Metal catalysts hydrocarbon reactions

Comparisons of the activities of various metal catalysts for reactions of hydrocarbons involving hydrogen as a reactant or product reveal activity patterns which are strongly dependent on the particular reaction considered. Several examples are discussed in the following subsections of this article. 

In the late 1980s, however, the discovery of a noble metal catalyst that could tolerate and destroy halogenated hydrocarbons such as methyl bromide in a fixed-bed system was reported (52,53). The products of the reaction were water, carbon dioxide, hydrogen bromide, and bromine. Generally, a scmbber would be needed to prevent downstream equipment corrosion. However, if the focus of the control is the VOCs and the CO rather than the methyl bromide, a modified catalyst formulation can be used that is able to tolerate the methyl bromide, but not destroy it. In this case the methyl bromide passes through the bed unaffected, and designing the system to avoid downstream effects is not necessary. Destmction efficiencies of hydrocarbons and CO of better than 95% have been reported, and methyl bromide destmctions between 0 and 85% (52). 

The metallic catalysts for exliaust pollution control are designed to perform three functions. The air/fuel ratio employed in combustion engines creates exhaust products which are a mixture of hydrocarbons, carbon oxides, and niU ogen oxides. These must be rendered environmentally innocuous by reactions on the catalyst such as... 

Hydrogenolysis reactions of hydrocarbons on metal catalysts have been investigated in some detail. Extensive studies have been conducted on both alkanes and cycloalkanes. While a number of questions still remain with regard to mechanistic and kinetic details of the reactions, the general features seem reasonably clear. 

The articles by J. R. Anderson, J. H. Sinfelt, and R. B. Moyes and P. B. Wells, on the other hand, deal with a classical field, namely hydrocarbons on metals. The pattern of modem wTork here still very much reflects the important role in the academic studies of deuterium exchange reactions and the mechanisms advanced by pioneers like Horiuti and Polanyi, the Farkas brothers, Rideal, Tw igg, H. S. Taylor, and Turkevich. Using this method, Anderson takes ultrathin metal films with their separated crystallites as idealized models for supported metal catalysts. Sinfelt is concerned with hydrogcnolysis on supported metals and relates the activity to the percentage d character of the metallic bond. Moyes and Wells deal with the modes of chemisorption of benzene, drawing on the results of physical techniques and the ideas of the organometallic chemists in their discussions. 

After the catalytic runs no modification of mean particle size is observed for this last system. Conversly, Ru CO) deposited on silica-alumina is readily decomposed at 200°C to metallic particles of 1 nm mean size which are also catalysts for the F-T synthesis. The catalytic activity at 200°C is C i one tenth of the Y zeolite supported ones and methane is practically the only hydrocarbon formed. Electron microscopy examination of the catalyst after reaction reveals a drastic sintering of the... 

STAR [Steam Active Re-forming] A catalytic reforming process for converting aliphatic hydrocarbons to olefins or aromatic hydrocarbons. Hydrocarbons containing five or fewer carbon atoms are converted to olefins. Those containing six or more are dehydrocy-clized to aromatic hydrocarbons. The reactions take place in the vapor phase, in a fixed catalyst bed containing a noble metal catalyst, in the presence of steam. Demonstrated on a semi-commercial scale and offered for license by Phillips Petroleum Company. The first commercial plant was built for Coastal Chemicals in Cheyenne, WY, in 1992 another for Polibutenos Argentinos in 1996. 

In hydrocarbon reforming processes the vapour of an alkane is passed over a supported metal catalyst such as platinum on silica or alumina. Dehydrocyclization, isomerization and cracking reactions all take place to... 

For metal catalysts used for hydrogenations and, in combination with acid functions, in hydrocarbon reforming reactions, the advantage of nano-size metal particles has been well known. More recently it has been demonstrated that metals on... 

Although reference is made to other kinds of information pertinent to the mechanistic problems which are considered, the discussion emphasizes the stereochemical contributions to mechanism. The recent review of the Mechanism of the Hydrogenation of Unsaturated Hydrocarbons on Transition Metal Catalysts by Bond and Wells (5) may be consulted for a more detailed analysis of the kinetic and exchange data which are available as well as a briefer, and in some respects different, evaluation of the stereochemistry of these reactions. 

A common feature of any cyclization reaction is that a new intramolecular C—C bond is produced that would not have been formed in the absence of the catalyst. Those reactions in which one ring closure step is sufficient to explain the formation of a given cyclic product will be called simple cyclization processes, although their mechanism is, as a rule, complex. We shall distinguish those cases in which any additional skeletal rearrangement step(s) is (are) required to explain the process. Some specific varieties of hydrocarbon ring closure processes are not included. A recent excellent review deals with the formation of a second ring in an alkyl-substituted aromatic compound (12). Dehydrocyclodimerization reactions have also to be omitted—all the more since it is doubtful whether a metallic function itself is able to catalyze this process (13). 

As few as six different kinds of adsorption have been proposed as being responsible for a great variety of hydrocarbon transformations over metal catalysts (14). We fully accept this approach—that the character of primary adsorption determines the structure of the product. One of the main points that will be stressed is that very different reactions may often be concealed behind the expression cyclization. ... 

Stereochemical Approaches to Mechanisms of Hydrocarbon Reactions on Metal Catalysts... 

These critical aspects of the classical fluorous biphasic catalysis led in recent works to the development of protocols for the conversions with modified catalyst systems in non-fluorinated hydrocarbons as solvents. As part of the BMBE lighthouse project, Gladyzs and coworkers appHed this concept to C - C coupHng reactions (Suzuki reaction) and other metal-catalyzed addition reactions (hydrosilylation, selective alcoholysis of alkynes), which have direct relevance for the synthesis of fine chemicals and specialties [74]. 

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