Propane dehydrogenation catalyzed by single Lewis acid site in Sn-Beta zeolite

Abstract

The gap between supply and demand of propylene has become more and more evident, because of a large consumption of the downstream products derived from propylene. Propane dehydrogenation (PDH) constitutes an important alternative for the production of propylene, and thus considerable attention has been paid to the development of eco-friendly and cost-efficient catalysts for this process. Herein, we discover that the Sn-Beta zeolite with Lewis acid sites can activate the C-H bond, and exhibits high catalytic performance in the PDH. XRD, STEM, and XPS characterizations confirm that Sn species are incorporated into the zeolite framework, and H2-TPR suggests that there is a strong interaction between Sn species and zeolite framework. It is found that the Lewis acid is the active site for dehydrogenation reaction, and the Brønsted acid is responsible for cracking reaction. The dehydrogenation rate/cracking rate is positively proportional to the L/B ratio, and a high L/B ratio is beneficial for the propane dehydrogenation reaction. The Na-Sn-Beta-30 catalyst possessing the highest amount of Lewis acid but the lowest Brønsted/Lewis ratio, exhibits the best performance in the PDH, which delivers propane conversion of 40% and propylene selectivity of 92%. Most importantly, these Sn-Beta zeolites are extremely stable without any detectable deactivation under the harsh reaction condition for 72 h. Density functional theory calculations reveal that both Sn and adjacent O atom or OH group cooperativelyact as the active sites. The PDH occurs through the direct reaction mechanism in which hydrogen molecule is produced by the direct coupling of H atom of primary C3H7 motif with the Brønsted proton in closed sites or the proton of water in open sites. It seems that open sites are more reactive than the closed ones, and the intrinsic enthalpy barriers are calculated to be 242 ~ 301 kJ/mol depending on the hydroxylation extents. These efficient Sn-Beta zeolites could provide a new possibility for the development of a new generation of PDH catalysts with a high stability for the production of propylene.