Highly Dispersed CeO _x ‐Modified SSZ‐13 Zeolite for Enhanced Methanol‐to‐Olefins Reaction

ABSTRACT

In methanol‐to‐olefins (MTO) reactions, extending the catalyst lifetime remains a critical challenge for industrial applications. Herein, we develop a synergistic synthetic strategy integrating a micro‐liquid film (MLF) reactor, crystal seed assistance, and ligand protection to efficiently incorporate cerium species into SSZ‐13 zeolite, thereby yielding highly dispersed CeO _x nanocluster‐modified SSZ‐13 zeolites (Ce‐SSZ‐13). The CeO _x loading effectively modulated the acid properties by weakening Brønsted acid strength while generating additional weak Lewis acid sites. The Ce‐SSZ‐13 zeolite featuring a 1 wt% Ce loading showed excellent catalytic performance at a weight hourly space velocity of 1 h ⁻¹ and 400°C, with a long catalyst lifetime of 10.4 h and a 91.3% selectivity of light olefins. Notably, the catalyst lifetime was enhanced by 41.1% compared with the unmodified SSZ‐13 zeolite, accompanied by a significantly reduced coke formation rate of 0.081 mg·min ⁻¹ . It was revealed that the appropriate acidity of Ce‐SSZ‐13 zeolites efficiently suppressed hydrogen transfer and aromatization processes in MTO reactions and stabilized key hydrocarbon pool intermediates, thereby shifting the reaction pathway toward the olefin cycle. These findings provide an effective strategy for rationally designing high‐performance SSZ‐13 catalysts for MTO reactions and highlight the critical role of acid modulation of SSZ‐13 zeolites.