Fischer-Tropsch hydrogenation

Fischer-Tropsch hydrogenation to a mixture of straight chain aliphatic, olefinic and oxygenated hydrocarbons. Despite an enormous amount of research during the past two decades, this is still not an economically viable process except in special circumstances, such as in South Africa. " ... 

The catalytic activity of zeolites in alkane to olefin reactions, photochemical conversion reactions, Fischer-Tropsch hydrogenation, isocyana-tion, carbonylation, and related chemistry make up the last theme. An important focus of this is to explore the utility of zeolites as selective heterogeneous catalysts for reactions that involve Group VIII metals. The mechanistic nature of some of this chemistry is presented, along with the characterization of supported organometallic transition metal complexes. 

Figure 18 Scheme representing reactions proposed to occur during the propagation steps of the Fischer-Tropsch hydrogenation of CO to propylene on a metal surface. 

Ultrasonic irradiation of iron pentacarbonyl in decane solution in the presence of silica gel produces a silica-supported amorphous nanostructured iron.io The iron particles range in size from 3 to 8 pm. This catalyst is a very active material for Fischer-Tropsch hydrogenation of CO. Figure 2 compares the activity (in terms of turnover frequency of CO molecules converted per catalytic site per second) of silica-supported nanophase iron and conventional silica-supported iron (prepared by the incipient wetness method) as a function of temperature. 

It has been noted that the ultrasonically generated iron nanoparticles showed higher catalytic activity towards specific reactions. Suslick and coworkers [26] tested the catalytic activity of sonochemically synthesised iron particles for Fischer-Tropsch hydrogenation reaction and compared the activity with that of commercial samples. The efficiency of the sonochemically produced iron particles was about 2-5 times higher than that of the commercial samples. 

Fischer-Tropsch reaction The catalytic reaction of hydrogen and carbon monoxide (synthesis gas ) to produce high-molecular weight hydrocarbons. 

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). 

Propanol has been manufactured by hydroformylation of ethylene (qv) (see Oxo process) followed by hydrogenation of propionaldehyde or propanal and as a by-product of vapor-phase oxidation of propane (see Hydrocarbon oxidation). Celanese operated the only commercial vapor-phase oxidation faciUty at Bishop, Texas. Since this faciUty was shut down ia 1973 (5,6), hydroformylation or 0x0 technology has been the principal process for commercial manufacture of 1-propanol ia the United States and Europe. Sasol ia South Africa makes 1-propanol by Fischer-Tropsch chemistry (7). Some attempts have been made to hydrate propylene ia an anti-Markovnikoff fashion to produce 1-propanol (8—10). However, these attempts have not been commercially successful. 

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). 

Fischer-Tropsch. Caibon monoxide is catalyticaily hydrogenated to a mixtuie of straight-chain aliphatic, olefinic, and oxygenated hydrocarbon molecules in the Fischer-Tropsch reaction (eq. 11) (see Fuels, synthetic). 

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. 

These reactors for hquids and liquids plus gases employ small particles in the range of 0.05 to 1.0 mm (0.0020 to 0.039 in), the minimum size hmited by filterability. Small diameters are used to provide as large an interface as possible since the internal surface of porous pellets is poorly accessible to the hquid phase. Solids concentrations up to 10 percent by volume can be handled. In hydrogenation of oils with Ni catalyst, however, the sohds content is about 0.5 percent, and in the manufacture of hydroxylamine phosphate with Pd-C it is 0.05 percent. Fischer-Tropsch slurry reac tors have been tested with concentrations of 10 to 950 g catalyst/L (0.624 to 59.3 IbiTi/fF) (Satterfield and Huff, Chem. Eng. Sci., 35, 195 [1980]). 

A hst of 74 GLS reacdions with hterature references has been compiled by Shah Gas-Liquid-Solid Reactions, McGraw-HiU, 1979), classified into groups where the solid is a reactant, or a catalyst, or inert. A hst of 75 reactions made by Ramachandran and Chaudhari (Three-Phase Chemical Reactors, Gordon and Breach, 1983) identifies reactor types, catalysts, temperature, and pressure. They classify the processes according to hydrogenation of fatty oils, hydrodesulfurization, Fischer-Tropsch reactions, and miscellaneous hydrogenations and oxidations. 

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. 

Steam reforming of CH4 CH4 + H2O = CO + 3H2 NH3 synthesis from the elements Hydrogenation of CO and CO2 to form hydrocarbons (Fischer-Tropsch syndresis)... 

Modified Fischer-Tropsch reduction of carbon monoxide with hydrogen. ... 

As a constituent of synthesis gas, hydrogen is a precursor for ammonia, methanol, Oxo alcohols, and hydrocarbons from Fischer Tropsch processes. The direct use of hydrogen as a clean fuel for automobiles and buses is currently being evaluated compared to fuel cell vehicles that use hydrocarbon fuels which are converted through on-board reformers to a hydrogen-rich gas. Direct use of H2 provides greater efficiency and environmental benefits. ... 

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