis gas", Co and Os catalysts.
1924 Fischer and Tropsch report about the preparation of hydrocarbons over an Fe catalyst, the catalyst deactivates rapidly.
1936 The first 4 plants are commissioned (200,000 t/year capacity), Pichler finds that by increasing the pressure to 15 bar, the lifetime of the catalyst increases
plants and a total of 700,000 t/year; Co catalyst (Co, ThO2, MgO, Kieselguhr)
1955 Sasol I starts (combination of fixed and fluid bed reactors)
1994 Shell starts operating plant in Malaysia (SMDS process)
2005 Several large GTL processes under construction 8
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3. Fischer-Tropsch Process
Fischer-Tropsch Synthesis
Biomass
Coal
Natural Gas
Feedstock
Gasification
Steam Reforming (Higher hydrocarbons to hydrogen and carbon monoxide)
Syn Gas Generation
Converting mixture of hydrogen and carbon monoxide to liquid hydrocarbons
Fischer-Tropsch Process
Gasoline
Biodiesel
Synthetic lubricants
Chemicals (higher hydrocarbon)
Fuels 8
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4. Fischer-Tropsch Synthesis
Process Basics
Developed during WW II in order to satisfy the demand for fuel with the abundant coal supply.
High pressure hydrogenation of CO over metal or transition metal carbide catalysts.
The process leads to oligomer like large saturated and mostly unbranched alkanes, as well as some oxygenates.
Fe, Co and Ru are the most widely use catalysts.
Alkali metal oxide promoters seem essential for good catalytic performance.
The two main catalytic functions are –CO bond activation and dissociation – Formation of C-C and C-H bonds
Using conventional FT technology the process ranges in carbon efficiency from 25 to 50 percent and a thermal efficiency of about 50%. 8
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5. Fischer-Tropsch Synthesis
Reactions during F-T Synthesis 8
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6. Fischer-Tropsch Synthesis8
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7. Fischer-Tropsch Synthesis
Comparison of F-T Fuel with Conventional fuels 8
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8. Fischer-Tropsch Synthesis
Current Challenges and Capability
Challenges in commercial industrialization of F-T synthesis
Technical
Process efficiency and Feedstock yield
Commercial
Integration into the present energy mix
Funding
Sustainability concerns
Capabilities of the present F-T technology
Close to zero sulphur diesel
Economically viable
8% blend made mandatory, expected to reach 20% blend by the end of 2017 and up to 50% blend by 2025.
Multiple full-scale industries all across the globe to produce liquid compounds from gas/biomass 8
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9. Fischer-Tropsch Synthesis
Catalysts Today and Tomorrow
Presently used catalysts
Cobalt based catalysts
Actively used with natural gas as feedstock
Very sensitive to poisoning
Iron based catalysts
Used when the feedstock is coal or biomass
Suitable for high temperature operations
Ruthenium catalysts
Most efficient
Operates at low temperatures
Produces liquid fuels of high molecular weight
Catalysts under research
Bimetallic catalyst like Fe-Co.
Self deactivating and regenerative catalysts.
Promoters for catalysis enhancement. 8
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10. Fischer-Tropsch Synthesis
RESEARCH FRONTIERS
Syngas Generation
1950: Only proven option was Lurgi and this was used by Sasol.
Today: Many options but most produce low H2/CO ratio ( ). Commercial versions of most have reached their maximum size.
Future: Molten Iron or Molten Salt, Compact Gasifier, Ionic Membrane Separation
Fischer Tropsch Synthesis
Improve Reactor design.
Improve Catalyst (ca. 50% of operating cost)
Find a cheaper metal.
Increase catalyst life.
Viable bifunctional catalyst.
Increase loading without loss of conversion/metal
Improve Process.
Wax/slurry separation 8
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11. Unit Cost Production of GTL Fuel, $/Barrel
Fischer-Tropsch Synthesis
COST AND ECONOMICS
Typical costs in a F-T plant
Syngas generation: 65-70%
Fischer Tropsch Synthesis: 24-21%
Upgrading to fuels: 19-9%
Unit Cost Production of GTL Fuel, $/Barrel
It is generally agreed that FT plants can be profitable only at very low gas prices and relatively high crude oil prices.
According to a 2015 estimate, FT fuels could be economical when natural gas is at $15/MCF (1 MCF = 1000 ft3) and oil is at $120 per barrel
Cost Component
Refinery
GTL
Natural Gas
$4.00
+ Crude Oil
$17.00
+ Operating Costs
2.50
3.00
Total Cash Costs
19.50
7.00
+ Capital Recovery, Taxes
6.50
12.00
Total Cost to Produce
$26.00
$19.00 8
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12. Fischer-Tropsch Synthesis
World Consumption of F-T Fuels 8
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13. Fischer-Tropsch Synthesis
ENVIRONMENTAL BENEFITS
A carbon neutral process
Reduced nitrous compounds
Reduced sulphur compounds
Addresses the crisis of crude oil and climate change
Cetane rating (energy stored) 75-90% higher than that required for petrochemical derived diesel fuel
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14. Thermo-Chemical Conversion
Successful F-T Synthesis in Companies
Company
Location
Size (BPD)
Products
Sasol
South Africa
124,000
Light olefins and gasoline
Mossgas
22,500
Gasoline and diesel
Shell
Malaysia
20,000 (12,500 pre-1997)
Lubricants, Waxes, chemicals, diesel
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PROCESSING