Mechanism and Kinetics of n-Butane Dehydrogenation to 1,3-Butadiene Catalyzed by Isolated Pt Sites Grafted onto ≡SiOZn–OH Nests in Dealuminated Zeolite Beta

Abstract

An interest in the on-purpose production of 1,3-butadiene (1,3-BD) has grown, as a consequence of the decline in naphtha cracking for the production of ethene and propene, products that can now be produced economically by thermal dehydrogenation of ethane and propane contained in natural gas. In this study, the mechanism and kinetics of n-butane dehydrogenation to 1,3-BD are explored over atomically distributed Pt sites grafted onto dealuminated zeolite BEA (DeAlBEA) in the form of (≡Si–O–Zn)4–6Pt complexes. Reaction of n-butane dehydrogenation carried out at 823 K with 2.53 kPa n-butane/He and a weight-hourly space velocity (WHSV) of 14.5 h–1 produced 1,3-BD with a turnover frequency of 0.45 mol 1,3-BD (mol Pt)−1 s–1. Space-time studies and identification of the reaction intermediates suggest that n-butane first undergoes dehydrogenation primarily to 1-butene, which then rapidly isomerizes to produce an equilibrated mixture of 1-butene and 2-butene. 1-Butene then undergoes secondary dehydrogenation to produce 1,3-BD. We report, here, a detailed study of the kinetics of n-butane dehydrogenation to butenes and 1-butene dehydrogenation to 1,3-BD over isolated Pt sites. Both reactions exhibit a Langmuir–Hinshelwood dependence on n-butane and 1-butene partial pressures, respectively. Comparison of effective forward rate constants of n-butane dehydrogenation to butenes (k1f) and butene dehydrogenation to 1,3-BD (k2f) shows that the isolated Pt sites grafted onto DeAlBEA exhibit a very high activity for sequential dehydrogenation of n-butane to 1,3-BD relative to other Pt-based catalysts previously reported.