Fischer-Tropsch conversion chemicals

Rofer-Depoorter, C. K., Water Gas Shift from Fischer Tropsch, in Catalytic Conversions of Synthesis Gas and Alcohols to Chemicals, edited hy R. G. Herman, Plenum, New York, 1984. 

In view of the size of operation being contemplated, it is unlikely that homogeneous catalysts will play a primary role in the production of synthetic oil. However, from the standpoint of the chemical industry, the complex mixture of products obtained from the classical Fischer-Tropsch process is generally unattractive owing to the economic constraints imposed by costly separation/purification processes. What is needed is a catalyst system for the selective conversion of CO/H2 mixtures to added-... 

Gas-to-liquids (GTL) is the chemical conversion of natural gas into petroleum products. Gas-to-liquid plants use Fischer-Tropsch technology, which first converts natural gas into a synthesis gas, which is then fed into the Fischer-Tropsch reactor in the presence of a catalyst, producing a paraffin wax that is hydro-cracked to products (see also Chapter 7). Distillate is the primary product, ranging from 50% to 70% of the total yield. 

Fischer-Tropsch synthesis making use of cobalt-based catalysts is a hotly persued scientific topic in the catalysis community since it offers an interesting and economically viable route for the conversion of e.g. natural gas to sulphur-free diesel fuels. As a result, major oil companies have recently announced to implement this technology and major investments are under way to build large Fischer-Tropsch plants based on cobalt-based catalysts in e.g. Qatar. Promoters have shown to be crucial to alter the catalytic properties of these catalyst systems in a positive way. For this reason, almost every chemical element of the periodic table has been evaluated in the open literature for its potential beneficial effects on the activity, selectivity and stability of supported cobalt nanoparticles. 

Reasons for interest in the catalyzed reactions of NO, CO, and COz are many and varied. Nitric oxide, for example, is an odd electron, hetero-nuclear diatomic which is the parent member of the environmentally hazardous oxides of nitrogen. Its decomposition and reduction reactions, which occur only in the presence of catalysts, provide a stimulus to research in nitrosyl chemistry. From a different perspective, the catalyzed reactions of CO and COz have attracted attention because of the need to develop hydrocarbon sources that are alternatives to petroleum. Carbon dioxide is one of the most abundant sources of carbon available, but its utilization will require a cheap and plentiful source of hydrogen for reduction, and the development of catalysts that will permit reduction to take place under mild conditions. The use of carbon monoxide in the development of alternative hydrocarbon sources is better defined at this time, being directly linked to coal utilization. The conversion of coal to substitute natural gas (SNG), hydrocarbons, and organic chemicals is based on the hydrogen reduction of CO via methanation and the Fischer-Tropsch synthesis. Notable successes using heterogeneous catalysts have been achieved in this area, but most mechanistic proposals remain unproven, and overall efficiencies can still be improved. 

The reactions are catalyzed by transition metals (cobalt, iron, and ruthenium) on high-surface-area silica, alumina, or zeolite supports. However, the exact chemical identity of the catalysts is unknown, and their characterization presents challenges as these transformations are carried out under very harsh reaction conditions. Typically, the Fischer-Tropsch process is operated in the temperature range of 150°C-300°C and in the pressure range of one to several tens of atmospheres [66], Thus, the entire process is costly and inefficient and even produces waste [67]. Hence, development of more economical and sustainable strategies for the gas-to-liquid conversion of methane is highly desirable. 

Several different processes have been proposed for the conversion of solid organic wastes to a more usable liquid or gaseous form to be utilized as fuel or petrochemical feedstocks. Principally the commonly discussed processes involve the biological conversion to alcohols, the catalytic chemical conversion to methanol or Fischer-Tropsch liquids via a carbon monoxide and hydrogen synthesis gas, or the thermochemical formation of gases or oxygenated liquids by pyrolysis. Pyrolysis is defined as the decomposition of organic material at elevated temperatures. The process to be described uses a very special case of pyrolysis. 

Reduction of CO to compounds containing C—H and/or C—C bonds has been actively studied because these reductions are important in the conversion of coal-derived CO into fuels and organic chemicals. Reactions in this class include methanation, MeOH synthesis, and Fischer-Tropsch (F-T) synthesis, e.g., equations (b)-(d) equation (d) yields a range of hydrocarbon and oxygenate (ROH and polyol) products. 

A great many reactions in physics and chemistry proceed via chain mechanisms. This large family of mechanisms includes free radical and ionic polymerization, Fischer Tropsch synthesis, gas phase pyrolysis of hydrocarbons, and catalytic cracking. Nuclear reactions, of both the power generating and the explosive kind, are also chain processes. Notice that chemical chain reactions can be catalytic or non-catalytic, homogeneous or heterogeneous. One is almost tempted to say that chain reactions are the preferred route of conversion in nature. 

General Synthesis Scheme. A schematic diagram of a plant producing synthetic liquid fuels and chemicals from coal via the Fischer-Tropsch synthesis is shown in Fig. 11-3. Gasification of coal with steam and oxygen is followed by a purification step to eliminate solids, sulfur compounds, and most of the carbon dioxide. Two stages of synthesis are employed to attain a high conversion of the synthesis gas. Recovery and treatment of primary... 

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