Fischer hydrocarbon synthesis

Fischer-Tropsch Process. The Hterature on the hydrogenation of carbon monoxide dates back to 1902 when the synthesis of methane from synthesis gas over a nickel catalyst was reported (17). In 1923, F. Fischer and H. Tropsch reported the formation of a mixture of organic compounds they called synthol by reaction of synthesis gas over alkalized iron turnings at 10—15 MPa (99—150 atm) and 400—450°C (18). This mixture contained mostly oxygenated compounds, but also contained a small amount of alkanes and alkenes. Further study of the reaction at 0.7 MPa (6.9 atm) revealed that low pressure favored olefinic and paraffinic hydrocarbons and minimized oxygenates, but at this pressure the reaction rate was very low. Because of their pioneering work on catalytic hydrocarbon synthesis, this class of reactions became known as the Fischer-Tropsch (FT) synthesis. 

A number of chemical products are derived from Sasol s synthetic fuel operations based on the Fischer-Tropsch synthesis including paraffin waxes from the Arge process and several polar and nonpolar hydrocarbon mixtures from the Synthol process. Products suitable for use as hot melt adhesives, PVC lubricants, cormgated cardboard coating emulsions, and poHshes have been developed from Arge waxes. Wax blends containing medium and hard wax fractions are useful for making candles, and over 20,000 t/yr of wax are sold for this appHcation. 

In the mid-1930s Universal Oil Products reported (33,34) that gasoline of improved quaHty could be produced by cracking the high boiling fractions of Fischer Hquids, and a consortium, the Hydrocarbon Synthesis, Inc., entered into an agreement with Ruhrchemie to Hcense the Fischer synthesis outside Germany. 

The second reaction is called the Fischer-Tropsch synthesis of hydrocarbons. Depending on the conditions and catalysts, a wide range of hydrocarbons from very light materials up to heavy waxes can be produced. Catalysts for the Fischer-Tropsch reaction iaclude iron, cobalt, nickel, and mthenium. Reaction temperatures range from about 150 to 350°C reaction pressures range from 0.1 to tens of MPa (1 to several hundred atm) (77). The Fischer-Tropsch process was developed iadustriaHy under the designation of the Synthol process by the M. W. Kellogg Co. from 1940 to 1960 (83). 

Fischer-Tropsch Waxes. Polymethylene wax [8002-74-2] production is based on the Fischer-Tropsch synthesis, which is basicaHy the polymerisation of carbon monoxide under high pressure and over special catalysts to produce hydrocarbons (see Fuels, synthetic-liquid fuels). 

The first demonstration of catalytic conversion of synthesis gas to hydrocarbons was accompHshed ia 1902 usiag a nickel catalyst (42). The fundamental research and process development on the catalytic reduction of carbon monoxide was carried out by Fischer, Tropsch, and Pichler (43). Whereas the chemistry of the Fischer-Tropsch synthesis is complex, generalized stoichiometric relationships are often used to represent the fundamental aspects ... 

Other synthetic methods have been investigated but have not become commercial. These include, for example, the hydration of ethylene in the presence of dilute acids (weak sulfuric acid process) the conversion of acetylene to acetaldehyde, followed by hydrogenation of the aldehyde to ethyl alcohol and the Fischer-Tropsch hydrocarbon synthesis. Synthetic fuels research has resulted in a whole new look at processes to make lower molecular weight alcohols from synthesis gas. 

Fischer-Tropsch Synthesis The best-known technology for producing hydrocarbons from synthesis gas is the Fischer-Tropsch synthesis. This technology was first demonstrated in Germany in 1902 by Sabatier and Senderens when they hydrogenated carbon monoxide (CO) to methane, using a nickel catalyst. In 1926 Fischer and Tropsch were awarded a patent for the discovery of a catalytic technique to convert synthesis gas to liquid hydrocarbons similar to petroleum. 

As an example of the chemical signihcance of the process technology, the products of die Fischer-Tropsch synthesis, in which a signihcant amount of gas phase polymerization occurs vary markedly from hxed bed operation to the fluidized bed. The hxed bed product contains a higher proportion of straight chain hydrocarbons, and the huidized bed produces a larger proportion of branched chain compounds. 

During the late seventies and early eighties, when oil prices rose after the 1973 war, extensive research was done to change coal to liquid hydrocarbons. However, coal-derived hydrocarbons were more expensive than crude oils. Another way to use coal is through gasification to a fuel gas mixture of CO and H2 (medium Btu gas). This gas mixture could be used as a fuel or as a synthesis gas mixture for the production of fuels and chemicals via a Fischer Tropsch synthesis route. This process is... 

Synthesis gas consists of a nonhydrocarhon mixture (H2,CO) ohtain-ahle from more than one source. It is included in this chapter and is further noted in Chapter 5 in relation to methane as a major feedstock for this mixture. This chapter discusses the use of synthesis gas obtained from coal gasification and from different petroleum sources for producing gaseous as well as liquid hydrocarbons (Fischer Tropsch synthesis). 

Hydrocarbons from Synthesis Gas (Fischer Tropsch Synthesis, FTS)... 

Many chemicals are produced from synthesis gas. This is a consequence of the high reactivity associated with hydrogen and carhon monoxide gases, the two constituents of synthesis gas. The reactivity of this mixture was demonstrated during World War II, when it was used to produce alternative hydrocarbon fuels using Fischer Tropsch technology. The synthesis gas mixture was produced then hy gasifying coal. Fischer Tropsch synthesis of hydrocarbons is discussed in Chapter 4. 

Dr. Moeller A methanation plant does not have a problem of selectivity. Whether you operate at low or high temperature, when using a nickel catalyst you will form only methane and no higher hydrocarbon. But with the Fischer-Tropsch synthesis, you have a wide range of possible products which can be formed. If you want to have a certain product, you must keep your temperature at a certain constant value. 

Figure 8.17. Hydrocarbon distribution of the products formed by Fischer-Tropsch synthesis over cobalt-based catalysts and by additional hydrocracking, illustrating how a two-stage concept enables optimization of diesel fuel yield. [Adapted from S.T. Sie,...

Ruthenium is a known active catalyst for the hydrogenation of carbon monoxide to hydrocarbons (the Fischer-Tropsch synthesis). It was shown that on rathenized electrodes, methane can form in the electroreduction of carbon dioxide as weU. At temperatures of 45 to 80°C in acidihed solutions of Na2S04 (pH 3 to 4), faradaic yields for methane formation up to 40% were reported. On a molybdenium electrode in a similar solution, a yield of 50% for methanol formation was observed, but the yield dropped sharply during electrolysis, due to progressive poisoning of the electrode. 

This section covers recent advances in the application of three-phase fluidization systems in the petroleum and chemical process industries. These areas encompass many of the important commercial applications of three-phase fluidized beds. The technology for such applications as petroleum resid processing and Fischer-Tropsch synthesis have been successfully demonstrated in plants throughout the world. Overviews and operational considerations for recent improvements in the hydrotreating of petroleum resids, applications in the hydrotreating of light gas-oil, and improvements and new applications in hydrocarbon synthesis will be discussed. 

Tsubaki N., Sakota H., and Takahashi S. 2004. Production method of Fischer-Tropsch synthesis catalyst and hydrocarbon. Japanese Patent Application JP2004237254. 

Huang, X. W., Elbashir N. O., and Roberts, C. B. 2004. Supercritical solvent effects on hydrocarbon product distributions from Fischer-Tropsch synthesis over an alumina-supported cobalt catalyst. Industrial Engineering Chemistry Research 43 6369-81. 

Weller, S. E. 1947. Kinetics of carbiding and hydrocarbon synthesis with cobalt Fischer-Tropsch catalysts. J. Am. Chem. Soc. 69 2432-36. 

Arcuri, K. B., andLeviness, S. C. 2003. The regeneration of hydrocarbon synthesis catalyst, a partial review of the related art published during 1930 to 1952. Paper presented at the AIChE Spring National Meeting, New Orleans, April 2. www.fischer-tropsch.org. 

Bertole, C. J., Kiss, G., and Mims, C. A. 2004. The effect of surface-active carbon on hydrocarbon selectivity in the cobalt-catalyzed Fischer-Tropsch synthesis. J. Catal. 223 309-18. 

Fischer-Tropsch synthesis can be regarded as a surface polymerization reaction since monomer units are produced from the reagents hydrogen and carbon monoxide in situ on the surface of the catalyst. Hence, a variety of hydrocarbons (mainly n-paraffines) are formed from hydrogen and carbon monoxide by successive addition of C, units to hydrocarbon chains on the catalyst surface (Equation 12.1). Additionally, carbon dioxide (Equation 12.3) and steam (Equations 12.1 and 12.2) are produced C02 affects the reaction just a little, whereas H20 shows a strong inhibiting effect on the reaction rate when iron catalysts are used. 

Van der Laan, G.P., Beenackers, A.A.C.M. 1999. Hydrocarbon selectivity model for the gas-solid Fischer-Tropsch synthesis on precipitated iron catalysts. Ind. Eng. Chem. Res. 38 1277. 

Sarup, B., and Wojciechowski, B.W. 1989. Studies of the Fischer-Tropsch synthesis on a cobalt catalyst. II. Kinetics of carbon monoxide conversion to methane and to higher hydrocarbons. Can. J. Chem. Eng. 67 62-74. 

---