1. 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

2. Outline  Intro/Historical Background  Definition  Reaction type/Mechanism  Use/Industrial Importance  Technology/Reactors  Catalysis  Conclusion

3. History  Sabatien & Senderens (1902) produced mixture of hydrocarbons  Not favorable at the time  No single product formed  Priority given to methanol and ammonia

4. 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

5. 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

6. Source: http://wiredspace.wits.ac.za/jspui/bitstream/10539/11587/4/Chapter%202%20-%20Literature%20review%20-%20FTS.pdf

7. Reaction steps  Associative adsorption of CO and splitting of C/O bond  Dissociative adsorption of 2H 2  Transfer of 2H to the oxygen to yield H 2 O  Desorption of H 2 O  Transfer of 2H to the carbon to yield CH 2

8. Main reactions

9. Main reactions cont..

10. Useful Products  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 Source: http://large.stanford.edu/courses/2010/ph240/liu1/

11. 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

12. 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

13. 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/

14. Catalysis cont.. I. Nickel(Ni) -Promotes Methane formation -Generally not desired I. Ruthenium(Ru)  High molecular weight Hydrocarbons  High Cost  Not generally used Source:http://periodictable.com/Elements/027/

15. 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

16. Cost Source: http://www.tc2.ch.tum.de/fileadmin/tuchtc2/www/ICP1/ICP1_1314/9-FT_synthesis- 2013_PW.pdf

17. 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

18. Questions?

19. Sources http://www.ebah.com.br/content/ABAAABOMcAL/fischer2013tropsch-catalysis-the-basis-for-an- emerging-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/Basics1- CoalGasification-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-technology- work-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