Introduction to

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

Natural Gas Gasification

CHEN 4470
Process Design
Practice

Steam Reforming

CH4 + H2O CO + 3H2 (Ni Catalyst)

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

A combination of Steam Reforming and Partial Oxidation

Coal Gasification
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Process Design
Practice

2(-CH-) + O2 2CO + H2

H/C Ratio

Produces Leaner Syngas (Lower H2:CO Ratio)

Ash

Non-flammable material in coal complicates

Gasifier design

Impurities (Sulfur)

Necessitates greater syngas cleanup

Biomass Gasification
CHEN 4470
Process Design
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2(-CH-) + O2 2CO + H2

H/C Ratio

Similar issues to coal

Ash

Biomass aggressively forms ash

Impurities (Sulfur, Nitrogen)

Necessitates greater syngas cleanup

Moisture

High moisture levels lower energy efficiency

Size Reduction

The fibrous nature of biomass makes size reduction

difficult

Syngas Processing
CHEN 4470
Process Design
Practice

Water Gas Shift Reaction

CO + H2O CO2 + H2

Purification

Particulates

Sulfur (<1 ppm) - ZnO Sorbent

Nitrogenates (comparable to Sulfur

compounds)

BTX (Below dew point)

CHEN 4470
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GTL Technology and

Syngas Processing

Fischer Tropsch Synthesis

CHEN 4470
Process Design
Practice

Introduction and History

Reactions and Products
Catalysts and Reactors
Mechanism and ASF plot
Economy

Fischer Tropsch Synthesis

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

FTS Industrial History

CHEN 4470
Process Design
Practice

Germany

1923,
1934,
1938,
U.S.A
1950,

Franz Fischer and Hans Tropsch

first commercial FT plant
8,000 barrels per day (BPD)
Brownsville, 5,000 BPD

South Africa
1955, Sasol One, 3,000 BPD
1980, 1982, Sasol Two and Sasol Three, 25,000 BPD

Malaysia and Qatar

1993, Shell, Bintulu, 12,500 BPD
2007, Sasol, Oryx GTL, 35,000 BPD

China, Nigeria etc.

CHEN 4470
Process Design
Practice

Fischer Tropsch
Synthesis
CO + 2H2 (CH2) + H2O

Fischer Tropsch Synthesis

CHEN 4470
Process Design
Practice

Introduction and History

Reactions and Products
Catalysts and Reactors
Mechanism and ASF plot
Economy

Reactions in FTS
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Practice

CHEN 4470
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Standard LTFT
product distribution

CHEN 4470
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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 Synthesis

CHEN 4470
Process Design
Practice

Introduction and History

Reactions and Products
Catalysts and Reactors
Mechanism and ASF plot
Economy

Fischer-Tropsch Catalysts
CHEN 4470
Process Design
Practice

Fused Iron Catalysts HTFT

Alkali promotion needed

Products are high olefinic
Cheapest
Reactor: Fluidized bed

Iron
oxide
K2O
MgO or
Al2O3

1500
C
Air

Molten
Magnetite
(Fe3O4)

Cooled rapidly
Crushed in a ball
mill

Fused
Iron

Fischer-Tropsch Catalysts
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Process Design
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Precipitated iron catalysts - LTFT

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

Supported cobalt catalysts - LTFT

Incipient wetness impregnation method

Oxide support: silica, alumina, titania or zinc
oxide
Products: predominantly paraffins
Low resistance towards contaminants

Co(NO3)2

Support

Drying

Calcinati
on

Support
ed Co
Cat.

CHEN 4470
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Practice

Comparison of Co and Fe
LTFTS Catalyst

FTS Reactors
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Practice

FTS Reactors
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LTFT Reactors
CO + H2 (CH2) + H2O + 145 kJ/mol
1800 oC Adiabatic Temperature Rise

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Fixed Bed (Gas Phase Reaction Media)

Shell SMDS

Excellent reactant transport

Simple design
Poor product extraction, heat dissipation
Limited scale-up
Potential for thermal runaway

Slurry Bed (Liquid Phase Reaction Media)

Sasol SPR

Thermal uniformity
Excellent product extraction
Excellent economies of scale
Requires separation of wax (media) from catalyst

Fischer Tropsch Synthesis

CHEN 4470
Process Design
Practice

Introduction and History

Reactions and Products
Catalysts and Reactors
Mechanism and ASF plot
Economy

CHEN 4470
Process Design
Practice

FTS Polymerization Process

Steps

Reactant adsorption

Chain initiation

Chain growth

Chain termination

Product desorption

Readsorption and further

reaction

CHEN 4470
Process Design
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FTS Polymerization process

steps
Reactant adsorption
Chain initiation
Chain growth

Chain termination
Product desorption
Readsorption and further
reaction

CHEN 4470
Process Design
Practice

FTS Polymerization Process

Steps

FTS Mechanisms

Alkyl mechanism

Alkenyl mechanism

CO insertion

Enol mechanism

FTS Mechanisms
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The Alkyl mechanism

1i). CO chemisorbs dissociatively

1ii). C hydrogenates to CH, CH2, and CH3

2). The chain initiator is CH3 and the chain propagator is

CH2

3i). Chain termination to alkane is by -hydrogenation

3ii). Chain termination to alkene is by -dehydrogenation

FTS Mechanisms
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The Alkenyl Mechanism

1i). CO chemisorbs dissociatively

1ii). C hydrogenates to CH, CH2
1iii). CH and CH2 react to form CHCH2
2i). Chain initiator is CHCH2 and chain propagator is CH2
2ii). The olefin in the intermediate shifts from the 2
position to the 1 position
3). Chain terminates to alkene is by -hydrogenation

FTS Mechanisms
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The CO Insertion Mechanism

1i). CO chemisorbs non-dissociatively

1ii). CO hydrogenates to CH2(OH)
1iii). CH2(OH) hydrogenates and eliminates water, forming CH3
2i). Chain initiator is CH3, and propagator is CO
2ii). Chain propagation produces RC=O
2iii). RC=O hydrogenates to CHR(OH)
2iv). CHR(OH) hydrogenates and eliminates water, forming CH2R
3i). CH2CH3R terminates to alkane by -hydrogenation
3ii). CH2CH3R terminates to alkene by -dehydrogenation
3iii). CHR(OH) terminates to aldehyde by dehydrogenation
3iv). CHR(OH) terminates to alcohol by hydrogenation

FTS Mechanisms
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The Enol Mechanism

1i). CO chemisorbs non-dissociatively

1ii). CO hydrogenates to CH(OH) and CH 2(OH)
2i). Chain initiator is CH(OH) and chain propagator is CH(OH) and
CH2(OH)
2ii). Chain propagation is by dehydration and hydrogenation to CR(OH)
3i). chain termination to aldehyde is by desorption
3ii). Chain termination to alkane, alkene, and alcohol, is by
hydrogenation

CHEN 4470
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FTS Mechanisms ASF Plot

Propagation is exclusively by the addition of one monomer

i + i = 1 (by definition)

Propagation probability is independent of carbon number

FTS Mechanisms - ASF Plot

CHEN 4470
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= Rp / (Rp + Rt)

The weight fraction of a chain of length n, Wn, can be

measured as a function of the chain growth probability.
Wn = nn-1(1- )

The logarithmic relation is as follows:

ln (Wn / n) = nln + ln((1- )/ )

CHEN 4470
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Standard FTS Product

Distribution

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

(bPCO) 2, the reaction rate is proportional to the ratio of P

H2

PCO .

Both denominators involve partial pressure of CO, indicating COs

general status being a (reversible) catalyst poison.
Both kinetic equations indicate hydrogenation as the rate-limiting step.

Fischer Tropsch Synthesis

CHEN 4470
Process Design
Practice

Introduction and History

Reactions and Products
Catalysts and Reactors
Mechanism and ASF plot
Economy

FTS Economics
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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

20% to 25% of total production cost is due to operating costs

$5 per BBL for Natural Gas, $10 per BBL for Coal or Biomass

Raw Material Cost

Waste or stranded resources are preferred
At market value ($4.50 / MMBTU), natural gas costs $45 / BBL

At market value ($70 / ton), coal costs $35 / BBL

At market value ($30 / ton), biomass costs $30 / BBL

XTL technology Economy

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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)

Recycle, power and heat integration

CO2 transport and storage

Syncrude Upgrading
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Extraction and Purification

Terminal Olefins, Oxygenates, and FT Wax have high value

Hydrocracking

Converts wax into liquid fuels

Oligomerization

Converts light olefins to liquid fuels

Other Reactions

Alkylation, Isomerization, Aromatization, etc.

Polymerization

HTFT ethylene and propylene can be made into polymers

Hydrogenation

Promoted fuel stability

Reference
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www.fischer-tropsch.org
Book: Fischer Tropsch Technology
Review Articles:

The Fischer-Tropsch process 1950-2000 (Dry, 2002)

High quality diesel via the FischerTropsch process a
review (Dry, 2001)
Kinetics and Selectivity of the FischerTropsch
Synthesis: A Literature Review (Gerard, 1999)
Design, synthesis, and use of cobalt-based FischerTropsch synthesis catalysts (Iglesia, 1997)

CHEN 4470
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