氢氧化钠-氟硅酸铵改性HZSM-5催化甲醇制丙烯

doi:10.3866/PKU.WHXB201504302

Abstract

Abstract:

A sequential modification by sodium hydroxide (NaOH) and ammonium hexafluorosilicate ((NH₄)₂SiF₆) solution was used for preparing MTP (methanol to propylene reaction) catalyst for the first time. The parent and modified samples were characterized by diverse techniques including powder X-ray diffraction (XRD), X-ray fluorescence (XRF) spectroscopy, N₂ adsorption-desorption, transmission electron microscopy (TEM), and NH₃ temperature-programmed desorption (NH₃-TPD). The effect of modification on the physicochemical properties, such as framework, chemical composition, texture, and acidity, were investigated in detail. The results showed that the mesopore volume of the zeolite catalyst increased significantly following sequential NaOH and (NH₄)₂SiF₆ modification. The acidity was also modulated effectively. The composite modification method successfully overcame the disadvantages associated with individual simple alkali and (NH₄)₂SiF₆ treatments. For instance, using a simple alkali treatment would destroy the framework of the zeolite easily, whereas using a simple (NH₄)₂SiF₆ treatment would only modify the external surface of the zeolite owing to the limited diffusion of the ammonium hexafluorosilicate molecule. When used in MTP reaction, the induction period of the composite modified sample was greatly shortened, and the initial selectivity for propylene increased to 43% under the following operating conditions: T=470 ℃, p=0.1 MPa (p_MeOH=50 kPa), and weight hourly space velocity (WHSV)=2 h^-1. Moreover, the composite modified zeolite catalyst exhibited significantly improved stability, and the catalytic lifespan was triple that of the parent sample.

Key words: Alkali treatment, Ammonium hexafluorosilicate, Composite modification, Mesopore, Acidity, Methanol to propylene

HU Si, ZHANG Qing, YIN Qi, ZHANG Ya-Fei, GONG Yan-Jun, ZHANG Ying, WU Zhi-Jie, DOU Tao. Catalytic Conversion of Methanol to Propylene over HZSM-5 Modified by NaOH and (NH₄)₂SiF₆[J].Acta Phys. -Chim. Sin., 2015, 31(7): 1374-1382.

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Catalytic Conversion of Methanol to Propylene over HZSM-5 Modified by NaOH and (NH₄)₂SiF₆

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Catalytic Conversion of Methanol to Propylene over HZSM-5 Modified by NaOH and (NH₄)₂SiF₆