Hydrocarbon reactions cyclohexane dehydrogenation

Quantitative estimation of cyclohexane in the presence of benzene and aUphatic hydrocarbons may be accompHshed by a nitration-dehydrogenation method described in Reference 61. The mixture is nitrated with mixed acid and under conditions that induce formation of the soluble mononitroaromatic derivative. The original mixture of hydrocarbons then is dehydrogenated over a platinum catalyst and is nitrated again. The mononitro compounds of the original benzene and the benzene formed by dehydrogenation of the cyclohexane dissolve in the mixed acid. The aUphatic compound remains unattacked and undissolved. This reaction may be carried out on a micro scale. 

Additional evidence to this scheme was reported applying temporal analysis of products. This technique allows the direct determination of the reaction mechanism over each catalyst. Aromatization of n-hexane was studied on Pt, Pt—Re, and Pd catalysts on various nonacidic supports, and a monofunctional aromatization pathway was established.312 Specifically, linear hydrocarbons undergo rapid dehydrogenation to unsaturated species, that is, alkenes and dienes, which is then followed by a slow 1,6-cyclization step. Cyclohexane was excluded as possible intermediate in the dehydrocyclization network. 

The mechanism of benzene hydrogenation has been studied with the aid of [14-C]labelled hydrocarbons.The reverse process, cyclohexane dehydrogenation, has been the subject of twelve papers by Tetenyi et al., published between 1961 and 1974. The results of these have been summarized in a review by Tetenyi.In both systems the point of interest was whether the intermediates cyclohexene and cyclohexadiene were formed during the reaction. From experiments in which a 1 1 mixture of labelled [14-C]cyclohexane and inactive cyclohexene was allowed to react in the presence of Ni, Pt, and Rh catalysts, it was deduced that [14-C]-cyclohexene was produced from cyclohexane. Thus, a stepwise mechanism was proposed, involving both cyclohexene and cyclohexadiene as intermediates. 

Cyclohexane dehydrogenation represents another classical example for isotopic studies. Balandin s sextet mechanism predicted direct dehydrogenation of cyclohexane over several metals, assuming a planar reactive chemisorption of the reactant. Cyclohexene is also readily dehydrogenated to benzene. The use of hydrocarbons labelled with established the true reaction pathway. T6tenyi and co-workers[ °di] reacted a mixture of [ 0]-cyclohexane and inactive cyclohexene on different metals and measured the specific radioactivity of the fractions (cyclohexane, cH, cyclohexene, cH= and benzene, Bz) in the product at low conversion values (Table The... 

Reactions. The most important commercial reaction of cyclohexane is its oxidation (ia Hquid phase) with air ia the presence of soluble cobalt catalyst or boric acid to produce cyclohexanol and cyclohexanone (see Hydrocarbon oxidation Cyclohexanoland cyclohexanone). Cyclohexanol is dehydrogenated with 2iac or copper catalysts to cyclohexanone which is used to manufacture caprolactam (qv). 

The activity of granulated rhenium catalyst, obtained from copolymer carbonisate, has been investigated in reactions of cyclohexane or ethylbenzene dehydrogenation in bed -packed quartz tube reactor at the plug flow conditions at temperatures from 650 to 900 K, the reagents feed of 30 - 100 ml/min and initial hydrocarbons partial pressure of 0.5 kPa. 

These results have profound effects for the selective catalytic dehydrogenation of cyclohexane to benzene, a prototypical hydrocarbon conversion reaction. On Pt(lll), the intermediates, cyclohexene and a species, have been identified and the rate constants for some of the sequential reaction steps measured [56]. Adsorption and reaction studies of cyclohexane [39], cyclohexene [44], 1,3-cyclo-hexadiene [48], and benzene [39] on the two Sn/Pt(lll) alloys provide a rational basis for understanding the role of Sn in promoting higher selectivity for this reaction. One example of structure sensitivity is shown in Fig. 2.7, in which a monolayer of cyclohexyl (C H ) was prepared by electron-induced dissociation (EID) of physi-orbed cyclohexane to overcome the completely reversible adsorption of cyclohexane... 

The dehydrogenation of hexane to hexene or cyclohexane (reactions 5 and 6) only becomes appreciable at temperatures approaching 800 °K. The dehydrogenation to methylcyclopentane however appears to be thermodynamically feasible at temperatures as low as 350 °K. One cannot place too much reliance on this particular result since the affinity of formation of methylcyclopentane is known less accurately than the others. These three reactions, however, scarcely affect the synthesis of aromatic compounds in the reaction since the ethylenes and cycloparaffins are thermodynamically unstable relative to aromatic hydrocarbons above 550 °K, and they decompose spontaneously to form aromatics at this temperature. They can therefore only appear as intermediates in reaction (9) above 550 °K. 

Cyclohexane can be dehydrogenated to benzene and also benzene can be hydrogenated to cyclohexane, but these reactions cannot be controlled to give the intermediate olefin and diene. Cyclohexene and cyclohexadiene exhibit the characteristic addition reactions of unsaturated hydrocarbons. Cyclohexatriene, or benzene, shows unexpected properties in that it exhibits saturated properties imder ordinary conditions and gives some of the addition reactions of uhsaturated hydrocarbons with extreme difficulty. 

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