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Acta Phys. -Chim. Sin.  2016, Vol. 32 Issue (7): 1785-1794    DOI: 10.3866/PKU.WHXB201604152
Article     
Deactivation and Regeneration of HZSM-5 Zeolite in Methanol-to-Propylene Reaction
HU Si1, ZHANG Qing2, GONG Yan-Jun2, ZHANG Ying1, WU Zhi-Jie2, DOU Tao2
1 Department of Materials Science and Engineering, College of Science, China University of Petroleum-Beijing, Beijing 102249, P. R. China;
2 The Key Laboratory of Catalysis, China National Petroleum Corporation, China University of Petroleum-Beijing, Beijing 102249, P. R. China
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Abstract  

The cause of the deactivation of a methanol-to-propylene (MTP) catalyst after multiple reaction cycles was studied. On this basis, a facile and effective approach, i.e., secondary crystallization, was proposed and applied to the regeneration of the catalyst. The HZSM-5 zeolite catalysts before and after regeneration were characterized by a series of techniques, including powder X-ray diffraction (XRD), X-ray fluorescence (XRF), X-ray photoelectron spectroscopy (XPS), N2 adsorption, 27Al magic-angle spinning nuclear magnetic resonance (27Al MAS NMR), temperature-programmed desorption of ammonia (NH3-TPD), and infrared spectroscopy of adsorbed pyridine (Py-IR). The physicochemical properties, such as framework, silica/alumina ratio, texture, and acidity, of the deactivated catalysts and the regenerated ones were investigated in detail. The catalytic performance of the zeolites in MTP conversion was tested under operating conditions of T = 470 ℃, p = 0.1 MPa (pMeOH = 30 kPa) and weight hourly space velocity (WHSV) = 1 h-1. The collapse of the zeolite structure and loss of active sites were found to be the essential reasons for the decline in catalyst activity after multiple reaction cycles. By regeneration via secondary crystallization, the relative crystallization, specific surface area, pore volume and acidity of the HZSM-5 catalyst were increased prominently. Meanwhile, the destroyed crystal structure and acid sites of the deactivated catalyst were restored effectively. Thus, the regenerated catalyst again exhibited excellent methanol conversion capacity and propylene selectivity in the MTP reaction.



Key wordsMethanol      Propylene      ZSM-5 zeolite      Deactivation      Regeneration      Secondary crystallization     
Received: 20 January 2016      Published: 15 April 2016
MSC2000:  O643.3  
Fund:  

The project was supported by the National Key Basic Research Program of China (973) (2012CB215002) and National Natural Science Foundation of China (21206192, 21276278).

Corresponding Authors: DOU Tao     E-mail: doutao@cup.edu.cn
Cite this article:

HU Si, ZHANG Qing, GONG Yan-Jun, ZHANG Ying, WU Zhi-Jie, DOU Tao. Deactivation and Regeneration of HZSM-5 Zeolite in Methanol-to-Propylene Reaction. Acta Phys. -Chim. Sin., 2016, 32(7): 1785-1794.

URL:

http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/10.3866/PKU.WHXB201604152     OR     http://www.whxb.pku.edu.cn/Jwk_wk/wlhx/Y2016/V32/I7/1785

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