Platinum oxide, catalytic dehydrogenation

Searching for a better catalyst than platinum to oxidize methanol to COad ° y be a new direction of the catalyst search. If such a catalyst is combined with a good catalyst for COad oxidation to C02> the overall catalytic activity may exceed that of platinum based catalysts. Platinum has catalytic activities for both reactions to some extent. For each reaction, however, platinum is not necessarily the best. Palladium may be a good catalyst to oxidize methanol to COad because it is known as a good catalysts for dehydrogenation of hydrocarbons. 

Consequently, by choosing proper conditions, especially the ratios of the carbonyl compound to the amino compound, very good yields of the desired amines can be obtained [322, 953]. In catalytic hydrogenations alkylation of amines was also achieved by alcohols under the conditions when they may be dehydrogenated to the carbonyl compounds [803]. The reaction of aldehydes and ketones with ammonia and amines in the presence of hydrogen is carried out on catalysts platinum oxide [957], nickel [803, 958] or Raney nickel [956, 959,960]. Yields range from low (23-35%) to very high (93%). An alternative route is the use of complex borohydrides sodium borohydride [954], lithium cyanoborohydride [955] and sodium cyanoborohydride [103] in aqueous-alcoholic solutions of pH 5-8. 

The catalytic dehydrogenation of lower alkanes was first developed more than fifty years ago using chromia/alumina systems [1]. Although there has been development of new processes [2 - 6], the catalyst technology has tended to remain with either modified chromia/alumina or modified platinum/alumina catalysts. Therefore it seemed appropriate to re-examine the possibility of using oxide systems other than chromia to effect the alkane to alkene transition. Supported vanadium pentoxide has been extensively studied for the oxidative dehydrogenation of propane to propene [7-10] but rarely for the direct dehydrogenation reaction [6]. 

The heat delivered by the formation of platinum oxide measured by DTA and the dehydrogenation rate of cyclohexane over these platinum modified catalytic membranes show that e pH value of impregnating solutions... 

The catalytic system used in the Pacol process is either platinum or platinum/ rhenium-doped aluminum oxide which is partially poisoned with tin or sulfur and alkalinized with an alkali base. The latter modification of the catalyst system hinders the formation of large quantities of diolefins and aromatics. The activities of the UOP in the area of catalyst development led to the documentation of 29 patents between 1970 and 1987 (Table 6). Contact DeH-5, used between 1970 and 1982, already produced good results. The reaction product consisted of about 90% /z-monoolefins. On account of the not inconsiderable content of byproducts (4% diolefins and 3% aromatics) and the relatively short lifetime, the economics of the contact had to be improved. Each diolefin molecule binds in the alkylation two benzene molecules to form di-phenylalkanes or rearranges with the benzene to indane and tetralin derivatives the aromatics, formed during the dehydrogenation, also rearrange to form undesirable byproducts. 

Reactions over chromium oxide catalysts are often carried out without the addition of hydrogen to the reaction mixture, since this addition tends to reduce the catalytic activity. Thus, since chromium oxide is highly active for dehydrogenation, under the usual reaction conditions (temperature >500°C) extensive olefin formation occurs. In the following discussion we shall, in the main, be concerned only with skeletally distinguished products. Information about reaction pathways has been obtained by a study of the reaction product distribution from unlabeled (e.g. 89, 3, 118, 184-186, 38, 187) as well as from 14C-labeled reactants (89, 87, 88, 91-95, 98, 188, 189). The main mechanistic conclusions may be summarized. Although some skeletal isomerization occurs, chromium oxide catalysts are, on the whole, less efficient for skeletal isomerization than are platinum catalysts. Cyclic C5 products are of never more than very minor impor-... 

Platinum also is used extensively as a catalyst in hydrogenation, dehydrogenation, oxidation, isomerization, carbonylation, and hydrocracking. Also, it is used in organic synthesis and petroleum refining. Like palladium, platinum also exhibits remarkable abdity to absorb hydrogen. An important application of platinum is in the catalytic oxidation of ammonia in Ostwald s process in the manufacture of nitric acid. Platinum is installed in the catalytic converters in automobile engines for pollution control. 

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