Acta Phys. -Chim. Sin. ›› 2015, Vol. 31 ›› Issue (5): 965-972.doi: 10.3866/PKU.WHXB201503024

• CATALYSIS AND SURFACE SCIENCE • Previous Articles     Next Articles

Regulation of Pore Structure and Acidity of a ZSM-5 Catalyst for Dehydration of Glycerol to Acrolein

PAN Wen-Ya1, HUANG Liang1, QIN Feng1, ZHUANG Yan2, LI Xue-Mei2, MA Jian-Xue2, SHEN Wei1, XU Hua-Long1   

  1. 1 Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Department of Chemistry, Fudan University, Shanghai 200433, P. R. China;
    2 Shanghai Huayi Acrylic Acid Ltd. Co., Shanghai 200137, P. R. China
  • Received:2014-12-09 Revised:2015-02-11 Published:2015-05-08
  • Contact: SHEN Wei, XU Hua-Long;
  • Supported by:

    The project was supported by the Science and Technology Commission of Shanghai Municipality for International Collaboration Project, China (14120700700) and Funding of Key Laboratory, China (11JC1400400).


Pore structure and acidity of ZSM-5 catalysts were successfully regulated by alkali treatment. ZSM- 5 was etched in 0.2 mol·L- 1 NaOH solution at 65 and 85 ℃. Micro-mesoporous ZSM-5 catalysts were successfully prepared with a high density of acidic sites. The activity and stability were significantly enhanced with alkali-treated ZSM-5, giving a conversion of glycerol above 95%, with selectivity for acrolein of 78% after 10 h compared with a ZSM-5-at85 (alkali-treated at 85 ℃) catalyst. Characterization of N2 adsorption and desorption isotherms, X-ray diffraction (XRD), 27Al mass atomic spectroscopy-nuclear magnetic resonance (27Al MAS-NMR), and transmission electron microscopy (TEM) were performed to interpret the morphology and surface properties. The results reveal that the Si in the framework of ZSM-5 was leached out by alkali treatment, and many mesopores were formed on the ZSM-5 surface. However, the MFI topology did not change and Al was mainly integrated within the framework. X-ray photoelectron spectroscopy (XPS), X-ray fluorescence (XRF), and NH3-temperature-programed desorption (NH3-TPD) experiments demonstrated that the molar ratio of Si/ Al on the external surface was lower than that in the framework, indicating that more Si on the external surface of ZSM-5 was leached by alkali treatment, while the acidic density increased because of the lower molar ratio of Si/Al near newly formed mesopores. ZSM-5 catalysts with mesopores and higher acidic density enhance reactant diffusion and coking tolerance, which improves the activity and stability during glycerol dehydration.

Key words: Micro-mesoporous ZSM-5, Surface acidity, Alkali treatment, Dehydration of glycerol, Acrolein


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