Citation: HU Si, ZHANG Qing, XIA Zhi, NG Yan-Jun, XU Jun, DENG Feng, DOU Tao. Catalytic Conversion of Methanol to Propylene over (NH₄)₂SiF₆-Modified Nanosized HZSM-5 Zeolite[J]. Acta Physico-Chimica Sinica, ;2012, 28(11): 2705-2712. doi: 10.3866/PKU.WHXB201207171 shu

Catalytic Conversion of Methanol to Propylene over (NH₄)₂SiF₆-Modified Nanosized HZSM-5 Zeolite

HU Si ¹ ,
ZHANG Qing ¹ ,
XIA Zhi ² ,
NG Yan-Jun ^1, ,
XU Jun ³ ,
DENG Feng ³ ,
DOU Tao ^1,2,

1.
1 The Key Laboratory of Catalysis of CNPC, China University of Petroleum-Beijing, Beijing 102249, P. R. China;
2 Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, P. R. China;
3 Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, P. R. China

Received Date: 25 May 2012
Available Online: 17 July 2012
Fund Project: 国家重点基础研究发展计划(973)项目(2012CB215002) (973)项目(2012CB215002) 国家自然科学基金(10979076, 21176255) (10979076, 21176255) 国际科技合作与交流专项项目(2010DFB40440)资助 (2010DFB40440)

(NH₄)₂SiF₆-modified nanosized HZSM-5 zeolite was prepared and investigated as a catalyst formethanol to propylene conversion. The effects of this modification on the framework, textural propertiesand acidity of both the parent and the modified HZSM-5 zeolite were investigated by powder X-raydiffraction (XRD), ²⁷Al magic angle spinning nuclear magnetic resonance (²⁷Al MAS NMR), X-rayfluorescence (XRF), X-ray photoelectron spectroscopy (XPS), N₂ adsorption, transmission electronmicroscopy (TEM), temperature-programmed desorption of ammonia (NH₃-TPD), and infraredspectroscopy of adsorbed pyridine (Py-IR). The catalytic performance of these materials on the methanolto propylene (MTP) conversion process was tested under operating conditions of T=450℃, p=0.1 MPa(p_MeOH=50 KPa) and WHSV=1 h^-1. The results showed that surface aluminum on the nanosized ZSM-5zeolite could be selectively removed by the (NH₄)₂SiF₆ solution and that the number of acidic sites on theHZSM-5 zeolite gradually decreased with increasing (NH₄)₂SiF₆ concentration. Moreover, after modification with an optimally concentrated (NH₄)₂SiF₆ solution, an obvious increase in specific surface area as well asmesopore volume was observed for the nanosized HZSM-5 with a resulting dramatic improvement in thecatalytic performance of this material for the MTP reaction. Both the propylene selectivity and propylene/ethylene (P/E) mass ratio resulting from use of the modified HZSM-5 increased significantly to 45.1% and8.0, as compared to results of 28.8% and 2.6 obtained with the original material. In addition, the catalyticlifespan of the modified zeolite was double that of the original.
- Nanosized ZSM-5,
- Dealumination,
- Pore structure,
- Acidity,
- Propylene selectivity,
- Catalytic lifetime
1. [1]
  
  (1) Inagaki, S.; Takechi, K.; Kubota, Y. Chem. Commun. 2010, 46,2662. doi: 10.1039/b925408k
2. [2]
  (2) Schneider, M.; Schmidt, F.; Burgfels, G.; Buchold, H.; Möller,F.W. Process for Preparing Lower Olefins. Eur. Pat. 0448000,1991.
3. [3]
  (3) Koempel, H.; Liebner,W. Lurgi's Methanol to Propylene (MTP)Report on a SuccessfulCommercialisation. In Studies in Surface Science and Catalysis; Noronha, F. B., Schmal, M.,Sousa-Aguiar, E. F. Eds.; Elsevier: Frankfurt, 2007; Vol. 167, pp261-267.
4. [4]
  (4) Zhao, T. S.; Takemoto, T.; Tsubaki, N. Catal. Commun. 2006, 7,647. doi: 10.1016/j.catcom.2005.11.009
5. [5]
  (5) Wu,W. Z.; Guo,W. Y.; Xiao,W. D.; Luo, M. Chem. Eng. Sci.2011, 66, 4722. doi: 10.1016/j.ces.2011.06.036
6. [6]
  (6) Bjørgen, M.; Joensen, F.; Lillerud, K. P.; Olsbye, U.; Svelle, S.Catal. Today 2009, 142, 90. doi: 10.1016/j.cattod.2009.01.015
7. [7]
  (7) Bjørgen, M.; Svelle, S.; Joensen, F.; Nerlov, J.; Kolboe, S.;Bonino, F.; Palumbo, L.; Bordiga, S.;Olsbye, U. J. Catal. 2007,249, 195. doi: 10.1016/j.jcat.2007.04.006
8. [8]
  (8) Lee, K. Y.; Lee, H. K.; Ihm, S. K. Top. Catal. 2010, 53, 247.doi: 10.1007/s11244-009-9412-0
9. [9]
  (9) 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
10. [10]
  (10) 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
11. [11]
  (11) 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
12. [12]
  (12) Kim, J.; Choi, M.; Ryoo, R. J. Catal. 2010, 269, 219. doi: 10.1016/j.jcat.2009.11.009
13. [13]
  (13) Firoozi, M.; Baghalha, M.; Asadi, M. Catal. Commun. 2009, 10,1582. doi: 10.1016/j.catcom.2009.04.021
14. [14]
  (14) 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.]
15. [15]
  (15) 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
16. [16]
  (16) Choi, M.; Na, K.; Kim, J.; Sakamoto, Y.; Terasaki, O.; Ryoo, R.Nature 2009, 461, 246. doi: 10.1038/nature08288
17. [17]
  (17) Min, H. K.; Park, M. B.; Hong, S. B. J. Catal. 2010, 271, 186.doi: 10.1016/j.jcat.2010.01.012
18. [18]
  (18) Triantafillidis, C. S.; Vlessidis, A. G.; Nalbandian, L.;Evmiridis, N. P. Microporous Mesoporous Mat. 2001, 47, 369.doi: 10.1016/S1387-1811(01)00399-7
19. [19]
  (19) Han, S.; Shihabi, D. S.; Chang, C. D. J. Catal. 2000, 196, 375.doi: 10.1006/jcat.2000.3037
20. [20]
  (20) Kumar, S.; Sinha, A. K.; Hegde, S. G.; Sivasanker, S. J. Mol. Catal. A 2000, 154, 115. doi: 10.1016/S1381-1169(99)00360-X
21. [21]
  (21) 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.]
22. [22]
  (22) Wu,W.;Wu,W. G.; Li, L. F.; Yang,W.;Wu, G. Acta Petrolei Sinica (Petroleum Processing Section) 2010, 26, 189.[吴伟, 吴维果, 李凌飞, 杨巍, 武光. 石油学报(石油加工), 2010, 26, 189.]
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) van Grieken, R.; Sotelo, J. L.; Menéndez, J. M.; Melero, J. A.Microporous Mesoporous Mat. 2000, 39, 135. doi: 10.1016/S1387-1811(00)00190-6
25. [25]
  (25) 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
26. [26]
  (26) Svelle, S.; Joensen, F.; Nerlov, J.; Olsbye, U.; Lillerud, K. P.;Kolboe, S.; Bjørgen, M. J. Am. Chem. Soc. 2006, 128, 14770.doi: 10.1021/ja065810a
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Catalytic Conversion of Methanol to Propylene over (NH₄)₂SiF₆-Modified Nanosized HZSM-5 Zeolite