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The Fischer–Tropsch process is a collection of chemical reactions that converts a mixture of carbon monoxide and hydrogen into liquid hydrocarbons. It was first developed by Franz Fischer and Hans Tropsch at the "KaiserWilhelm-Institut für Kohlenforschung" in Mülheim an der Ruhr, Germany in 1925. The process, a key component of gas to liquids technology, produces a synthetic lubrication oil and synthetic fuel, typically from coal, natural gas, or biomass. The Fischer–Tropsch process has received intermittent attention as a source of low-sulfur diesel fuel and to address the supply or cost of petroleum-derived hydrocarbons.
1 Reaction mechanism 2 Feedstocks: gasification 2.1 Feedstocks: GTL 2.2 Process conditions 2.3 Design of the Fischer-Tropsch process reactor 2.4 Product distribution 2.5 Catalysts 2.6 LTFT and HTFT 3 History 4 Commercialization 4.1 Sasol 4.2 PetroSA 4.3 Shell middle distillate synthesis 4.4 Ras Laffan, Qatar 4.5 UPM (Finland) 4.6 Rentech 4.7 Other 5 Research developments 5.1 U.S. Air Force certification 5.2 Carbon dioxide reuse 6 Process efficiency 7 See also 8 References 9 Further reading 10 External links
The Fischer–Tropsch process involves a series of chemical reactions that produce a variety of hydrocarbons, ideally with to the formula (CnH(2n+2)). The more useful reactions produce alkanes as follows:
depending upon the energy source of the gasification process.e. such as migratory insertion. H2. Chain growth reaction thus appears to involve both ‘olefin insertion’ as well as ‘CO-insertion’. Feedstocks: GTL Carbon monoxide for FT catalysis is derived from hydrocarbons. most coal-based plants rely on the feed coal to supply all the energy requirements of the Fischer– Tropsch process. CO. This conversion is called gasification and the product is called synthesis gas ("Syn gas"). the hydrocarbons are low molecular weight materials that often would be discarded or flared. are reactions that form C-C bonds. hydroxycarbene (HCOH). i. This ratio is adjusted via the water-gas shift reaction. In addition to alkane formation. Furthermore. methylene (CH2). the hydrogenolysis (cleavage with H2) of C-O bonds. Coal-based Fischer– Tropsch plants produce varying amounts of CO2. Using 14C-labelled ethyene and propene over cobalt catalysts results in incorporation of these olefins into the growing chain. methyl (CH3). but homogeneous Fischer–Tropsch catalysts are poorly developed and of no commercial importance. Stranded gas provides relatively cheap gas. GTL is economically viable when the gas price is relatively cheap on an energy equivalency basis to oil. For one CH2-group produced CO + 2H2 → (CH2) + H2O. The growth of the hydrocarbon chain may be visualized as involving a repeated sequence in which hydrogen atoms are added to carbon and oxygen. and hydroxymethylidyne (COH). hydroxymethyl (CH2OH). suitable as diesel fuel. Many related stoichiometric reactions have been simulated on discrete metal clusters. However. possibly into oxide and carbide ligands. Synthesis gas obtained from coal gasification tends to have a H2/CO ratio of ~0.(2n + 1) H2 + n CO → CnH(2n+2) + n H2O where n is typically 10-20. several reactions are necessary • Associative adsorption of CO • Splitting of the C/O-bond • 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 The conversion of CO to alkanes involves hydrogenation of CO. and the formation of C-C bonds.7 compared to the ideal ratio of ~2. Other potential intermediates are various C-1 fragments including formyl (CHO). competing reactions give small amounts of alkenes. the C/O-bond is split and a new C/C-bond is formed. and critical to the production of liquid fuels. Feedstocks: gasification Fischer–Tropsch plants associated with coal or related solid feedstocks (sources of carbon) must first convert the solid fuel into gaseous reactants. as well as alcohols and other oxygenated hydrocarbons.. Addition of isotopically labelled alcohol to the feed stream results in incorporation of alcohols into product. This observation establishes the facility of C-O bond scission. Fischer Tropsch intermediates and elemental reactions Converting a mixture of H2 and CO into aliphatic products obviously should be a multi-step reaction with several sorts of intermediates. Such reactions are assumed to proceed via initial formation of surfacebound metal carbonyls. The CO ligand is speculated to undergo dissociation. Most of the alkanes produced tend to be straight-chain. GTL is viable provided gas remains relatively cheaper than oil. . and alkanes. In gas to liquids (GTL) technology. The formation of methane (n = 1) is unwanted. methylidyne (CH).
For cobalt-based catalysts the optimal H2:CO ratio is around 1. First. but the benefits may not justify the additional costs of high-pressure equipment. Entrained flow reactor: Important requirement of the reactor for Fischer Tropsch process is to remove the heat of the reaction. the Fischer–Tropsch process is operated in the temperature range of 150–300 °C (302–572 °F). Since large amounts of products formed are in liquid state this type reactor can also be termed as trickle flow reactor system. the temperature is usually maintained at the low to middle part of the range.1. Synthesis gas is bubbled through the waxy products and finely divided catalyst which is suspended in the liquid medium. Higher temperatures lead to faster reactions and higher conversion rates but also tend to favor methane production.This also provides agitation of the contents of the reactor. Catalyst particle size reduces diffusional heat and mass transfer limitations. Increasing the pressure leads to higher conversion rates and also favors formation of long-chained alkanes. and higher pressures can lead to catalyst deactivation via coke formation. Even higher pressures would be favorable. This reactivity can be important for synthesis gas derived from coal or biomass. another important reaction is steam reforming. Fixed Bed Reactor is suitable to operate at low temperatures and has upper temperature limit of 530 K. Excess temperature leads to carbon deposition and hence blockage of the reactor. Typical pressures range from one to several tens of atmospheres. Four types of reactors are discussed: Multi tubular fixed bed reactor: This type of reactor contains number of tubes with small diameter. Slurry Reactors: Heat removal is done by internal cooling coils.The formation of heavy waxes should be avoided since this condenses on the catalyst and forms agglomeration. These tubes contains catalyst and are surrounded by boiling water which removes the heat of reaction. reactant gases entering a Fischer–Tropsch reactor must be desulfurized. both of which are desirable. Several reactions are employed to adjust the H2/CO ratio. For this reason. which provides a source of hydrogen at the expense of carbon monoxide: H2O + CO → H2 + CO2 For Fischer–Tropsch plants that use methane as the feedstock. which tend to have relatively low H2:CO ratios (<1).This leads to fluidization. which converts the methane into CO and H2: H2O + CH4 → CO + 3 H2 Process conditions Generally.Hence risers are operated over 570 K. Most important is the water gas shift reaction. Iron-based catalysts promote the water-gas-shift reaction and thus can tolerate lower ratios.Lower . Otherwise.Several reactions are required to obtain the gaseous reactants required for Fischer–Tropsch catalysis.8–2. sulfur-containing impurities deactivate ("poison") the catalysts required for Fischer–Tropsch reactions. A variety of synthesis-gas compositions can be used. This type of reactor contains two banks of heat exchangers which removes heat. Design of the Fischer-Tropsch process reactor Efficient removal of heat from the reactor is basic need of the Fischer-Tropsch reactors since these reactions are characterized by high exothermicity. remaining is removed by products and recycle of the system.
Examination of the above equation reveals that methane will always be the largest single product so long as alpha is less than 0. to be used as such. Therefore.and circulating catalyst(riser) reactors: These are used for high temperature Fischer Tropsch synthesis (nearly 340o C) to produce low molecular weight olefinic hydrocarbons on alkalised fused iron catalysts. In general. 3. Today slurry phase (bubble column) low temperature Fischer Tropsch synthesis is regarded by many authors as the most efficient process for Fischer Tropsch clean Diesel production. The bubble column reactor with a powdered iron slurry catalyst and a CO-rich syngas was particularly developed to pilot plant scale by Kölbel at the Rheinpreuben Company in 1953. Sasol has operated 16 advanced reactors of this type with a capacity of Approx. ‘riser reactor’. for production of liquid transportation fuels it may be necessary to crack some of the Fischer–Tropsch products.50. α is the chain growth probability or the probability that a molecule will continue reacting to form a longer chain. Recently (since 1990) low temperature Fischer Tropsch slurry processes are under investigation for the use of iron and cobalt catalysts. Now the circulating catalyst process is being replaced by the superior Sasol advanced fluid bed technology. A large scale Fischer Tropsch Hydrocol plant (3. It was improved by Sasol for successful operation.5. Increasing α increases the formation of longchained hydrocarbons. C7 production. A high temperature process with a circulating iron catalyst (‘Circulating fluid bed’. Such efforts have met with only limited success. or to be hydrocracked and isomerised to mainly Diesel fuel by Exxon and Sasol. The fluid bed technology (as adapted from catalytic cracking of heavy petroleum distillates)was introduced by Hydrocarbon Research in the years 1946–1950 and named ‘Hydrocol’ process. Early experiments with cobalt-catalyst particles suspended in oil have been performed by Fischer. This Fischer Tropsch technology is also under development by the Statoil Company (Norway) for use on a vessel to convert associated gas at offshore oil fields into a hydrocarbon liquid. Due to technical problems and lacking economy at increasing petroleum availability this development was discontinued. by increasing α close to one. however. α is largely determined by the catalyst and the specific process conditions.50. some researchers have proposed using zeolites or other catalyst substrates with fixed sized pores that can restrict the formation of hydrocarbons longer than some characteristic size (usually n<10). The very long-chained hydrocarbons are waxes. South Africa. Fluid bed Fischer Tropsch synthesis has recently been very successfully reinvestigated by Sasol.000 tons per annum each.temperature in reactor leads to more viscous product and higher (> 570 K) gives undesirable products spectrum.000 tons per annum is now in operation and even larger ones are being built (nearly 8. Texas. which are solid at room temperature. which can be expressed as: Wn/n = (1 − α)2αn −1 where Wn is the weight fraction of hydrocarbons containing n carbon atoms. particularly for the production of a hydrocarbon wax.30. At Secunda. The process is now used for mainly olefins C2. However separation of the product from catalyst is a problem. In order to avoid this. One reactor with a capacity of 5.  Product distribution In general the product distribution of hydrocarbons formed during the Fischer–Tropsch process follows an Anderson–Schulz–Flory distribution. the total amount of methane formed can be minimized compared to the sum of all of the various long-chained products.00. This way they can drive the reaction so as to minimize methane formation without producing lots of long-chained hydrocarbons. Fluid-bed. ‘entrained catalyst process’) was introduced by the Kellogg Company and a respective plant built at Sasol in 1956.000 tons per annum) operated during the years 1951–1957 in Brownsville. This new development can be regarded as an important progress in Fischer Tropsch technology.000 tons per annum). .
Ruthenium as a Fischer Tropsch catalyst:It is most active working at the lowest reaction temperature. Thus a low catalyst porosity with small pore diameters as obtained from fused magnetite (plus promotors) after reduction with hydrogen is appropriate. Cobalt-based catalysts are highly active. thus providing the simplest catalytic system of Fischer Tropsch synthesis. however. Natural gas has a high hydrogen to carbon ratio.The second direction of iron catalyst development has aimed at highest catalyst activity to be used at low reaction temperature where most of the hydrocarbon product is in the liquid phase under reaction conditions. without any promotors. but the formulation depends on the primary metal. 0.g. Fischer–Tropsch catalysts are sensitive to poisoning by sulfur-containing compounds. Typically. The catalyst particles moving around in the reactor are small (particle diameter 100 mm) and carbon deposition on the catalyst does not disturb reactor operation. The working catalyst is only obtained when – after reduction with hydrogen– in the initial period of synthesis several iron carbide phases and elemental carbon are formed whereas iron oxides are still present in addition to some metallic iron. it acts as a Fischer Tropsch catalyst as the pure metal. 340oC). alumina. Cobalt catalysts are more active for Fischer–Tropsch synthesis when the feedstock is natural gas.% K2O).g. Promotors also have an important influence on activity.Thus iron catalysts are very flexible. the average molecular weight of the product is so low that no liquid product phase occurs under reaction conditions. including potassium. Iron as catalyst:Fischer Tropsch iron catalysts need alkali promotion to attain high activity and stability (e. and ruthenium. Al2O3 for structural promotion and maybe some manganese can be applied for selectivity control (e. Synthesis gases derived from these hydrogen-poor feedstockes has a low-hydrogen-content and require the water-gas-shift reaction. addition of SiO2.g. Group 1 alkali metals. which remain in the metallic state during synthesis. recovering the olefins for use as chemicals in e. so the water-gas-shift is not needed for cobalt catalysts. Nickel can also be used.5 wt. although iron may be more suitable for certain applications.Addition of Cu for reduction promotion. Iron catalysts are preferred for lower quality feedstocks such as coal or biomass. high olefinicity). the olefin to parafin ratio increases. In addition to the active metal the catalysts typically contain a number of "promoters." including potassium and copper. also can be very selectively hydrocracked to a high quality Diesel fuel. polymerization processes is advantageous today. Alkali oxides on cobalt catalysts generally cause activity to drop severely even with very low alkali loadings. or zeolites. but tends to favor methane formation ("methanation"). Cobalt-based catalysts are more sensitive than for their iron counterparts. iron catalysts tend to form a number of phases. Ru). Control of these phase transformations can be important in maintaining catalytic activity and preventing breakdown of the catalyst particles. including various oxides and carbides during the reaction. Alkali metal oxides and copper are common promotors. are a poison for cobalt catalysts but are promoters for iron catalysts. One direction has aimed at a low molecular weight olefinic hydrocarbon mixture to be produced in an entrained phase or fluid bed process (Sasol Synthol process).Due to the relatively high reaction temperature (approx. Catalysts are supported on high-surface-area binders/supports such as silica. It produces the highest molecular weight hydrocarbons (‘polymethylene synthesis’ Pichler and Buffleb performing thus the chain growth reaction in the cleanest mode. which is refined to marketable wax materials at Sasol. Unlike the other metals used for this process (Co.Catalysts A variety of catalysts can be used for the Fischer–Tropsch process. In addition. However. iron. where mechanistic conclusions . Ni. For maximising the overall gasoline yield the olefins C3. C5+ and CO2 selectivity increase while methane and C2-C4 selectivity decrease. but the most common are the transition metals cobalt. A high content of a carrier provides mechanical strength and wide pores for easy mass transfer of the reactants in the liquid product filling the pores.With iron catalysts two directions of selectivity have been pursued. The main product fraction then is a paraffin wax. such catalysts are obtained through precipitation from nitrate solutions. C4 have been oligomerised at Sasol. iron vs cobalt.
e. steps of reaction and corresponding kinetic schemes. Germany used the Fischer–Tropsch process during World War II to produce ersatz (replacement) fuels. many refinements and adjustments were made. converting the CO/H2 mixture to aliphatic (long chain) hydrocarbons in a ‘one step reaction’. U. sources of natural gas far from major cities which are impractical to exploit with conventional gas pipelines and LNG technology. Qatar. Systematic Fischer Tropsch studies with ruthenium catalysts should contribute substantially to the further exploration of the fundamentals of Fischer Tropsch synthesis.746.google. with iron as the catalyst. Several companies are developing the process to enable practical exploitation of so-called stranded gas reserves. Malaysia. otherwise. The United States Bureau of Mines.should be the easiest – much easier than e. published 1930. working at the Kaiser-Wilhelm-Institut for Chemistry in the 1920s.e. Low-Temperature Fischer–Tropsch (LTFT) is operated at lower temperatures and uses a cobalt based catalyst. It will be seen in the next section that the kinetic principle of ‘selective inhibition’ might be the common feature which applies. (Not related to a company of the same name in Canada) Commercialization The Fischer–Tropsch process has been applied in large-scale gas–liquids and coal–liquid facilities such as Shell's Pearl GTL facility in Ras Laffan.g. In particular. Missouri in 1946. This process is best known for being used in the first integrated Gas-to-Liquid (GTL) plant operated and built by Shell in Bintulu. the uncertain and volatile price of crude oil..464 (http://www. Fischer and Tropsch filed a number of patents. Alfred August Aicher obtained several patents for improvements to the process in the 1930s and 1940s. The term ‘one step reaction’ means that reaction intermediates are not desorbed from the catalyst surface. reaction intermediates.There is an interesting question to consider: what features have the metals nickel.com/patents/US1746464). high operation and maintenance costs. Fischer–Tropsch production accounted for an estimated 9% of German war production of fuels and 25% of the automobile fuel. the direct sale of natural gas to consumers would become much more profitable. i. the selectivity changes to mainly methane at elevated temperature.Like with nickel.S.in spite of differences in catalyst composition. applied 1926. iron.  LTFT and HTFT High-temperature Fischer–Tropsch (or HTFT) is operated at temperatures of 330°C–350°C and uses an ironbased catalyst. employed seven Operation Paperclip synthetic fuel scientists in a Fischer–Tropsch plant in Louisiana. This process was used extensively by Sasol in their coal-to-liquid plants (CTL). Such large facilities are susceptible to high capital costs. Its high price and limited world resources exclude industrial application. and environmental concerns.. the use of natural gas as a feedstock becomes practical only with use of "stranded gas". In Britain. It was commercialized by Brabag in Germany in 1936.g. Being petroleum-poor but coal-rich. Aicher's company was named Synthetic Oils Ltd. cobalt and ruthenium in common to let them be – and only them – Fischer Tropsch catalysts. it is amazing that the much carbided alkalized iron catalyst gives this reaction similarly as the just metallic ruthenium catalyst. . In particular. History Since the invention of the original process by Fischer and Tropsch. in a program initiated by the Synthetic Liquid Fuels Act. Patent 1.
 The GTL plant uses the F-T process.000 barrels a day plant that completed semi-commercial demonstration in 2011.000 barrels per day (1. a South African company which. which maximizes catalyst activity and life. An order has reportedly been placed for a 1400-bbl/day modular GTL plant using the technology of a company called Velocys. Louisiana using natural gas from tight shale formations in Louisiana and Texas as feedstock. 2012 Sasol announced plans to build a 96. indications show capital costs. In Australia. Ras Laffan. The technology can be used to convert natural gas. Shell middle distillate synthesis One of the largest implementations of Fischer–Tropsch technology is in Bintulu. The use of microchannel reactors scales down the size of the reaction hardware and overcomes the heat and mass transport problems associated with conventional FT technology. While no smaller scale plant is currently in commercial operation. Fluidized bed gasification with FTpilot in Güssing. including most of the country's diesel fuel. The first commercial plant opening in 1952. Linc Energy commenced construction in 1999 of the world's first gas–liquid plant operating on synthesis gas produced by underground coal gasification. The scale is 12. paving the way to begin commercial preparation. Burgenland. The refinery is a 36.000 barrels a day plant in Westlake.Conventional FT reactors have been optimized for massive coal-to-liquids and gas–liquid facilities such as Shell's Pearl GTL facility. PetroSA PetroSA. The planned complex will include a refinery and a chemical plant. but little oil. Austria In December. Costs are estimated to be between 11 and 12 billion dollars with $2 billion in tax relief being contributed by the state of Louisiana. and produced liquids in 2008. a country with large coal reserves. Sasol uses coal and now natural gas as feedstocks and produces a variety of synthetic petroleum products. biomass or coal into synthetic fuels. Malaysia. has the world's largest Gas to Liquids complexes at Mossel Bay in South Africa. operating costs and size could all be reduced relative to conventional FT facilities. in a joint venture.900 m3/d). Enhanced heat transfer inside the microchannels reactor allows for optimal temperature control. won project innovation of the year award at the Petroleum Economist Awards in 2008. 40 miles south of Johannesburg. This Shell facility converts natural gas into low-sulfur Diesel fuels and food-grade wax. These slurry bed and fixed-bed reactors are much larger than the sizes needed for biofuel facilities or for smaller-scale natural-gas fields. Sasol The largest scale implementation of Fischer–Tropsch technology are in a series of plants operated by Sasol in South Africa. Qatar .
and Germany. a company specializing in biomass gasification. Waste Management and Processors. Ontario. the facility produces about 10 barrels per day (1.The new LTFT facility Pearl GTL which began operation in 2011 at Ras Laffan. was funded by the state to implement Fischer–Tropsch technology licensed from Shell and Sasol to convert so-called waste coal (leftovers from the mining process) into low-sulfur diesel fuel. Florida. Colorado.6 m3/d) of fuels from natural gas.000 m3) of oil equivalent in natural gas liquids and ethane.000 L) of diesel and jet fuel from the Fischer–Tropsch process using natural gas and coal at its demonstration plant near Tulsa. as well as gas-to-liquid plants internationally. and does not appear to be continuing work on their FT process and the proposed commercial facilities. Port St.500. Rentech A demonstration-scale Fischer–Tropsch plant is owned and operated by Rentech.000 m3/d). Commercial-scale facilities are planned for Rialto. low sulfur fuel has been tested extensively by the United States Department of Energy (DOE) and the United States Department of Transportation (DOT). The company went bankrupt in 2011 due to impracticalities in the process. Oklahoma. and White River. The first GTL plant in Ras Laffan was commissioned in 2007 and is called Oryx GTL and has a capacity of 34 000 bbl/day. Natchez. Research developments Choren Industries has built an Fischer–Tropsch plant in Germany that converts biomass to syngas and fuels using the Shell Fischer–Tropsch process structure. some coal-producing states have invested in Fischer–Tropsch plants. Oryx GTL is a joint venture between Qatar Petroleum and Sasol. China. Joe. California. Air Force certification Syntroleum.S. Biomass gasification (BG) and Fischer–Tropsch (FT) synthesis can in principle be combined to produce renewable transportation fuels (biofuels). Most recently. UPM (Finland) In October 2006. a publicly traded United States company.000 barrels per day (22.000 US gallons (1. Syntroleum has been working with the United States Air Force to develop a synthetic jet fuel blend that will help the Air Force to reduce .. has produced over 400. the ultra-clean. converting natural gas to petroleum liquids at a rate of 140. uses cobalt catalysts at 230°C. Syntroleum is working to commercialize its licensed Fischer–Tropsch technology via coal-toliquid plants in the United States. The plant utilizes the Sasol slurry phase distillate process which uses a cobalt catalyst. U. Rentech closed down their pilot plant in 2013. Inc. Mississippi. Qatar. with additional production of 120. Using natural gas as a feedstock.000 barrels (19. Located in Commerce City. Inc. using waste biomass resulting from paper and pulp manufacturing processes as source material. in partnership with ClearFuels. Other In the United States. In Pennsylvania. Finnish paper and pulp manufacturer UPM announced its plans to produce biodiesel by the Fischer–Tropsch process alongside the manufacturing processes at its European paper and pulp plants.
 Carbon dioxide reuse Carbon dioxide is not a typical feedstock for F-T catalysis. an effort to develop secure domestic sources for the military energy needs. California for the first time powered solely by a 50–50 blend of JP-8 and Syntroleum's FT fuel. a generic term for this type of process Hubbert peak Industrial gas Karrick process Steam methane reforming Synthetic Liquid Fuels Program Unconventional oil Wood gas . a B-52 took off from Edwards Air Force Base. The Air Force. The seven-hour flight test was considered a success. unsaturated hydrocarbons are also produced. On December 15. The Pentagon hopes to reduce its use of crude oil from foreign producers and obtain about half of its aviation fuel from alternative sources by 2016. the B-1B. Process efficiency Using conventional FT technology the process ranges in carbon efficiency from 25 to 50 percent and a thermal efficiency of about 50% for CTL facilities idealised at 60% with GTL facilities at about 60% efficiency idealised to 80% efficiency. the C-17 Globemaster III. ceria functions as a reverse water gas shift catalyst. With iron-based catalysts short-chain.its dependence on imported petroleum. The goal of the flight test program is to qualify the fuel blend for fleet use on the service's B-52s. Upon introduction to the catalyst's support. further increasing the yield of the reaction. which is the United States military's largest user of fuel. Hydrogen and carbon dioxide react over a cobaltbased catalyst. This program is part of the Department of Defense Assured Fuel Initiative. The test program concluded in 2007. producing methane. and eventually every airframe in its inventory to use the fuel by 2011. 2006. such as zeolites. See also Air separation Algae fuel Bergius process Biogasoline Biomass to liquid Carbon neutral fuel Fischer assay Future energy development Hydrogenation. and then flight test and qualification on other aircraft. began exploring alternative fuel sources in 1999. With the B-52 now approved to use the FT blend. The short chain hydrocarbons were upgraded to liquid fuels over solid acid catalysts.
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