ZSM-5 Catalysts for MTO: Effect and Optimization of the Tetrapropylammonium Hydroxide Concentration on Synthesis and Performance

ACS Omega. 2022 Jun 15;7(25):21654-21663. doi: 10.1021/acsomega.2c01539. eCollection 2022 Jun 28.

Abstract

Light olefin production from methanol using various zeolite catalysts has industrial and economic importance considering the growth of the petrochemical market. Zeolites are generally synthesized using various organic templates as structure-directing agents (SDAs). In this study, synthesis of a series of ZSM-5 zeolites was performed systematically using the microwave-assisted crystallization method, and these samples were analyzed in detail to understand the effect of the SDA concentration. Powder diffraction, N2 adsorption, scanning electron microscopy, ammonia adsorption desorption, and 27Al and 29Si NMR spectroscopies were used for the characterization. The organic SDA tetrapropyl ammonium hydroxide (TPAOH/SiO2 mole ratio = 0.0500) is found to have an optimum concentration against the silica precursor for achieving the highest crystallinity, suitable morphology, ideal pore size, effective pore volume, and tuned microporous/mesoporous area. For samples with a template concentration ratio of 0.050 or higher, 29Si and 27Al NMR data revealed the presence of an intact ZSM-5 structure. Using a fixed bed reactor at 500 °C and atmospheric pressure, the catalytic performance of the selected catalysts from the series is investigated for the methanol-to-olefin conversion reaction. The sample with the highest crystallinity showed the best conversion, selectivity toward light olefins, and time on stream stability. It is also worth noting that the highest crystallinity, micropore area, and micropore volume are reached for the optimum value rather than the highest template concentration. This allows for a reduction in the template concentration and a move closer to a synthesis pathway benign to environment and economics.