Citation: PAN Wen-Ya, HUANG Liang, QIN Feng, ZHUANG Yan, LI Xue-Mei, MA Jian-Xue, SHEN Wei, XU Hua-Long. Regulation of Pore Structure and Acidity of a ZSM-5 Catalyst for Dehydration of Glycerol to Acrolein[J]. Acta Physico-Chimica Sinica, ;2015, 31(5): 965-972. doi: 10.3866/PKU.WHXB201503024 shu

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

PAN Wen-Ya ¹ ,
HUANG Liang ¹ ,
QIN Feng ¹ ,
ZHUANG Yan ² ,
LI Xue-Mei ² ,
MA Jian-Xue ² ,
SHEN Wei ^1, ,
XU Hua-Long ^1,

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 Date: 9 December 2014
Available Online: 2 March 2015
Fund Project: 上海市科学技术委员会资助国际合作项目(14120700700) (14120700700)重点实验室基金(11JC1400400)资助 (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.
- Micro-mesoporous ZSM-5,
- Surface acidity,
- Alkali treatment,
- Dehydration of glycerol,
- Acrolein
1. [1]
  
  (1) Lourenço, J. P.; Macedo, M. I.; Fernandes, A. Catal. Commun. 2012, 19, 105. doi: 10.1016/j.catcom.2011.12.029
2. [2]
  (2) Benjamin, K.; Bastien, P.; Franck, D. ACS Catal. 2013, 3, 1819. doi: 10.1021/cs400354p
3. [3]
  (3) Behr, A.; Eilting, J.; Irawadi, K.; Leschinski, J.; Lindner, F. Green Chem. 2008, 10, 13. doi: 10.1039/B710561D
4. [4]
  (4) Pagliaro, M.; Ciriminna, R.; Kimura, H.; Rossi, M.; Pina, C. D. Angew. Chem. Int. Edit. 2007, 46, 4434.
5. [5]
  (5) Jo, B. Y.; Kim, E. J.; Moon, S. H. Appl. Catal. A: Gen. 2007, 332, 257. doi: 10.1016/j.apcata.2007.08.025
6. [6]
  (6) Luiz, G. P.; Rosiane, N. D.; Teresita, G. J. Catal. 2013, 300, 102. doi: 10.1016/j.jcat.2013.01.003
7. [7]
  (7) Kim, Y. T.; Jung, K. D.; Park, E. D. Microporous Mesoporous Mat. 2010, 131, 28. doi: 10.1016/j.micromeso.2009.11.037
8. [8]
  (8) Jia, C. J.; Liu, Y.; Schmidt, W.; Lu, A. H.; Schüth, F. J. Catal. 2010, 269, 71. doi: 10.1016/j.jcat.2009.10.017
9. [9]
  (9) Kim, Y. T.; Jung, K. D.; Park, E. D. Appl. Catal. A: Gen. 2011, 393, 275. doi: 10.1016/j.apcata.2010.12.007
10. [10]
  (10) Gu, Y. L.; Cui, N. Y.; Yu, Q. J. Appl. Catal. A: Gen. 2012, 429, 9.
11. [11]
  (11) Tsukuda, E.; Sato, S.; Takahashi, R.; Sodesawa, T. Catal. Commun. 2007, 8, 1349. doi: 10.1016/j.catcom.2006.12.006
12. [12]
  (12) Katryniok, B.; Paul, S.; Capron, M.; Lancelot, C.; Belliere- Baca, V.; Rey, P.; Dumeignil, F. Green Chem. 2010, 12, 1922. doi: 10.1039/c0gc00254b
13. [13]
  (13) Ning, L. L.; Ding, Y. J.; Chen, W. M.; ng, L. F.; Lin, R. H.; Lü, Y.; Xin, Q. Chin. J. Catal. 2008, 29, 212. [宁丽丽, 丁云杰, 陈维苗, 龚磊峰, 林荣和, 吕元, 辛勤. 催化学报, 2008, 29, 212.] doi: 10.1016/S1872-2067(08)60026-1
14. [14]
  (14) Lauriol-Garbey, P.; Loridant, S. Catal. Commun. 2011, 16, 170. doi: 10.1016/j.catcom.2011.09.026
15. [15]
  (15) Stoši?, D.; Bennici, S. Catal. Commun. 2012, 17, 23. doi: 10.1016/j.catcom.2011.10.004
16. [16]
  (16) Liu, Q. B.; Zhang, Z.; Du, Y.; Li, J. Catal. Lett. 2009, 127, 419. doi: 10.1007/s10562-008-9723-y
17. [17]
  (17) Suprun, W.; Lutecki, M.; Haber, T.; Papp, H. J. Mol. Catal. A: Chem. 2009, 309, 71. doi: 10.1016/j.molcata.2009.04.017
18. [18]
  (18) Okuno, M.; Matsunami, E.; Takahashi, T.; Kasuga, H. Catalysts for Gas-Phase Spin-Dehydration in Manufacture of Glycerin, Acrolein and Its Derivative, Contains Preset Amount of Binder and Crystalline Metallosilicate Containing Preset Ratio of Silicon and Specific Atom. Japanese Patent, JP2007301505-A, 22 Nov 2007.
19. [19]
  (19) Dubois, J. L.; Duquenne, C.; Hoelderich, W. Manufacturing Acrolein, Useful as Intermediate for Synthesis of Methionine and Acrylic Acid, by Dehydration of Glycerol in the Presence of Molecular Oxygen at Outside the Flammability Range. WO2006087083-A2, 24 Aug 2006.
20. [20]
  (20) Kim, Y. T.; Jung, K. D.; Park, E. D. Appl. Catal. A: Gen. 2011, 393, 5.
21. [21]
  (21) Chal, R.; Gerardin, C.; Bulut, M.; Donk, S. ChemCatChem 2011, 3, 67. doi: 10.1002/cctc.201000158
22. [22]
  (22) Massa, M.; Andersson, A.; Finocchio, E.; Busca, G.; Lenrick, F.; Wallenberg, L. R. J. Catal. 2013, 297, 93. doi: 10.1016/j.jcat.2012.09.021
23. [23]
  (23) Zhao, H.; Zhou, C. H.; Wu, L. M.; Lou, J. Y.; Li, N.; Yang, H. M.; Tong, D. S.; Yu, W. H. Applied Clay Science 2013, 74, 154. doi: 10.1016/j.clay.2012.09.011
24. [24]
  (24) Ogura, M.; Shinomiya, S. Y.; Tateno, J.; Nara, Y.; Kikuchi, E.; Matsukata, M. Chem. Lett. 2000, 29, 882.
25. [25]
  (25) Ogura, M.; Shinomiya, S. Y.; Tateno, J.; Nara, Y.; Nomura, M.; Kikuchi, E.; Matsukata, M. Appl. Catal. A: Gen. 2001, 219, 33. doi: 10.1016/S0926-860X(01)00645-7
26. [26]
  (26) Groen, J. C.; Peffer, L. A. A.; Moulijn, J. A.; Pérez-Ramírez, J. Chem. -Eur. J. 2005, 11, 4983.
27. [27]
  (27) Groen, J. C.; Zhu, W. D.; Brouwer, S.; Huynink, S. J.; Kapteijn, F.; Moulijn, J. A.; Pérez-Ramírez, J. J. Am. Chem. Soc. 2007, 129, 355. doi: 10.1021/ja065737o
28. [28]
  (28) Verboekend, D.; Pérez-Ramírez, J. Chem. -Eur. J. 2011, 17, 1137. doi: 10.1002/chem.v17.4
29. [29]
  (29) Ravishankar, R.; Kirschhock, C.; Schoeman, B. J.; Vanoppen, P.; Grobet, P. J.; Storck, S. J. Phys. Chem. B 1998, 102, 2633. doi: 10.1021/jp973147u
30. [30]
  (30) Zeolites Characterization and Catalysis: A Tutorial; Chester, A. W., Derouane, E. G. Eds. Springer-Verlag New York Inc.: New York, 2009; pp 358-365.
31. [31]
  (31) Kentgens, A. P.; Scholle, M. K.; Veeman, W. S. J. Chem. Phys. 1987, 87, 4357.
32. [32]
  (32) 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
33. [33]
  (33) Lietz, G.; Schnabel, K. H.; Peuker, C.; Gross, T. J. Catal. 1994, 148, 562. doi: 10.1006/jcat.1994.1242
34. [34]
  (34) Lutz, W.; Grossmann, A.; Bülow, M.; Gross, T. Cryst. Res. Tech. 1990, 25, 135.
35. [35]
  (35) Chai, S. H.; Wang, H. P.; Liang, Y.; Xu, B. Q. Green Chem. 2007, 9, 1130.
36. [36]
  (36) Corma, A.; Huber, G.W.; Sauvanaud, L.; O′Connor, P. J. Catal. 2008, 257, 163. doi: 10.1016/j.jcat.2008.04.016
37. [37]
  (37) Arita, Y.; Kasuga, H.; Kirishiki, K. Regeneration of Catalyst Used for Glycerin-Spin Dehydration for Manufacturing Glycerin Derivative, Involves Contacting Oxidizing Agent with Carbon-like Substance in Surface of Catalyst, and Removing Carbon-Like Substance. Japanese Patent, JP2008110298-A, 15 May 2008.
38. [38]
  (38) Possato, L. G.; Diniz, R. N.; Garetto, T.; Pulcinelli, S. H.; Santilli, C. V.; Martins, L. J. Catal. 2013, 300, 102. doi: 10.1016/j.jcat.2013.01.003
39. [39]
  (38) Possato, L. G.; Diniz, R. N.; Garetto, T.; Pulcinelli, S. H.; Santilli, C. V.; Martins, L. J. Catal. 2013, 300, 102. doi: 10.1016/j.jcat.2013.01.003
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]
  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
3. [3]
  Yanyang Li , Zongpei Zhang , Kai Li , Shuangquan Zang . Ideological and Political Design for the Comprehensive Experiment of the Synthesis and Aggregation-Induced Emission (AIE) Performance Study of Salicylaldehyde Schiff-Base. University Chemistry, 2024, 39(2): 105-109. doi: 10.3866/PKU.DXHX202307020
4. [4]
  Chunai Dai , Yongsheng Han , Luting Yan , Zhen Li , Yingze Cao . Preparation of Superhydrophobic Surfaces and Their Application in Oily Wastewater Treatment: Design of a Comprehensive Physical Chemistry Innovation Experiment. University Chemistry, 2024, 39(2): 34-40. doi: 10.3866/PKU.DXHX202307081
5. [5]
  Xinting XIONG , Zhiqiang XIONG , Panlei XIAO , Xuliang NIE , Xiuying SONG , Xiuguang YI . Synthesis, crystal structures, Hirshfeld surface analysis, and antifungal activity of two complexes Na(Ⅰ)/Cd(Ⅱ) assembled by 5-bromo-2-hydroxybenzoic acid ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1661-1670. doi: 10.11862/CJIC.20240145
6. [6]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
7. [7]
  Yuanpei ZHANG , Jiahong WANG , Jinming HUANG , Zhi HU . Preparation of magnetic mesoporous carbon loaded nano zero-valent iron for removal of Cr(Ⅲ) organic complexes from high-salt wastewater. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1731-1742. doi: 10.11862/CJIC.20240077
8. [8]
  Chuanming GUO , Kaiyang ZHANG , Yun WU , Rui YAO , Qiang ZHAO , Jinping LI , Guang LIU . Performance of MnO₂-0.39IrO_x composite oxides for water oxidation reaction in acidic media. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1135-1142. doi: 10.11862/CJIC.20230459
9. [9]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, 2024, 39(4): 280-285. doi: 10.3866/PKU.DXHX202309001
10. [10]
  Jie Li , Huida Qian , Deyang Pan , Wenjing Wang , Daliang Zhu , Zhongxue Fang . Efficient Synthesis of Anethaldehyde Induced by Visible Light. University Chemistry, 2024, 39(4): 343-350. doi: 10.3866/PKU.DXHX202310076
11. [11]
  Chi Li , Jichao Wan , Qiyu Long , Hui Lv , Ying Xiong . N-Heterocyclic Carbene (NHC)-Catalyzed Amidation of Aldehydes with Nitroso Compounds. University Chemistry, 2024, 39(5): 388-395. doi: 10.3866/PKU.DXHX202312016
12. [12]
  Honglian Liang , Xiaozhe Kuang , Fuping Wang , Yu Chen . Exploration and Practice of Integrating Ideological and Political Education into Physical Chemistry: a Case on Surface Tension and Gibbs Free Energy. University Chemistry, 2024, 39(10): 433-440. doi: 10.12461/PKU.DXHX202405073
13. [13]
  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
14. [14]
  Zizheng LU , Wanyi SU , Qin SHI , Honghui PAN , Chuanqi ZHAO , Chengfeng HUANG , Jinguo PENG . Surface state behavior of W doped BiVO₄ photoanode for ciprofloxacin degradation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 591-600. doi: 10.11862/CJIC.20230225
15. [15]
  Xinlong WANG , Zhenguo CHENG , Guo WANG , Xiaokuen ZHANG , Yong XIANG , Xinquan WANG . Enhancement of the fragile interface of high voltage LiCoO₂ by surface gradient permeation of trace amounts of Mg/F. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 571-580. doi: 10.11862/CJIC.20230259
16. [16]
  Weihan Zhang , Menglu Wang , Ankang Jia , Wei Deng , Shuxing Bai . 表面硫物种对钯-硫纳米片加氢性能的影响. Acta Physico-Chimica Sinica, 2024, 40(11): 2309043-. doi: 10.3866/PKU.WHXB202309043
17. [17]
  Zhuomin Zhang , Hanbing Huang , Liangqiu Lin , Jingsong Liu , Gongke Li . Course Construction of Instrumental Analysis Experiment: Surface-Enhanced Raman Spectroscopy for Rapid Detection of Edible Pigments. University Chemistry, 2024, 39(2): 133-139. doi: 10.3866/PKU.DXHX202308034
18. [18]
  Yukai Jiang , Yihan Wang , Yunkai Zhang , Yunping Wei , Ying Ma , Na Du . Characterization and Phase Diagram of Surfactant Lyotropic Liquid Crystal. University Chemistry, 2024, 39(4): 114-118. doi: 10.3866/PKU.DXHX202309033
19. [19]
  Lan Ma , Cailu He , Ziqi Liu , Yaohan Yang , Qingxia Ming , Xue Luo , Tianfeng He , Liyun Zhang . Magical Surface Chemistry: Fabrication and Application of Oil-Water Separation Membranes. University Chemistry, 2024, 39(5): 218-227. doi: 10.3866/PKU.DXHX202311046
20. [20]
  Ruilin Han , Xiaoqi Yan . Comparison of Multiple Function Methods for Fitting Surface Tension and Concentration Curves. University Chemistry, 2024, 39(7): 381-385. doi: 10.3866/PKU.DXHX202311023

Get Citation

PDF

XML

Metrics

PDF Downloads(316)
Abstract views(586)
HTML views(20)

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