Fischer-Tropsch Synthesis Biomass Syn Gas Liquid Fuels Fischer-Tropsch Synthesis 8 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

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 1944 9 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 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

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 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

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 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

Fischer-Tropsch Synthesis Reactions during F-T Synthesis 8 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

Fischer-Tropsch Synthesis 8 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

Fischer-Tropsch Synthesis Comparison of F-T Fuel with Conventional fuels 8 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 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 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

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 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

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 (1.6-2.1). 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 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

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 (@$0.50/MMBtu)   $4.00 + Crude Oil (@$17/Bbl) $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 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

Fischer-Tropsch Synthesis World Consumption of F-T Fuels 8 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

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 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

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 Centre for Sustainable Technologies Indian Institute of Science, Bangalore ; http://www.cst.iisc.ernet.in/ Supported by DBT, New Delhi. This is a Beta Version HOME 8

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