Fischer-Tropsch synthesis oxygenates

Successful applications of the oxygen-modified CNFs are reported on immobilization of metal complexes ]95], incorporation of small Rh particles [96], supported Pt and Ru CNFs by adsorption and homogeneous deposition precipitation ]97, 98], Co CNFs for Fischer-Tropsch synthesis ]99], and Pt CNFs for PEM fuel cells [100]. 

The primary product from Fischer-Tropsch synthesis is a complex multiphase mixture of hydrocarbons, oxygenates, and water. The composition of this mixture is dependent on the Fischer-Tropsch technology and considerable variation in carbon number distribution, as well as the relative abundance of different compound classes is possible. The primary Fischer-Tropsch product has to be refined to produce final products, and in this respect, it is comparable to crude oil. The primary product from Fischer-Tropsch synthesis can therefore be seen as a synthetic crude oil (syncrude). There are nevertheless significant differences between crude oil and Fischer-Tropsch syncrude, thus requiring a different refining approach.1... 

The Fischer-Tropsch synthesis, which may be broadly defined as the reductive polymerization of carbon monoxide, can be schematically represented as shown in Eq. (1). The CHO products in Eq. (1) are any organic molecules containing carbon, hydrogen, and oxygen which are stable under the reaction conditions employed in the synthesis. With most heterogeneous catalysts the primary products of the reaction are straight-chain alkanes, while the secondary products include branched-chain hydrocarbons, alkenes, alcohols, aldehydes, and carboxylic acids. The distribution of the various products depends on both the type of catalyst and the reaction conditions employed (4). 

For production of liquid hydrocarbons and oxygenated compounds other than methanol, shifting is usually carried to C0 H2 ratios in the range 1.8-2.4 and use is made of variants of Fischer-Tropsch synthesis ). 

Notably, once the oxygenated hydrocarbons have been converted into synthesis gas, it is then possible to carry out the subsequent conversion of synthesis gas into a variety of liquid products by well-established catalytic processes, such as the production of long-chain alkanes by Fischer-Tropsch synthesis and/or the production of methanol. 

It is also interesting that if the goal is to produce H2-CO gas mixtures, for instance in the Fischer-Tropsch synthesis, one needs to suppress the WGSR operating in the vapor phase or to operate at higher concentrations of the oxygenated reactant in water or to use a catalyst on which the rate of the WGSR is slow. 

In 1976 he was appointed to Associate Professor for Technical Chemistry at the University Hannover. His research group experimentally investigated the interrelation of adsorption, transfer processes and chemical reaction in bubble columns by means of various model reactions a) the formation of tertiary-butanol from isobutene in the presence of sulphuric acid as a catalyst b) the absorption and interphase mass transfer of CO2 in the presence and absence of the enzyme carboanhydrase c) chlorination of toluene d) Fischer-Tropsch synthesis. Based on these data, the processes were mathematically modelled Fluid dynamic properties in Fischer-Tropsch Slurry Reactors were evaluated and mass transfer limitation of the process was proved. In addition, the solubiHties of oxygen and CO2 in various aqueous solutions and those of chlorine in benzene and toluene were determined. Within the framework of development of a process for reconditioning of nuclear fuel wastes the kinetics of the denitration of efQuents with formic acid was investigated. 

To remove oxygen atoms, water or CO2 is formed as by-product, which in Table I is expressed in reactant loss as water. The synthesis of n-octane, representative for gasoline in the Fischer Tropsch synthesis, yields 57 %... 

Application of fluidized catalyst techniques to the Fischer-Tropsch synthesis (30) has yielded a process that produces chiefly (about 70%) motor gasoline, with minor amounts (about 30%) of fuel oil and oxygenated compounds. The fluidized iron catalyst process is outstanding because of its very high space-time yield and because it may be competitive with existing petroleum production and refining processes, if natural gas at 10 cents or less per 1000 cubic feet is available as the raw material for synthesis gas production. 

The char would be gasified under pressure with steam and oxygen, and the resulting gas after hydrogen sulfide removal would be used as raw material for the Fischer-Tropsch synthesis. 

During a study of the origin of oxygenates in Fischer-Tropsch synthesis in the presence of a cobalt catalyst, Roelen observed the formation of propanal and 3-penta-none when ethylene was added to the feed.1 The process now termed hydroformylation or oxo reaction is the metal-catalyzed transformation of alkenes with carbon monoxide and hydrogen to form aldehydes ... 

According to the Sachtler-Biloen mechanism, the Fischer-Tropsch reaction is initiated through CO adsorption followed by CO dissociation. Experimental evidence for the involvement of an oxygen-free intermediate exists it was observed that predeposited C is incorporated into the product during Fischer-Tropsch synthesis when CO was included in the feed gas (3). It is important to distinguish whether during the Fischer-Tropsch s)mthesis CO dissociation is strictly monomolecular or instead involves a reaction with Hads to produce an intermediate "HCO" formyl species that in a subsequent reaction decomposes to "CH" and Oads-Another question is how the rates of CO dissociation, chain growth, and termination depend on the catalyst surface structure. Thus, it is essential to know the relative values of the rate constants for these three elementary reactions. 

FIGURE 5 Anderson-Schulz-Flory distribution of the linear hydrocarbons, linear oxygenates (n-alcohols, n-aldehydes, and linear carboxylic acids), and methyl alkyl ketones formed in the Fischer-Tropsch synthesis on an iron-containing Fischer-Tropsch catalyst operating at a temperature of 498 K (plotted using log(lO)). 

The goal of using solid-state electrolytic reactors is not only to generate electrical power, but also to combine this with an industrially important catalytic reaction, such as dissociation of oxygen-containing compounds like NO [40,41], quantitative oxidation of NH3 to NO [42-44], oxidation of SO2 [45], and methanol [46], ethylene epoxidation [46], or Fischer-Tropsch synthesis [47]. The cross-flow reactor used in this type of study (Fig. 10) [48,49] has a solid electrolyte consisting of yttria-doped zirconia. The plates are electrically connected in series, with a varying number of plates in parallel. The oxidant flow channels... 

In summary, cluster-derived catalysts have been widely used in various types of CO-based reactions such as Fischer-Tropsch synthesis, methanol synthesis, hydroformylation, carbonylation, and water-gas shift reactions. The catalytic performances of cluster-derived species are evaluated in terms of higher activities and selectivities for lower olefins and oxygenates in CO hydrogenation, compared with those of metal complexes in solution and conventional metal catalysts (Table XIII). 

CO2 reforming of methane (equation 1) has been proposed as one of the most promising technologies for utilization of these two greenhouse gases, and this synthesis gas is suitable for Fischer-Tropsch synthesis and oxygenated chemicals. A serious problem is carbon deposition via Boudouard reaction (equation 2) and/or methane decomposition (equation 3). 

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