Aromatization of heptanes,ethylcyclopentane, and cycloheptane over “nonacidic” platinum-alumina catalyst. Comparison of the mechanisms of aromatization over chromia-alumina and over platinum-alumina catalysts

n-Heptane, 2- and 3-methylhexane, ethylcyclopentane, and cycloheptane were passed in the presence of hydrogen at 500 °C over “nonacidic” platinum-alumina catalyst containing 3% by weight of platinum. The conversion ranged between 12 and 26%, depending on the interval of time the product was removed for analysis. In the case of cycloheptane, however, the conversion amounted to 98% during the first 30 min on stream and with time, during the approximate period between 2 and 3 h, it decreased to 69%. The products from the reaction contained besides toluene, also hydrocarbons resulting from a skeletal isomerization and dehydrocyclization of the original hydrocarbons, and to a smaller extent from a bond shift process, and a repetitive 1,5-ring closure followed by hydrogenolysis. Using 1,1-dimethylcyclohexane as a model compound, it was shown that the skeletal isomerization accompanying the aromatization of the seven-carbon hydrocarbons does not proceed through cationic intermediates. A survey of the literature relating to the mechanism of aromatization of hydrocarbon over “nonacidic” chromia-alumina and platinum-alumina catalysts is presented, and the differences between the two mechanisms are discussed.