Citation: HU Si, ZHANG Qing, YIN Qi, ZHANG Ya-Fei, NG 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 Physico-Chimica Sinica, ;2015, 31(7): 1374-1382. doi: 10.3866/PKU.WHXB201504302 shu

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

HU Si ¹ ,
ZHANG Qing ² ,
YIN Qi ² ,
ZHANG Ya-Fei ² ,
NG Yan-Jun ² ,
ZHANG Ying ¹ ,
WU Zhi-Jie ² ,
DOU Tao ^2,

1.
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: 7 January 2015
Available Online: 30 April 2015
Fund Project: 国家重点基础研究发展规划项目(973) (2012CB215002) (973) (2012CB215002)国家自然科学基金(21206192)资助 (21206192)

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.
- Alkali treatment,
- Ammonium hexafluorosilicate,
- Composite modification,
- Mesopore,
- Acidity,
- Methanol to propylene
1. [1]
  
  (1) Koempel, H.; Liebner, W. Lurgi's Methanol to Propylene (MTP) Report on a Successful Commercialisation. In Studies in Surface Science and Catalysis; Noronha, F. B., Schmal, M., Sousa- Aguiar, E. F. Eds.; Elsevier: Frankfurt, 2007; Vol. 167, pp 261-267.
2. [2]
  (2) Stöcker, M. Microporous Mesoporous Mat. 1999, 29, 3. doi: 10.1016/S1387-1811(98)00319-9
3. [3]
  (3) Wen, P. Y.; Mei, C. S.; Liu, H. X.; Yang, W. M.; Chen, Q. L. Chemical Reaction Engineering and Technology 2007, 23, 385. [温鹏宇, 梅长松, 刘红星, 杨为民, 陈庆龄. 化学反应工程与工艺, 2007, 23, 385.]
4. [4]
  (4) Mei, C. S.; Wen, P. Y.; Liu, Z. C.; Liu, H. X.; Wang, Y. D.; Yang, W. M.; Xie, Z. K.; Hua, W. M.; Gao, Z. J. Catal. 2008, 258, 243. doi: 10.1016/j.jcat.2008.06.019
5. [5]
  (5) Wen, P. Y.; Mei, C. S.; Liu, H. X.; Yang, W. M.; Chen, Q. L. Chemical Reaction Engineering and Technology 2007, 23, 481. [温鹏宇, 梅长松, 刘红星, 杨为民, 陈庆龄. 化学反应工程与工艺, 2007, 23, 481.]
6. [6]
  (6) Wen, P. Y.; Mei, C. S.; Liu, H. X.; Yang, W. M.; Chen, Q. L. Acta Petrolei Sinica (Petroleum Processing Section) 2008, 24, 446. [温鹏宇, 梅长松, 刘红星, 杨为民, 陈庆龄. 石油学报(石油加工), 2008, 24, 446.]
7. [7]
  (7) Firoozi, M.; Baghalha, M.; Asadi, M. Catal. Commum. 2009, 10, 1582. doi: 10.1016/j.catcom.2009.04.021
8. [8]
  (8) Hu, S.; ng, Y. J.; Xu, Q. H.; Liu, X. L.; Zhang, Q.; Zhang, L. L.; Dou, T. Catal. Commum. 2012, 28, 95. doi: 10.1016/j.catcom.2012.08.011
9. [9]
  (9) Hu, S.; ng, Y. J.; Zhang, Q.; Zhang, J. L.; Zhang, Y. F.; Yang, F. Y.; Dou, T. Journal of Chemical Industry and Engineering (China) 2012, 63, 3889. [胡思, 巩雁军, 张卿, 张军亮, 张亚飞, 杨飞鹰, 窦涛. 化工学报, 2012, 63, 3889.]
10. [10]
  (10) Hu, S.; Shan, J.; Zhang, Q.; Wang, Y.; Liu, Y. S.; ng, Y. J.; Wu, Z. J.; Dou, T. Appl. Catal. A 2012, 445-446, 215.
11. [11]
  (11) Sun, X. Y.; Mueller, S.; Shi, H.; Haller, G. L.; Sanchez-Sanchez, M.; van Veen, A. C.; Lercher, J. A. J. Catal. 2014, 314, 21. doi: 10.1016/j.jcat.2014.03.013
12. [12]
  (12) Olsbye, U.; Svelle, S.; Bjorgen, M.; Beato, P.; Janssens, T. V. W.; Joensen, F.; Bordiga, S.; Lillerud, K. P. Angew. Chem. Int. Edit. 2012, 51, 5810. doi: 10.1002/anie.201103657
13. [13]
  (13) Zhang, Q.; Hu, S.; Zhang, L. L.; Wu, Z. J.; ng, Y. J.; Dou, T. Green Chem. 2014, 16, 77. doi: 10.1039/C3GC41327F
14. [14]
  (14) Zhao, T. S.; Takemoto, T.; Tsubaki, N. Catal. Commun. 2006, 7, 647. doi: 10.1016/j.catcom.2005.11.009
15. [15]
  (15) Guo, Q. S.; Mao, D. S.; Lao, Y. P.; Lu, G. Z. Chin. J. Catal. 2009, 30, 1248. [郭强胜, 毛东森, 劳嫣萍, 卢冠忠. 催化学报, 2009, 30, 1248.]
16. [16]
  (16) Mao, D. S.; Guo, Q. S.; Meng, T. Acta Phys. -Chim. Sin. 2010, 26, 2242. [毛东森, 郭强胜, 孟涛. 物理化学学报, 2010, 26, 2242.] doi: 10.3866/PKU.WHXB20100814
17. [17]
  (17) Mao, D. S.; Guo, Q. S.; Meng, T. Acta Phys. -Chim. Sin. 2010, 26, 338. [毛东森, 郭强胜, 孟涛. 物理化学学报, 2010, 26, 338.] doi: 10.3866/PKU.WHXB20100208
18. [18]
  (18) Zhu, X. L.; Lobban, L. L.; Mallinson, R. G.; Resasco, D. E. J. Catal. 2010, 271, 88. doi: 10.1016/j.jcat.2010.02.004
19. [19]
  (19) Zhao, L.; Shen, B. J.; Gao, F. S.; Xu, C. M. J. Catal. 2008, 258, 228. doi: 10.1016/j.jcat.2008.06.015
20. [20]
  (20) Groen, J. C.; Zhu, W. D.; Brouwer, S.; Huynink, S. J.; Kapteijn, F.; Moulijn, J. A.; Perez-Ramirez, J. J. Am. Chem. Soc. 2007, 129, 355. doi: 10.1021/ja065737o
21. [21]
  (21) Hu, S.; Zhang, Q.; Xia, Z.; ng, Y. J.; Xu, J.; Deng, F.; Dou, T. Acta Phys. -Chim. Sin. 2012, 28, 2705. [胡思, 张卿, 夏至, 巩雁军, 徐君, 邓风, 窦涛. 物理化学学报, 2012, 28, 2705.] doi: 10.3866/PKU.WHXB201207171
22. [22]
  (22) Zhao, G. L.; Teng, J.W.; Xie, Z. K.; Tang, Y.; Yang, W. M.; Chen, Q. L. Chin. J. Catal. 2005, 26, 1083. [赵国良, 滕加伟, 谢在库, 唐颐, 杨为明, 陈庆龄. 催化学报, 2005, 26, 1083.]
23. [23]
  (23) Song, M. J.; Zou, C. L.; Niu, G. X.; Zhao, D. Y. Chin. J. Catal. 2012, 33, 140. [宋明娟, 邹成龙, 牛国兴, 赵东元. 催化学报, 2012, 33, 140.] doi: 10.1016/S1872-2067(10)60283-5
24. [24]
  (24) Han, S.; Shihabi, D. S.; Chang, C. D. J. Catal. 2000, 196, 375. doi: 10.1006/jcat.2000.3037
25. [25]
  (25) Sun, C.; Du, J. M.; Liu, J.; Yang, Y. S.; Ren, N.; Shen, W.; Xu, H. L.; Tang, Y. Chem. Commun. 2010, 46, 2671. doi: 10.1039/b925850g
26. [26]
  (26) Qin, Z. X.; Shen, B. J.; Gao, X. H.; Lin, F.; Wang, B. J.; Xu, C. M. J. Catal. 2011, 278, 266. doi: 10.1016/j.jcat.2010.12.013
27. [27]
  (27) Bjørgen, M.; Joensen, F.; Lillerud, K. P.; Olsbye, U.; Svelle, S. Catal. Today 2009, 142, 90. doi: 10.1016/j.cattod.2009.01.015
28. [28]
  (28) Brogaard, R. Y.; Henry, R.; Schuurman, Y.; Medford, A. J.; Moses, P. G.; Beato, P.; Svelle, S.; Nørskov, J. K.; Olsbye, U. J. Catal. 2014, 314, 159. doi: 10.1016/j.jcat.2014.04.006
29. [29]
  (29) Liu, J.; Zhang, C. X.; Shen, Z. H.; Hua, W. M.; Tang, Y.; Shen, W.; Yue, Y. H.; Xu, H. L. Catal. Commun. 2009, 10, 1506. doi: 10.1016/j.catcom.2009.04.004
30. [30]
  (30) Choi, M.; Na, K.; Kim, J.; Sakamoto, Y.; Terasaki, O.; Ryoo, R. Nature 2009, 461, 246. doi: 10.1038/nature08288
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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