Fisher-Tropsch Process
Adnan Bashir
Bin Divakaransantha
Prakash Poudel
Semir Kelifa
Department of Chemical and Bio molecular Engineering,
University of Maryland
CHBE446
February 05, 2015
Outline

Intro/Historical Background

Definition

Reaction type/Mechanism

Use/Industrial Importance

Technology/Reactors

Catalysis

Conclusion
History

Sabatien & Senderens (1902)
produced mixture of hydrocarbons

Not favorable at the time

No single product formed

Priority given to methanol and
ammonia
History Cont.
Fischer and Tropsch

Used base catalyst like alkalized
iron and produced “synthol”

Temperature of about 400-450
Celsius and 150 atm

Higher hydrogen to CO ratio
produced better product

Tested this fluid like substance in
1922 NSU motorbike

Seated 2 people and outperformed
reference fuel
Catalyst video
History Cont..

Tested this fluid like substance in 1922
NSU motorbike

Seated 2 people and outperformed
reference fuel

Encouraging performance led to World
War II fuel supply

Fist plant made in Germany in 1934

By 1938 660,000 tons per-anum
produced
Source: http://wiredspace.wits.ac.za/jspui/bitstream/10539/11587/4/Chapter%202%20-%20Literature%20review%20-%20FTS.pdf
Reaction steps
 Associative
adsorption of CO and splitting of C/O bon
 Dissociative adsorption of 2H2
 Transfer of 2H to the oxygen to yield H2O
 Desorption of H2O
 Transfer of 2H to the carbon to yield CH2
Main reactions
Alkane formation
𝑛𝐶𝑂 + 2𝑛 + 1 𝐻2 → 𝐶𝑛 𝐻2𝑛+2 + 𝑛𝐻2 𝑂
 Favored by high 𝐻2 /CO ratio
 Strong hydrogenating catalyst is needed.
Alkene formation
𝑛𝐶𝑂 + 2𝑛𝐻2 → 𝐶𝑛 𝐻2𝑛 + 𝑛𝐻2 𝑂
 Favored by low 𝐻2 /CO ratio .
 Less strong hydrogenating catalyst is needed.
Main reactions cont..
Water-gas-shift reaction
𝐶𝑂 + 𝐻2 𝑂 → 𝐶𝑂2 + 𝐻2
 WGS activity is high in iron catalyst and
low in cobalt or ruthenium catalyst.
 Helpful to adjust 𝐻2 /CO ratio.
Useful Products
Source: http://large.stanford.edu/courses/2010/ph240/liu1/

Gas-to-liquids (GTL)

Biomass-to-liquids (BTL)

Coal to liquid (CTL)

Can be used to produce
I.
Deiseal Fuel/Jet
Fuel/Kerosene
II.
Waxes/Lubricants
III.
Naphtha/Gasoline/Detergent
Technology/ Reactors
Fixed Bed Reactors

Originally used

Challenges associated with
removal of heat
Fluidized Bed Reactors

Better temperature control

High yields for Gasoline and
light products
Source:http://www.altenergymag.com/emagazine/2014/02/india-sustainable-communities-proposal/2216
http://pubs.rsc.org/en/content/articlelanding/2015/cy/c4cy01547a#!divAbstract
Technology cont..
Slurry Reactors

Small catalyst particles
suspended in a liquid
with low vapor
pressure

Low Temperature

Flexible design

High yield for waxes
Source:http://www.altenergymag.com/emagazine/2014/02/india-sustainable-communities-proposal/2216
Catalysis

Based on Transition Metals

Iron(Fe)
-Low Cost
-Higher Water Gas Shift activity
-Suitable for lower syngas(H2/CO)

Cobalt(Co)
-More Active
-Less Water Gas Shift activity
-Higher Cost
Source:http://periodictable.com/Elements/027/
Catalysis cont..
Nickel(Ni)
-Promotes Methane
formation
-Generally not desired
I.
Ruthenium(Ru)

High molecular weight
Hydrocarbons
 High Cost
 Not generally used
I.
Source:http://periodictable.com/Elements/027/
Promoters

Fe Based Catalysts
- Promoted with Alkali metals
-to obtain high basicity, and to stabilize catalyst
-Higher alkali level higher the shift to longer chains
-Addition of copper: Enhances reducibility

Co Based Catalysts
-promoted with small amounts of noble metals
-reduces reduction temperature/pressure
-yields less olefins and oxygenated products
Cost
Source: http://www.tc2.ch.tum.de/fileadmin/tuchtc2/www/ICP1/ICP1_1314/9-FT_synthesis-
Conclusion

Process developed by Fischer and Tropsch

Many possibilities exist and it is still a research interest

Useful for production of clean energy and the future of
Biofuels

Different reactor technologies for different desirable
products

Catalysts utilized based on need and cost
Questions?
Sources
http://www.ebah.com.br/content/ABAAABOMcAL/fischer2013tropsch-catalysis-the-basis-for-anemerging-industry
http://wiredspace.wits.ac.za/jspui/bitstream/10539/11587/4/Chapter%202%20%20Literature%20review%20-%20FTS.pdf
http://en.wikipedia.org/wiki/Fischer%E2%80%93Tropsch_process
http://large.stanford.edu/courses/2010/ph240/liu1/
http://www.velocys.com/our_products_processes_ft.php
http://www.purdue.edu/discoverypark/energy/assets/pdfs/cctr/outreach/Basics1CoalGasification-Jun07.pdf
http://www.bp.com/content/dam/bp/pdf/Technology/Fischer_Tropsch_Technology.pdf
http://www.tc2.ch.tum.de/fileadmin/tuchtc2/www/ICP1/ICP1_1314/9-FT_synthesis-2013_PW.pdf
http://www.biofuelsdigest.com/bdigest/2012/11/20/little-big-tech-can-fischer-tropsch-technologywork-at-smaller-scale/
http://en.wikipedia.org/wiki/Fischer%E2%80%93Tropsch_process
http://www.netl.doe.gov/research/coal/energy-systems/gasification/gasifipedia/ftsynthesis
http://www.tc2.ch.tum.de/fileadmin/tuchtc2/www/ICP1/ICP1_1314/9-FT_synthesis-2013_PW.pdf