Citation: 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[J]. Acta Physico-Chimica Sinica, ;2016, 32(7): 1785-1794. doi: 10.3866/PKU.WHXB201604152 shu

Deactivation and Regeneration of HZSM-5 Zeolite in Methanol-to-Propylene Reaction

HU Si ^1, ,
ZHANG Qing ² ,
GONG Yan-Jun ² ,
ZHANG Ying ¹ ,
WU Zhi-Jie ² ,
DOU Tao ²

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

Received Date: 20 January 2016
Revised Date: 15 April 2016

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

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 (p_MeOH = 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.
- Methanol,
- Propylene,
- ZSM-5 zeolite,
- Deactivation,
- Regeneration,
- Secondary crystallization
1. [1]
2. [2]
3. [3]
4. [4]
5. [5]
6. [6]
7. [7]
8. [8]
9. [9]
10. [10]
11. [11]
12. [12]
13. [13]
14. [14]
15. [15]
16. [16]
17. [17]
18. [18]
19. [19]
20. [20]
21. [21]
22. [22]
23. [23]
24. [24]
25. [25]
26. [26]
27. [27]
1. [1]
  Xingyang LI , Tianju LIU , Yang GAO , Dandan ZHANG , Yong ZHOU , Meng PAN . A superior methanol-to-propylene catalyst: Construction via synergistic regulation of pore structure and acidic property of high-silica ZSM-5 zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1279-1289. doi: 10.11862/CJIC.20240026
2. [2]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
3. [3]
  Hengyi ZHU , Liyun JU , Haoyue ZHANG , Jiaxin DU , Yutong XIE , Li SONG , Yachao JIN , Mingdao ZHANG . Efficient regeneration of waste LiNi_0.5Co_0.2Mn_0.3O₂ cathode toward high-performance Li-ion battery. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 625-638. doi: 10.11862/CJIC.20240358
4. [4]
  Xinyu You , Xin Zhang , Shican Jiang , Yiru Ye , Lin Gu , Hexun Zhou , Pandong Ma , Jamal Ftouni , Abhishek Dutta Chowdhury . Efficacy of Ca/ZSM-5 zeolites derived from precipitated calcium carbonate in the methanol-to-olefin process. Chinese Journal of Structural Chemistry, 2024, 43(4): 100265-100265. doi: 10.1016/j.cjsc.2024.100265
5. [5]
  Guojie Xu , Fang Yu , Yunxia Wang , Meng Sun . Introduction to Metal-Catalyzed β-Carbon Elimination Reaction of Cyclopropenones. University Chemistry, 2024, 39(8): 169-173. doi: 10.3866/PKU.DXHX202401060
6. [6]
  Zhuoyan Lv , Yangming Ding , Leilei Kang , Lin Li , Xiao Yan Liu , Aiqin Wang , Tao Zhang . Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst. Acta Physico-Chimica Sinica, 2025, 41(4): 100038-. doi: 10.3866/PKU.WHXB202408015
7. [7]
  Yong Shu , Xing Chen , Sai Duan , Rongzhen Liao . How to Determine the Equilibrium Bond Distance of Homonuclear Diatomic Molecules: A Case Study of H₂. University Chemistry, 2024, 39(7): 386-393. doi: 10.3866/PKU.DXHX202310102
8. [8]
  Shanyuan Bi , Jin Zhang , Dengchao Peng , Danhong Cheng , Jianping Zhang , Lupeng Han , Dengsong Zhang . Improved N₂ selectivity for low-temperature NO_x reduction over etched ZSM-5 supported MnCe oxide catalysts. Chinese Chemical Letters, 2025, 36(5): 110295-. doi: 10.1016/j.cclet.2024.110295
9. [9]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
10. [10]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-. doi: 10.3866/PKU.WHXB202406012
11. [11]
  Jiali CHEN , Guoxiang ZHAO , Yayu YAN , Wanting XIA , Qiaohong LI , Jian ZHANG . Machine learning exploring the adsorption of electronic gases on zeolite molecular sieves. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 155-164. doi: 10.11862/CJIC.20240408
12. [12]
  Yiping HUANG , Liqin TANG , Yufan JI , Cheng CHEN , Shuangtao LI , Jingjing HUANG , Xuechao GAO , Xuehong GU . Hollow fiber NaA zeolite membrane for deep dehydration of ethanol solvent by vapor permeation. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 225-234. doi: 10.11862/CJIC.20240224
13. [13]
  Zijian Zhao , Yanxin Shi , Shicheng Li , Wenhong Ruan , Fang Zhu , Jijun Jiang . A New Exploration of the Preparation of Polyacrylic Acid by Free Radical Polymerization Based on the Concept of Green Chemistry. University Chemistry, 2024, 39(5): 315-324. doi: 10.3866/PKU.DXHX202311094
14. [14]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350
15. [15]
  Yongmei Liu , Lisen Sun , Zhen Huang , Tao Tu . Curriculum-Based Ideological and Political Design for the Experiment of Methanol Oxidation to Formaldehyde Catalyzed by Electrolytic Silver. University Chemistry, 2024, 39(2): 67-71. doi: 10.3866/PKU.DXHX202308020
16. [16]
  Ling Liu , Haibin Wang , Genrong Qiang . Curriculum Ideological and Political Design for the Comprehensive Preparation Experiment of Ethyl Benzoate Synthesized from Benzyl Alcohol. University Chemistry, 2024, 39(2): 94-98. doi: 10.3866/PKU.DXHX202304080
17. [17]
  Wanmin Cheng , Juan Du , Peiwen Liu , Yiyun Jiang , Hong Jiang . Photoinitiated Grignard Reagent Synthesis and Experimental Improvement in Triphenylmethanol Preparation. University Chemistry, 2024, 39(5): 238-242. doi: 10.3866/PKU.DXHX202311066
18. [18]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
19. [19]
  Xue Liu , Lipeng Wang , Luling Li , Kai Wang , Wenju Liu , Biao Hu , Daofan Cao , Fenghao Jiang , Junguo Li , Ke Liu . Cu基和Pt基甲醇水蒸气重整制氢催化剂研究进展. Acta Physico-Chimica Sinica, 2025, 41(5): 100049-. doi: 10.1016/j.actphy.2025.100049
20. [20]
  Junke LIU , Kungui ZHENG , Wenjing SUN , Gaoyang BAI , Guodong BAI , Zuwei YIN , Yao ZHOU , Juntao LI . Preparation of modified high-nickel layered cathode with LiAlO₂/cyclopolyacrylonitrile dual-functional coating. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1461-1473. doi: 10.11862/CJIC.20240189

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(835)
HTML views(107)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142