Industrial processes Fischer-Tropsch synthesis

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)). 

The catalytic partial oxidation of methane for the production of synthesis gas is an interesting alternative to steam reforming which is currently practiced in industry [1]. Significant research efforts have been exerted worldwide in recent years to develop a viable process based on the partial oxidation route [2-9]. This process would offer many advantages over steam reforming, namely (a) the formation of a suitable H2/CO ratio for use in the Fischer-Tropsch synthesis network, (b) the requirement of less energy input due to its exothermic nature, (c) high activity and selectivity for synthesis gas formation. 

This section covers recent advances in the application of three-phase fluidization systems in the petroleum and chemical process industries. These areas encompass many of the important commercial applications of three-phase fluidized beds. The technology for such applications as petroleum resid processing and Fischer-Tropsch synthesis have been successfully demonstrated in plants throughout the world. Overviews and operational considerations for recent improvements in the hydrotreating of petroleum resids, applications in the hydrotreating of light gas-oil, and improvements and new applications in hydrocarbon synthesis will be discussed. 

The most difficult problem to solve in the design of a Fischer-Tropsch reactor is its very high exothermicity combined with a high sensitivity of product selectivity to temperature. On an industrial scale, multitubular and bubble column reactors have been widely accepted for this highly exothermic reaction.6 In case of a fixed bed reactor, it is desirable that the catalyst particles are in the millimeter size range to avoid excessive pressure drops. During Fischer-Tropsch synthesis the catalyst pores are filled with liquid FT products (mainly waxes) that may result in a fundamental decrease of the reaction rate caused by pore diffusion processes. Post et al. showed that for catalyst particle diameters in excess of only about 1 mm, the catalyst activity is seriously limited by intraparticle diffusion in both iron and cobalt catalysts.1... 

In this work, a detailed kinetic model for the Fischer-Tropsch synthesis (FTS) has been developed. Based on the analysis of the literature data concerning the FT reaction mechanism and on the results we obtained from chemical enrichment experiments, we have first defined a detailed FT mechanism for a cobalt-based catalyst, explaining the synthesis of each product through the evolution of adsorbed reaction intermediates. Moreover, appropriate rate laws have been attributed to each reaction step and the resulting kinetic scheme fitted to a comprehensive set of FT data describing the effect of process conditions on catalyst activity and selectivity in the range of process conditions typical of industrial operations. 

Considerable attention has been paid to the application of CNTs as the catalyst support for Fischer Tropsch synthesis (FTS), mainly driven by utilization of the confinement effect (Section 15.2.3). In general, this process is a potential alternative to synthesize fuel (alkanes) or basic chemicals like alkenes or alcohols from syngas, which can be derived from coal or biomass. The broad product spectrum, which can be controlled only to a limited extent by the catalyst, prohibited its industrial realization so far, however, it is considered an important building block for future energy and chemical resource management based on renewables. 

Sluny bubble column reactors have many applications in both industrial and environmental processes. For example, they are used in the Fischer-Tropsch synthesis in industry, or in wastewater treatment. The most important applications of these reactors are presented in Table 3.8 (Shall et al, 1982). 

Gas-liquid bubble columns and gas-liquid-solid slurry bubble columns are widely used in the chemical and petrochemical industries for processes such as methanol synthesis, coal liquefaction, Fischer-Tropsch synthesis and separation methods such as solvent extraction and particle/gas flotation. The hydrodynamic behavior of gas-liquid bubble columns and gas-liquid-solid slurry bubble columns are of great importance for the design and scale-up of reactors. Although the hydrodynamics of the bubble and slurry bubble columns has been a subject of intensive research through experiments and computations, the flow structure quantification of complex multi-phase flows are still not well understood, especially in the three-dimensional region. In bubble and slurry bubble columns, the presence of gas bubbles plays an important role to induce appreciable liquid/solids mixing as well as mass transfer. The flows within these systems are divided into two... 

Interest in the Fischer-Tropsch synthesis was manifested by Russian investigators soon after the first information about it was published the synthesis was discussed at the Mendeleev Chemical Congress in 1934, and reviews were published both in book (148) and in journal (73,74,75, 82,84,146,234) form. The work has led to pilot plant studies full-scale industrial development of this process may have been achieved by 1950. There has been considerably more attention given to the performance of various catalysts and to the reaction mechanism, and, recently, to related processes, such as the hydropolymerization, mentioned above, and the hydrocondensation of olefins, rather than to such aspects of this process as preparation of synthesis gas,... 

Bubble column reactors (BCR) are widely used in chemical process industries to carry out gas-liquid and gas--liquid-solid reactions, the solid suspended in the liquid phase being most frequently a finely divided catalyst (slurry reactor). The main advantages of BCR are their simple construction, the absence of any moving parts, ease of maintenance, good mass transfer and excellent heat transfer properties. These favorable properties have lead to their application in various fields production of various chemical intermediates, petroleum engineering, Fischer-Tropsch synthesis, fermentations and waste water treatment. 

But how ubiquitous actually are alkalis in the promotion of reactions catalyzed at metal surfaces An examination of recent authoritative sources [6,7] shows that the majority of medium-to large-scale processes do not employ alkali promoters, even when one includes nonmetallic (i.e., metal oxide) catalysts. In a number of cases (e.g., steam reforming of naphtha) it seems clear that the role of alkali is simply to reduce the acidity of the oxide support. There are famous cases, of course, where the presence of alkali species on the catalytically active metal surface is critically important to the chemistry. Notable are ethene epoxidation (Ag-Cs), ammonia synthesis (Fe-K), acetoxylation of ethene to vinyl acetate (Pd, Pd/Au-K), and Fischer-Tropsch synthesis (Fe, Co, Ru-K). The first three are major industrial... 

Formally, ammonia synthesis is closely related to Fischer-Tropsch synthesis. Industrial operation involves the use of an iron catalyst promoted with calcium and potassium oxides. However, the reason we consider this process here is not directly in connection with alkali promotion of the catalyst. We are concerned with a remarkable achievement reported by Yiokari et al. [15], who use a ton-conducting electrolyte to achieve electrochemical promotion of a fully promoted ammonia synthesis catalyst operated at elevated pressure. Specifically, they make use of a fully promoted industrial catalyst that was interfaced with the proton conductor CaIno.iZro.903-a operated at 700K and 50 bar in a multipellet configuration. It was shown that under EP the catalytic rate could be increased by a factor of 13 when... 

Tungsten alloyed with nickel, cobalt, or rhodium in thin layers on alumina supports, also sulfided, is used on an industrial scale as a catalyst in crude oil processing (hydrotreating, hydrocracking, reforming, hydrodesulfurization, and hydrodenitrogenation), as well as in Fischer-Tropsch synthesis (alcohol formation from CO + H2). 

An interesting sequel to the Fischer-Tropsch synthesis is the so-called 0X0 reaction. Olefines derived from the Fischer-Tropsch process will react with carbon monoxide and hydrogen in the presence of cobalt carbonyl at temperatures of 110° to 150°C, under pressures of 150 to 200 atmospheres, to yield aldehydes. These can either be reduced to alcohols or oxidized to fatty acids, and they are derived from the petroleum industry... 

The reactions of carbon dioxide and water with carbonaceous species are well known reactions and have been employed in various chemical processes to control or remove unwanted carbonaceous material. The most important application is found in the gasification of coal, forming a mixture of hydrogen and carbon monoxide (syngas), which is also used in important industrial processes such as methanol synthesis and in the production of hydrocarbons (Fischer-Tropsch synthesis). In these reactions, alkali metal catalysts and promoters have been used extensively for their ability to activate water and carbon dioxide species, thus speeding up their reaction with carbon. Alkali metals are therefore a clear candidate for this study. A number of mechanisms have been suggested... 

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