Synthesis of hierarchical ZSM-11 and its catalytic performances during methanol to propylene

To solve the easy deactivation of zeolite catalyst in methanol to propylene (MTP) reaction, hierarchical ZSM-11 zeolite composed of loosely aggregating ultra-small nanocrystals (∼10 nm) were prepared using vinyltrimethoxysilane-methyl methacrylate (VTMS-MMA) copolymer latex as a “bond blocker”. The structure and texture properties of the as-synthesized zeolite were systematically characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption desorption, NH₃-TPD, and thermogravimetric analysis (TG). The results showed that as compared with the parent ZSM-11-0 without adding the latex, the hierarchically porous ZSM-11-x (1 ≤ x ≤ 3) zeolite synthesized with VTMS-MMA copolymer latex had a higher surface area, mesopore volume, and moderate acidity. Due to the nanocrystallization of the primary grain in the polycrystalline aggregates, the micropores channels in the as-synthesized ZSM-11-x (1 ≤ x ≤ 3) were effectively shortened and abundant intercrystalline mesopores resulted from loosely aggregating of the ultrasmall primary crystals were therefore introduced, which offered the optimized ZSM-11-1 catalysts with a longer catalyst life (46 h) and a higher propylene yield (∼40.5 %) in MTP.