Fischer catalysts

A topic of current interest is that of methane activation to give ethane or selected oxidation products such as methanol or formaldehyde. Oxide catalysts are used, and there may be mechanistic connections with the Fischer-Tropsch system (see Ref. 285). 

An important general method of preparing indoles, known as the Fischer Indole synthesis, consists in heating the phenylhydrazone of an aldehyde, ketone or keto-acld in the presence of a catalyst such as zinc chloride, hydrochloric acid or glacial acetic acid. Thus acrtophenone phenylhydrazone (I) gives 2-phenyllndole (I V). The synthesis involves an intramolecular condensation with the elimination of ammonia. The following is a plausible mechanism of the reaction ... 

A useful catalyst for asymmetric aldol additions is prepared in situ from mono-0> 2,6-diisopropoxybenzoyl)tartaric acid and BH3 -THF complex in propionitrile solution at 0 C. Aldol reactions of ketone enol silyl ethers with aldehydes were promoted by 20 mol % of this catalyst solution. The relative stereochemistry of the major adducts was assigned as Fischer- /ir o, and predominant /i -face attack of enol ethers at the aldehyde carbonyl carbon atom was found with the (/ ,/ ) nantiomer of the tartaric acid catalyst (K. Furuta, 1991). 

From carboxylic acids (Sections 15 8 and 19 14) In the pres ence of an acid catalyst alco hols and carboxylic acids react to form an ester and water This IS the Fischer esterification... 

Fischer esterification m which a phenol and a carboxylic acid condense m the pres ence of an acid catalyst is not used to prepare aryl esters... 

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. 

Goal Upgrading via Fischer-Tropsch. The synthesis of methane by the catalytic reduction of carbon monoxide and hydrogen over nickel and cobalt catalysts at atmospheric pressure was reported in 1902 (11). 

In the early 1920s Badische Arulin- und Soda-Fabrik aimounced the specific catalytic conversion of carbon monoxide and hydrogen at 20—30 MPa (200—300 atm) and 300—400°C to methanol (12,13), a process subsequendy widely industrialized. At the same time Fischer and Tropsch aimounced the Synth in e process (14,15), in which an iron catalyst effects the reaction of carbon monoxide and hydrogen to produce a mixture of alcohols, aldehydes (qv), ketones (qv), and fatty acids at atmospheric pressure. 

Natural Gas Upgrading via Fischer-Tropsch. In the United States, as in other countries, scarcities from World War II revived interest in the synthesis of fuel substances. A study of the economics of Fischer synthesis led to the conclusion that the large-scale production of gasoline from natural gas offered hope for commercial utiHty. In the Hydrocol process (Hydrocarbon Research, Inc.) natural gas was treated with high purity oxygen to produce the synthesis gas which was converted in fluidized beds of kon catalysts (42). 

K. Fischer, Comparison of I. G. Work on Eischer Synthesis, Technical OilMission Repod, Reel 13, Library of Congress, Washington, D.C., July 1941. H. Pichler, Medium Pressure Synthesis on Iron Catalyst, (Pat. Appl), Technical OilMission Report, Reel 100, Library of Congress, Washington, D.C., 1937-1943. 

M. E. Dry, "Fischer-Tropsch SyntEesis Over Iron Catalysts," paper presented at 1990 SpringyTLChP National Meetings Orlando, Fla., Mar. 18—22, 1990. 

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). 

J. H. Carstensen and P. S. Pedersen, "New Developments in HTS Catalyst Technology Solve the Fischer Tropsch Problem," AIChE Ammonia Safety Symposium, San Francisco, Calif., Nov. 1989, American Institute of Chemical Engineers, New York, 1990. 

Sasol Fischer-Tropsch Process. 1-Propanol is one of the products from Sasol s Fischer-Tropsch process (7). Coal (qv) is gasified ia Lurgi reactors to produce synthesis gas (H2/CO). After separation from gas Hquids and purification, the synthesis gas is fed iato the Sasol Synthol plant where it is entrained with a powdered iron-based catalyst within the fluid-bed reactors. The exothermic Fischer-Tropsch reaction produces a mixture of hydrocarbons (qv) and oxygenates. The condensation products from the process consist of hydrocarbon Hquids and an aqueous stream that contains a mixture of ketones (qv) and alcohols. The ketones and alcohols are recovered and most of the alcohols are used for the blending of high octane gasoline. Some of the alcohol streams are further purified by distillation to yield pure 1-propanol and ethanol ia a multiunit plant, which has a total capacity of 25,000-30,000 t/yr (see Coal conversion processes, gasification). 

Synthetic Fuels. Hydrocarbon Hquids made from nonpetroleum sources can be used in steam crackers to produce olefins. Fischer-Tropsch Hquids, oil-shale Hquids, and coal-Hquefaction products are examples (61) (see Fuels, synthetic). Work using Fischer-Tropsch catalysts indicates that olefins can be made directly from synthesis gas—carbon monoxide and hydrogen (62,63). Shape-selective molecular sieves (qv) also are being evaluated (64). 

Heat Release and Reactor Stability. Highly exothermic reactions, such as with phthaHc anhydride manufacture or Fischer-Tropsch synthesis, compounded with the low thermal conductivity of catalyst peUets, make fixed-bed reactors vulnerable to temperature excursions and mnaways. The larger fixed-bed reactors are more difficult to control and thus may limit the reactions to jacketed bundles of tubes with diameters under - 5 cm. The concerns may even be sufficiently large to favor the more complex but back-mixed slurry reactors. 

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). 

Promoters. Many industrial catalysts contain promoters, commonly chemical promoters. A chemical promoter is used in a small amount and influences the surface chemistry. Alkali metals are often used as chemical promoters, for example, in ammonia synthesis catalysts, ethylene oxide catalysts, and Fischer-Tropsch catalysts (55). They may be used in as Httie as parts per million quantities. The mechanisms of their action are usually not well understood. In contrast, seldom-used textural promoters, also called stmctural promoters, are used in massive amounts and affect the physical properties of the catalyst. These are used in ammonia synthesis catalysts. 

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 ... 

Fig. 11. Optimum pressure/temperature ranges for Fischer-Tropsch synthesis processes showiag the various catalysts ia parentheses. To convert MPa to...

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