Steam-assisted synthesis of SAPO-34@ZSM-5 core-shell zeolite for enhancing the synergies of n-hexane-Methanol Co-Reaction to light olefins

Abstract

An alternative and promising route for the production of light olefins which realizes the objective of effective resource usage is the coupling conversion of n -hexane-methanol. The SAPO-34@ZSM-5 core-shell composite has been designed and fabricated by the steam-assisted crystallization (SAC) method for boosting the n -hexane-methanol synergies. SAC avoids the undesired phase transformation/dissolution of SAPO-34 caused by exposure to harsh basic conditions of the ZSM-5 precursor solution. In comparison with the nanosized ZSM-5 or physical mixture, the SAPO-34@ZSM-5 core-shell zeolite demonstrates a 32–38 wt% increase in the light olefin selectivity, a 28–67 wt% increase in the n -hexane conversion, and an 89–143% improvement in the catalyst lifetime under identical reaction conditions. With the aid of GC-MS analysis of carbonaceous deposits in spent catalysts, higher polymethylbenzenes concentration and lower polycyclic aromatic hydrocarbon (PHA) concentration are obtained from the extracted species of spent SAPO-34@ZSM-5 in comparison with that of other samples, which suggests the aromatic-based route to light olefins is enhanced and the carbonaceous deposition is slowed down. The core-shell configuration of the SAPO-34@ZSM-5 composite diminishes the diffusion rate of methanol towards the SAPO-34 core layer and increases the coupling of n -hexane derivatives with methanol in the hydrocarbon pool (HCP) route. The decreased number of acidic sites on the external surface of the SAPO-34 core layer may also be accounted for the inhibited carbon deposition. • SAPO-34@ZSM-5 is synthesized firstly by a steam-assisted crystallization method. • Core-shell structure of SAPO-34@ZSM-5 enhances the synergistic effect of reactants. • Core-shell structure of SAPO-34@ZSM-5 slows down coking inside the SAPO-34 core layer. • A synergistic path for n-hexane-methanol co-reaction on SAPO-34@ZSM-5 is proposed.