Industrial processes Fischer-Tropsch process

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-... 

Another important application of iron is as an industrial catalyst. It is used in catalyst compositions in the Haber process for synthesis of ammonia, and in Fischer-Tropsch process for producing synthetic gasoline. 

Methane is the principal gas found with coal and oil deposits and is a major fuel and chemical used is the petrochemical industry. Slightly less than 20% of the worlds energy needs are supplied by natural gas. The United States get about 30% of its energy needs from natural gas. Methane can be synthesized industrially through several processes such as the Sabatier method, Fischer Tropsch process, and steam reforming. The Sabatier process, named for Frenchman Paul Sabatier (1854—1941), the 1912 Nobel Prize winner in chemistry from France, involves the reaction of carbon dioxide and hydrogen with a nickel or ruthenium metal catalyst C02 + 4H2 —> CH4 + 2H20. 

In industrial practice, three-phase catalytic reactors are often used, with gases like such as H2, H2O, NH3 or O2 as reactants. The process can be classified on the basis of these gases as hydrogenation, hydration, amination, oxidation, etc [3]. Among these processes, hydrogenation is by far the most important multiphase catalytic reaction. Recently, liquid- -phase methanol synthesis and the Fischer-Tropsch process were commercialized respectively... 

The history of the oxo reaction is also noteworthy. It was developed originally in Germany in the years following World War 1. At that time, the German chemical industry was faced with inadequate supplies of petroleum. Many German chemists therefore turned to research on ways by which hydrocarbons could be synthesized from smaller building blocks, particularly carbon monoxide and hydrogen derived from coal. The success achieved was remarkable and led to alkane and alkene syntheses known as the Fischer-Tropsch process ... 

The oil industry has to enrich crude oil with hydrogen to produce lighter petroleum products. Today, the vast majority of hydrogen in refineries is produced by steam methane reforming, this production accounts for approximately 1% ( 0.3 Gt) of the C02 world emissions. For comparison, it is approximately equal to 15% of avoided C02 emissions thanks to the world nuclear reactors fleet. Besides, the tradition Fischer-Tropsch process to produce synfuels has a poor conversion yield and is a large C02 emitter one-third of the resource is used to produce the hydrogen required for the process, when another third is used to produce the energy required for the process. Two-thirds of the carbon resource is therefore converted directly into C02, and not into fuel. 

At present, the Fischer-Tropsch process is employed in industry to convert standard natural gas into synthetic gasoline, diesel, or jet fuel [65], It involves a series of chemical reactions that lead to a variety of hydrocarbons ... 

Iron catalysts have found only limited use in usual hydrogenations, although they play industrially important roles in the ammonia synthesis and Fischer-Tropsch process. Iron catalysts have been reported to be selective for the hydrogenation of alkynes to alkenes at elevated temperatures and pressures. Examples of the use of Raney Fe, Fe from Fe(CO)5, and Urushibara Fe are seen in eqs. 4.27,4.28, and 4.29, respectively. 

Dimerization and codimerization reactions are widely used on an industrial scale either to provide chemicals of high added value or to upgrade by-product olefinic streams coming from various hydrocarbon cracking processes (steam or catalytic cracking) or hydrocarbon forming processes (Fischer-Tropsch synthesis or methanol condensation) (e. g., according to eq. (1)). 

Where the Fischer-Tropsch process has been used on an industrial scale, iron or cobalt are the essential catalyst components. Technical catalysts also contain oxidic promoters, such as alumina and potassium oxide. Ruthenium and nickel are most attractive for academic research since they produce the simplest product packages. Nickel is used for methanation (production of substitute natural gas and removal of carbon monoxide impurities from hydrogen). 

This process will allow the recycling of solid waste to produce a useful product. High pressure and temperature combined with hydrogen can convert most types of domestic and industrial wastes back into products that are currently obtained from fossil coal and oil. No volatile polluting chemicals will be vented into the atmosphere. The metals can be recovered for further use and the ceramic materials will be converted into a product difficult to distinguish from natural rocks. This type of process will not solve all the solid waste disposal problems, but will provide a potential method for recovery of valuable products from waste. When implemented, it will dramatically reduce the amount of solid waste placed in landfills. This process also has the potential to reduce the amount of oil and coal mined to provide the carbon compounds needed to manufacture all petrochemical derived materials. This waste reduction process is a variation on the Fischer-Tropsch process, mentioned on page 101, in use commercially to produce hydrocarbon materials from coal. 

Another alternative to attain synthetic liquid fuels is the coal-to-liquid route achieved through the Fischer-Tropsch process [ 108], a proven technology for which raw materials are plentiful and available almost anywhere. Therefore, it is very likely that this technology will be used to provide some of the liquid fuel in the future. Nevertheless, it first has to be overcome some of its current drawbacks, e.g. relatively high costs and serious ecological concerns. For this reason, this technology has only been used at an industrial level up to now in countries with restricted economies such as World War II Germany or South Africa under apartheid. 

Various unsaturated compounds can be inserted into the metal alkyl, aryl, and alkenyl complexes to give new organometallic complexes having various functional groups. The insertions of carbon monoxide (CO) and isocyanide (CNR) into transition metal-carbon a-bond are particularly important processes, since a carbon unit can be increased in the process and the acyl type complexes formed by the insertion processes can be subjected to further transformations to synthesize useful organic compounds. For example, the CO inserhon constitutes a fundamental step in industrially important processes such as hydroformylation of olefins, acetic acid synthesis from methanol and CO, Fischer-Tropsch process, amidocarbonylation, olefin and CO copolymerizahon processes as well as in a variety of laboratory syntheses of carbonyl containing compounds. 

For the Pier methanol synthesis, sec von Nagel, Methanol, Treibstoffe, pp. 7-11. For the Fischer-Tropsch process, see the references to oil-from-coal chemistry above (note 18) and Stokes, Opting for Oil, pp. 217-230. For the use of carbon monoxide at Du Pont, see Reader, Imperial Chemical Industries A History, volume 2, p. 321. 

Water gas is used extensively in the industry for the manufacture of ammonia, methanol, hydrogen (for hydrotreating, hydrocracking of petroleum fractions and other hydrogenations in the petroleum refining and petrochemical industry), hydrocarbons (by the Fischer-Tropsch process) and metals (by the reduction of the oxide ore). 

Industrial Fischer-Tropsch processes generally consist of three main stages syngas generation, FTS, and refining of the hydrocarbon products (Scheme 12.3). Syngas can be readily produced by steam reforming... 

While various Allied programs for the transfer of industrial know-how ("Paperclip," "FIAT") ended in the middle of 1947, comparable Soviet programs continued much longer. So, for example, in late 1950 the plant management of the Synthesis Plant Schwarzheide obtained from the SAG administration "Synthese" a contract to present a documentation of the Fischer-Tropsch process within two years. ... 

Industrial production. Hydrogen can be produced commercially by several processes. Historically, it was first produced from coke oven gas, and in Germany by the Fischer-Tropsch process and to a lesser extent by the Messerschmidtt process. The hydrogen was separated from the coke oven gas (i.e., 56 vol.% H, 26 vol.% CH, 7 vol.% CO and others) by liquefaction and used afterwards in ammonia synthesis. The Fischer-Tropsch process... 

The coke oven gas process was replaced by more modern technologies. The Fischer-Tropsch process is now only used by the South African company SASOL to produce synthetic gasoline, while the third process, despite attempts to utilize a fluidized bed , is now totally abandoned. Today most of the hydrogen gas produced industrially is obtained by four major... 

As of 2011, the Republic of South Africa s synthetic fuels industry and all confirmed liquefaction projects under way were employing some variant of this process and for understandable reasons. In a world in which liquid fuels and gas are important sources of energy, the Fischer-Tropsch process has the advantage of producing both petroleum liquids and a high volume of natural gas liquids and ethane. 

Important unfunctionalized acyclic alkenes used in industry are ethene (C2) and propene (C3), isomeric butenes (C4), octenes (Cg), and olefins up to a chain length of C g. In general, a distinction is made between short-chain (C3, C4), medium-chain (C5-C42), and long-chain (C13-C19) 0x0 products. Some linear a-olefins (LAOs), such as 1-butene, 1-hexene, 1-octene, or 1-decene, can be extracted selectively from Fischer- Tropsch processes. As exemplarily conducted in Sasol s SYNTHOL process, a range of olefins with a broad distribution of odd and even carbon numbers can be obtained [9, 10]. In the case of low-cost ethylene, dimerization may produce 1-butene. Trimerization or tetramerization produces 1-hexene and/or 1-octene [11]. 

The required terminal olefins used as substrates for the hydroformylation, such as 1-pentene or 1-octene, are available in large scales and can be derived either from Sasol s Fischer-Tropsch process or from the shell higher olefins process (SHOP), respectively [43, 44]. Alternatively, trimerization or tetramerization of ethylene affords 1-hexene [45] or 1-octene [46]. Dimerization of butadiene in methanol in the presence of a Pd catalyst (telomerization) is another industrially used access for the manufacture of 1-octene [46]. 1-Octene can also be produced on a large scale from 1-heptene via hydroformylation, subsequent hydrogenation, and dehydration (Scheme 6.2) [44]. This three-step homologation route is also valuable for the production of those higher olefins that bear an odd number of C atoms. (X-Olefins can also be derived from internal olefins by cross-metathesis reaction with ethylene [47]. 

The third method was the Fischer-Tropsch process, which had been developed in the 1930s to an industrial stage operation (first plant in 1936). 

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