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Co/H-ZSM5 catalyzes propane dehydrogenation and aromatization reactions. Initial product selectivities, product site-yields, and the 13 C content and distribution in the products of 2- 13 C-propane show that propane undergoes two primary reactionssdehydrogenation to propene and H2 and cracking to methane and ethene. Propene and ethene then form aromatics via oligomerization-cracking reactions and both ethene and propene hydrogenate to form ethane and propane, respectively, via both hydrogen transfer from coadsorbed intermediates and dissociative adsorption of H2. These reaction pathways resemble those occurring on H-ZSM5, but Co cations provide an alternate pathway for the removal of hydrogen atoms in adsorbed intermediates as H2 .A kinetic model was used to describe experimental rates based on these observations and to obtain rate constants for individual reaction steps as a function of Co content and H2 concentration. H2 inhibits propane dehydrogenation to propene and alkene conversion to aromatics, and increases the rate and the rate constant for ethene hydrogenation. Rate constants were obtained for propane reactions on H-ZSM5 and Co/H-ZSM5 (Co/Al ) 0.05-0.22). Propane dehydrogenation (k1), ethene hydrogenation (k3), and alkene dehydrocyclization (k4) rate constants increased with increasing Co/Al ratio, because Co cations catalyze both the recombinative desorption of H2 and its microscopic reverse, the dissociative adsorption of H 2. Co cations increase the reversibility of hydrogen adsorption-desorption steps, and in this manner, they increase the deuterium content in all products of C3H8-D2 reactions. Propane cracking rate constants (k2) were not influenced by Co cations, because cracking occurs on acid sites and its stoichiometry and mechanism do not require hydrogen.

Kinetics and Reaction Pathways for Propane Dehydrogenation and Aromatization on Co/H-ZSM5 and H-ZSM5