High-Yield Synthesis of Hierarchical SAPO-34 by Recrystallization Method for Efficient Methanol-to-Olefin Reactions

Abstract

Prolonging the lifetime of SAPO-34 catalysts and enhancing their olefin selectivity in methanol-to-olefin (MTO) reactions are critical yet challenging objectives. Here, a series of hierarchical SAPO-34 catalysts were synthesized using a straightforward recrystallization method. The incorporation of triethylamine into the recrystallization mother liquor facilitated the formation of mesopores, achieving a high solid yield of up to 90%. Notably, the addition of phosphoric acid and ammonium polyvinyl phosphate alcohol during the recrystallization process significantly enhanced the crystallinity and regularity of the hierarchical SAPO-34 crystals, consequently increasing the mesopore size. Due to the substantially improved mass transfer efficiency and moderated acidity, the SP34-0.14P-0.06R catalysts exhibited a prolonged operational life of 344 min and 80.3% selectivity of ethylene and propylene at a WHSV of 2h-1. This performance markedly surpasses that of the parent SP34 catalyst, which demonstrated a lifetime of 136 min and a selectivity of 78.0%. Remarkably, the SP34-0.14P-0.06R maintained a lifetime of 166 minutes even at a high WHSV of 10h-1, which is more than 5-fold greater than that of the original microporous SP34. This research offers valuable insights into the design and development of hierarchically porous zeolites with high yields, enhancing the efficiency of MTO reactions and other applications.

Keywords: SAPO-34; hierarchical pore; light olefins; methanol-to-olefin; recrystallization.