Catalysts, dehydrogenation commercial type

In view of these considerations, a large amount of effort is reported in the scientific press on the development of a process to produce benzene from n-hexane by combined cyclization and dehydrogenation. w-Hexane has a low Research octane number of only 24.8 and can be separated in fair purities from virgin naphthas by simple distillation. Recently, an announcement was made of a process in the laboratory stage for aromatiza-tion of n-hexane (16). The process utilizes a chromia-alumina catalyst at 900° F., atmospheric pressure, and a liquid space velocity of about one volume of liquid per volume of catalyst per hour. The liquid product contains about 36% benzene with 64% of hexane plus olefin. The catalyst was shown to be regenerable with a mixture of air and nitrogen. The tests were made on a unit of the fixed-bed type, but it was indicated that the fluid technique probably could be used. If commercial application of this or similar processes can be achieved economically, it could be of immense help in relieving the benzene short-age. 

Traditionally, ethanol has been made from ethylene by sulfation followed by hydrolysis of the ethyl sulfate so produced. This type of process has the disadvantages of severe corrosion problems, the requirement for sulfuric acid reconcentration, and loss of yield caused by ethyl ether formation. Recently a successful direct catalytic hydration of ethylene has been accomplished on a commercial scale. This process, developed by Veba-Chemie in Germany, uses a fixed bed catalytic reaction system. Although direct hydration plants have been operated by Shell Chemical and Texas Eastman, Veba claims technical and economic superiority because of new catalyst developments. Because of its economic superiority, it is now replacing the sulfuric acid based process and has been licensed to British Petroleum in the United Kingdom, Publicker Industries in the United States, and others. By including ethanol dehydrogenation facilities, Veba claims that acetaldehyde can be produced indirectly from ethylene by this combined process at costs competitive with the catalytic oxidation of ethylene. 

A recent paper of Casanave et al. [87] describes the use of Silicalite-1 in a-alumina (type 5, Introduction) membrane for selective hydrogen passage in the dehydrogenation of isobutane over a commercial Pt/Sn/y-alumina catalyst. 

This type of reactor has been used in the past to study solid-catalyzed gaseous reactions. Tajbl, Simons, and Carberry (3) used a CSTCR to study the highly exothermic oxidation of carbon monoxide on a commercial palladium catalyst. Ford and Perlmutter (2) used a CSTCR with a catalytic wall to study sec-butyl alcohol dehydrogenation. In both studies, the authors found that data were obtained more easily and accurately with a CSTCR. 

Catalysts were prepared by impregnation of Pt inside the pore structure of carbon fibers. Care was taken to eliminate the active metal from the external surface of the support. A very high dispersion of Pt was measured. Four reactions were carried out in a fixed-bed reactor competitive hydrogenation of cyclohexene and 1-hexene, cyclization of 1-hexene, n-heptane conversion and dehydrogenation of cyclohexanol. Three types of carbon fibers with a different pore size and Pt-adsorption capacity along with a Pt on activated carbon commercial catalyst were tested. The data indicate a significant effect of the pore size dimension on the selectivity in each system. The ability to tailor the pore structure to achieve results drastically different from those obtained with established supports is demonstrated with heptane conversion. Pt on open pore carbon fibers show higher activity with the same selectivity as compared with Pt on activated carbon catalysts. 

ABSTRACT. Polysilanes, (-SiRR -)n, represent a class of inorganic polymers that have unusual chemical properties and a number of potential applications. Currently the most practical synthesis is the Wurtz-type coupling of a dihalosilane with an alkali metal, which suffers from a number of limitations that discourage commercial development. A coordination polymerization route to polysilanes based on a transition metal catalyst offers a number of potential advantages. Both late and early metal dehydrogenative coupling catalysts have been reported, but the best to date appear to be based on titanocene and zirconocene derivatives. Our studies with transition metal silicon complexes have uncovered a number of observations that are relevant to this reaction chemistry, and hopefully important with respect to development of better catalysts. We have determined that many early transition metal silyl complexes are active catalysts for polysilane synthesis from monosilanes. A number of structure-reactivity correlations have been established, and reactivity studies have implicated a new metal-mediated polymerization mechanism. This mechanism, based on step growth of the polymer, has been tested in a number of ways. All proposed intermediates have now been observed in model reactions. 

This paper describes the development of an improved version of the IR cell-recycle reactor (type (ii)) which is to be used to study the mechanism and kinetics of reactions of 2-propanol on various alumina catalysts. While this reaction does not have direct commercial implications (dehydration or dehydrogenation), it exhibits many of the characteristics which make it very suitable to demonstrate the usefulness of the IR technique. 

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