Abstract

Over HMOR zeolites, hydrogen inhibits n-butane isomerization which occurs through a bimolecular pathway and has practically no effect on n-hexane isomerization, of which the reaction mechanism is intramolecular. The large inhibiting effect found with butane isomerization is certainly related to the demanding character of the bimolecular process: two sec-butyl carbenium ions are necessary for the alkylation step. Hydrogen could react with carbenium ions limiting their concentration. Over sulfated zirconia hydrogen has also an inhibiting effect on n-butane isomerization, this effect being particularly pronounced at low temperature, and has no effect on n-hexane isomerization. It is suggested that the differences in the butane isomerization mechanisms proposed in the literature in the case of sulfated zirconia are mainly due to the ``diluent'' gas used (nitrogen and hydrogen) and for a small part to the reaction temperature.

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