Mesoporogen-Free Synthesis of Hierarchical SAPO-34 with Low Template Consumption and Excellent Methanol-to-Olefin Conversion

Significant interest has emerged in the development of nanometer-sized and hierarchical silicoaluminophosphate zeolites (SAPO-34) because of their enhanced accessibility and improved catalytic activity for methanol-to-olefin (MTO) conversion. A series of nanometer-sized SAPO-34 catalysts with tunable hierarchical structures was synthesized in a Al₂O₃/H₃PO₄/SiO₂/triethylamine(TEA)/H₂O system by using a mesoporogen-free nanoseed-assisted method. The nanometer-sized hierarchical S_H-3.0 catalyst (TEA/Al₂O₃=3.0) possessed the highest crystallinity, highest abundance of intracrystalline meso-/macropores, and the most suitable acidity among all obtained catalysts, showing the highest ethylene and propylene selectivity of 85.4 %. This is the highest reported selectivity for MTO reactions under similar conditions. Detailed analysis of the coke produced during the reaction revealed that the small-sized methyl-substituted benzene and bulky methyl-substituted pyrene were mainly located inside the crystals instead of on the surface of the crystals, which provided further insight into understanding the deactivation of the SAPO-34 catalyst during MTO reaction. Significantly, the simple and cost-effective synthetic process and superb catalytic performance of the nanometer-sized hierarchical SAPO-34 is promising for their practical large-scale application for MTO conversion.