Novel platinum/KL catalysts for the aromatization of N-hexane.

Abstract

Finally, regeneration of Pt/KL catalysts was studied for sulfur poisoned catalysts. While air effectively burned off coke deposits, sintering of Pt resulted. An oxychlorination treatment effectively redispersed the Pt.

The role of morphology of Pt inside the L-zeolite channels was found to play an important role on catalytic stability. Series of catalysts were prepared by incipient wetness and vapor phase impregnation and characterized by a variety of techniques, including H2 chemisorption, EXAFS, FTIR of adsorbed CO, MCP ring opening, and TEM and tested by both pulse and flow mode n-hexane reaction. While both catalysts exhibited small Pt clusters inside the channels of the L-zeolite, the IWI had a fraction near the surface region large enough to block channels. Under reaction, the IWI catalysts deactivated to about half the initial activity. However, VPI had Pt clusters small enough to reside in the lobes of the ellipsoid cages of the channels; these catalysts were remarkably stable. Addition of a small amount of thulium to KL was found to aid in dispersing the Pt. Using TPO, thulium was found to act a sulfur getter.

A number of studies were conducted to understand the underlying reasons for the uniqueness of Pt/KL for its high activity and selectivity for benzene production. Catalytic screening of basic supported Pt catalysts revealed that aromatization passes through dehydrogenated intermediates, including hexenes. Pt/KL was found to more efficiently convert hexenes to benzene than nonmicroporous basic supported Pt catalysts. The role of L-zeolite was found to protect the Pt clusters from bimolecular pathways leading to the deposition of coke on the surface of the Pt. Sulfur deactivates Pt/KL by agglomeration of Pt clusters and the formation of Pt-S, breaking up Pt ensembles required for aromatization.

Electronic modification to Pt by exchanging the zeolite cation from potassium to lithium was studied by shape resonance XANES, microcalorimetry, and pulse neopentane hydrogenolysis. Addition of lithium resulted in a shift of the Fermi level of Pt away from the antibonding state of Pt-H, strengthening the chemisorption bond. Increased hydrogenolysis rates were observed for both neopentane and n-hexane aromatization experiments at the expense of aromatization.