Steam-dealuminated, OSDA-free RHO and KFI-type zeolites as catalysts for the methanol-to-olefins reaction

Abstract

RHO and KFI-type zeolites are synthesized in the absence of organic structure-directing agents (OSDAs), post-synthetically dealuminated via high temperature (600–800 °C) steam treatments, and evaluated as catalysts for converting methanol-to-light olefins (MTO). The proton forms of the as-made zeolites deactivate rapidly when tested for the MTO reaction (conducted at 400 °C and atmospheric pressure) due to their high aluminum content. Steam treatments lead to improvements in olefin selectivities and catalyst lifetimes with samples steamed at 600 °C giving the best combination of lifetime and olefin selectivity. Zeolite characterizations by 27Al NMR, 29Si NMR and argon physisorption indicate that the steam treatments extract framework aluminum, leading to reductions in the total number of Brønsted acid sites and the creation of mesopores that can facilitate transport of reactants. Poisoning of the acid sites external to the 8MR pores of the zeolites by treatments with trimethylphosphite results in longer catalyst lifetimes but do not affect the observed olefin selectivities, suggesting that olefins do not undergo secondary dimerization or methylation reactions at these sites.