Citation: Yao Xuting, Huang Xin, Lin Yuxia, Liu Yueming. Deactivated TS-1 as Efficient Catalyst for Hydration of Cyclohexene to Cyclohexanol[J]. Acta Chimica Sinica, ;2020, 78(10): 1111-1119. doi: 10.6023/A20060246 shu

Deactivated TS-1 as Efficient Catalyst for Hydration of Cyclohexene to Cyclohexanol

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China

Corresponding author: Liu Yueming, ymliu@chem.ecnu.edu.cn
Received Date: 18 June 2020
Available Online: 3 September 2020
Fund Project: Project supported by the National key Research and Development Program of China (No. 2016YFB0701100)The National key Research and Development Program of China 2016YFB0701100

Figures(14)

Cyclohexanol is an important chemical intermediate material. At present, ZSM-5 is mainly used as a catalyst in the industry to produce cyclohexanol by one-step hydration of cyclohexene. Its core is the development of high-performance catalysts. TS-1 is a high efficient catalyst for industrial liquid-phase ammoniation of cyclohexanone, which shows a typical Brønsted acidity after deactivation. Based on this, we applied the deactivated TS-1 as catalyst for cyclohexene hydration reaction, and investigated systematically the effects of reaction time, reaction temperature, catalyst dosage and mass ratio of water to oil on the hydration reaction of cyclohexene. The results showed that the deactivated TS-1 could offer a high catalytic performance with 11.0% yield and 99.8% selectivity towards cyclohexanol under the optimized reaction conditions, which indicated that the deactivated TS-1 is a high-performance catalyst and possesses the characteristics of high activity, high selectivity and high stability. Combined with nitric acid treating modification, potassium ion exchange experiment and the characterization techniques such as UV-Vis (UV-visible spectroscopy), FT-IR (Fourier transform infrared spectrometer), ²⁹Si MAS NMR (²⁹Si magic angle solid nuclear magnetic resonance), and NH₃-TPD (temperature-programmed desorption of ammonia), it was found that the deactivated TS-1 possesses two kinds of Brønsted acid sites, whereas its real active center for the hydration reaction of cyclohexene is silanol group adjacent to titanium hydroxyl group (Si-OH(Ti)). The structure of this Brønsted acid site is completely different from the skeleton bridge Brønsted acid site (Si-(OH)-Al) of ZSM-5 zeolite, meanwhile shows relatively weak acid strength. The unique acid property of Si-OH(Ti) could promote the main reaction path of cyclohexanol formation and inhibit the side reaction path of cyclohexene isomerization in cyclohexene hydration reaction, which determined its characteristic of high cyclohexanol selectivity. The discovery and application of the special Brønsted acid site of the deactivated TS-1 waste catalyst can provide a new idea for resource utilization of solid waste resources of spent catalyst.
- deactivated TS-1,
- cyclohexanol,
- cyclohexene,
- hydration reaction,
- Brønsted acid site
1. [1]
  Guo, Z. W.; Jin, H. B.; Tong, Z. M. Chem. Prog. 2006, 25, 852 (in Chinese).
2. [2]
  Hiroshi, F.; Fujinao, M.; Masao, K. JP02040334, 1990 [Chem. Abstr. 1990, 112, 216297].
3. [3]
  Yang, X. D.; Wang, X. M.; Gao, S. B.; Wang, A. J. Acta Chim. Sinica 2017, 75, 479 (in Chinese).
4. [4]
  Fang, W. J.; Xie, W. J.; Xing, Y.; Guo, Y. S.; Lin, R. S. Acta Chim. Sinica 2009, 67, 6 (in Chinese).
5. [5]
  Fukuoka, Y.; Mitsui, O. JP60104031A, 1985 [Chem. Abstr. 1985, 103, 123067].
6. [6]
  Tojo, M.; Fukuoka, Y. JP61180735A, 1986 [Chem. Abstr. 1986, 106, 17969].
7. [7]
  Wang, H.; Fan, W. B.; Li, Y. C.; Dong, M.; Li, J. F.; Wang, G. F.; Qin, Z. F.; Wang, J. G. Acta Chim. Sinica 2016, 74, 529 (in Chinese).
8. [8]
  Qiao, M. H.; Zong, B. N.; Cheng, S. J.; Zeng, Y.; Pei, Y.; Fan, K. N. Acta Chim. Sinica 2019, 77, 1054 (in Chinese).
9. [9]
  Taramasso, M.; Perego, G.; Notari, B. US 4410501A, 1983[Chem. Abstr. 1983, 95, 206272].
10. [10]
  Nijhuis, T. A.; Huizinga, B. J.; Makkee, M.; Moulijin, J. A. Ind. Eng. Chem. Res. 1997, 151, 355.
11. [11]
  Sun, B. Pet. Ref. Chem. Ind. 2005, 36, 54 (in Chinese).
12. [12]
  Ishida, H. Catal. Surv. Jpn. 1997, 1, 241. doi: 10.1023/A:1019037316000
13. [13]
  Su, J.; Xiong, G.; Zhou, J. C.; Liu, W. H.; Zhou, D. H.; Wang, G. R.; Wang, X. S.; Guo, H. C. J. Catal. 2012, 288, 1. doi: 10.1016/j.jcat.2011.12.006
14. [14]
  Fang, X. Q.; Wang, Q.; Zheng, A. M.; Liu, Y. M.; Wang, Y. N.; Deng, X. J.; Wu, H. H.; Deng, F.; He, M. Y.; Wu, P. Catal. Sci. Techonol. 2012, 2, 2433. doi: 10.1039/c2cy20446k
15. [15]
  Wang, Y.; Liu, Y. M.; Li, X. H.; Wu, H. H.; He, M. Y.; Wu, P. J. Catal. 2009, 266, 258. doi: 10.1016/j.jcat.2009.06.016
16. [16]
  Vayssilov, G. N. Catal. Rev. Sci. Eng. 1997, 39, 209. doi: 10.1080/01614949709353777
17. [17]
  Blasco, T.; Camblor, M. A.; Corma, A. J. Am. Chem. Soc. 1993, 115, 11806. doi: 10.1021/ja00078a020
18. [18]
  Notari, B. Catal. Today 1993, 18, 163. doi: 10.1016/0920-5861(93)85029-Y
19. [19]
  Liu, Z. F.; Davis, R. J. J. Phys. Chem. 1994, 98, 1253. doi: 10.1021/j100055a035
20. [20]
  Liu, Y. Q.; Li, Y. X.; Wu, W. Pet. Ref. Chem. Ind. 2002, 5, 41 (in Chinese).
21. [21]
  Itoh, M.; Hattori, H.; Tanabe, K. J. Catal. 1974, 35, 225. doi: 10.1016/0021-9517(74)90201-2
22. [22]
  Lin, L. F.; Qiu, C. F.; Zhuo, Z. X.; Zhang, D. W.; Zhao, S. F.; Wu, H. H.; Liu, Y. M.; He, M. Y. J. Catal. 2014, 309, 136. doi: 10.1016/j.jcat.2013.09.011
23. [23]
  Lin, L. F.; Zhao, S. F.; Zhang, D. W.; Fan, H.; Liu, Y. M.; He, M. Y. ACS Catal. 2015, 5, 4048. doi: 10.1021/cs501967r
24. [24]
  Corma, A.; Orchillés, A. V. Micro. Meso. Mater. 2000, 35, 21.
25. [25]
  Emeis, C. A. J. Catal. 1993, 141, 347. doi: 10.1006/jcat.1993.1145
26. [26]
  Barzetti, T.; Selli, E.; Moscotti, D.; Forni, L. J. Chem. Soc., Faraday Trans. 1996, 92, 1401. doi: 10.1039/ft9969201401
27. [27]
  Post, J. G.; Van Hooff, J. H. C. Zeolites 1984, 4, 9. doi: 10.1016/0144-2449(84)90065-4
28. [28]
  Farneth, W. E.; Gorte, R. J. Chem. Rev. 1995, 95, 615. doi: 10.1021/cr00035a007
29. [29]
  Al-Dughaither, A. S.; de Lasa, H. Ind. Eng. Chem. Res. 2014, 53, 15303. doi: 10.1021/ie4039532
30. [30]
  Wu, P.; Tatsumi, T.; Komatsu, T.; Yashima, T. J. Phys. Chem. B 2001, 105, 2897. doi: 10.1021/jp002816s
31. [31]
  Liu, H.; Lu, G. Z.; Guo, Y. L.; Guo, Y.; Wang, J. S. Catal. Today 2004, 93, 353.
32. [32]
  Qi, Y. Y.; Ye, C. B.; Zhuang, Z.; Xin, F. Micro. Meso. Mater. 2011, 142, 661. doi: 10.1016/j.micromeso.2011.01.012
33. [33]
  Wang, Y.; Liu, Y. M.; Li, X. H.; Wu, H. H.; He, M. Y.; Wu, P. J. Catal. 2009, 266, 258. doi: 10.1016/j.jcat.2009.06.016
34. [34]
  Zhuo, Z. X.; Lin, L. F.; Deng, X. J.; Wang, Y. N.; Liu, Y. M. Chin. J. Catal. 2013, 34, 604.
35. [35]
  Tozzola, G.; Mantegazza, M. A.; Ranghino, G.; Petrini, G.; Bordiga, S.; Ricchiardi, G.; Lamberti, C.; Zulian, R.; Zecchina, A. J. Catal. 1998, 179, 64. doi: 10.1006/jcat.1998.2205
36. [36]
  Ricchiardi, G.; Damin, A.; Bordiga, S.; Lamberti, C.; Spano, G.; Rivetti, F.; Zecchina, A. J. Am. Chem. Soc. 2001, 123, 11409. doi: 10.1021/ja010607v
37. [37]
  Camblor, M. A.; Corma, A.; Pérez-Pariente, J. J. Chem. Soc., Chem. Commun. 1993, 557.
38. [38]
  Wang, D. Z.; Shu, X. T.; He, M. Y. Chin. J. Catal. 2002, 23, 503 (in Chinese).
39. [39]
  Zhao, G. L.; Teng, J. W.; Xie, Z. K.; Jin, W. Q.; Yang, W. M.; Chen, Q. L.; Tang, Y. J. Catal. 2007, 248, 29. doi: 10.1016/j.jcat.2007.02.027
1. [1]
  Tao Wen , Tao Zhang , Changguo Sun , Jinyu Liu . Preparation of Dess-Martin Reagent and Its Application in Oxidizing Cyclohexanol. University Chemistry, 2024, 39(5): 20-26. doi: 10.3866/PKU.DXHX202309055
2. [2]
  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
3. [3]
  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
4. [4]
  Conghao Shi , Ranran Wang , Juli Jiang , Leyong Wang . The Illustration on Stereoisomers of Macrocycles Containing Multiple Chiral Centers via Tröger Base-based Macrocycles. University Chemistry, 2024, 39(7): 394-397. doi: 10.3866/PKU.DXHX202311034
5. [5]
  Runze Liu , Yankai Bian , Weili Dai . Qualitative and quantitative analysis of Brønsted and Lewis acid sites in zeolites: A combined probe-assisted 1H MAS NMR and NH3-TPD investigation. Chinese Journal of Structural Chemistry, 2024, 43(4): 100250-100250. doi: 10.1016/j.cjsc.2024.100250
6. [6]
  Zhanhui Yang , Jiaxi Xu . (m+n+…) or [m+n+…]cycloaddition?. University Chemistry, 2025, 40(3): 387-389. doi: 10.12461/PKU.DXHX202406032
7. [7]
  Keweiyang Zhang , Zihan Fan , Liyuan Xiao , Haitao Long , Jing Jing . Unveiling Crystal Field Theory: Preparation, Characterization, and Performance Assessment of Nickel Macrocyclic Complexes. University Chemistry, 2024, 39(5): 163-171. doi: 10.3866/PKU.DXHX202310084
8. [8]
  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
9. [9]
  Hongling Yuan , Jialin Xie , Jiawei Wang , Jixiang Zhao , Jiayan Liu , Qing Feng , Wei Qi , Min Liu . Cyclic Olefin Copolymer (COC): The Agile Vanguard in the Realm of Materials. University Chemistry, 2024, 39(7): 294-298. doi: 10.12461/PKU.DXHX202311041
10. [10]
  Hong Zheng , Xin Peng , Chunwang Yi . The Tale of Caprolactam Cyclic Oligomers: The Ever-changing Life of “Princess Cyclo”. University Chemistry, 2024, 39(9): 40-47. doi: 10.12461/PKU.DXHX202403058
11. [11]
  Jinghua Wang , Yanxin Yu , Yanbiao Ren , Yesheng Wang . Integration of Science and Education: Investigation of Tributyl Citrate Synthesis under the Promotion of Hydrate Molten Salts for Research and Innovation Training. University Chemistry, 2024, 39(11): 232-240. doi: 10.3866/PKU.DXHX202402057
12. [12]
  Zhiwen HUANG , Qi LIU , Jianping LANG . W/Cu/S cluster-based supramolecular macrocycles and their third-order nonlinear optical responses. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 79-87. doi: 10.11862/CJIC.20240184
13. [13]
  Fugui XI , Du LI , Zhourui YAN , Hui WANG , Junyu XIANG , Zhiyun DONG . Functionalized zirconium metal-organic frameworks for the removal of tetracycline from water. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 683-694. doi: 10.11862/CJIC.20240291
14. [14]
  Jiajun Lu , Zhehui Liao , Tongxiang Cao , Shifa Zhu . Synergistic Brønsted/Lewis acid catalyzed atroposelective synthesis of aryl-β-naphthol. Chinese Chemical Letters, 2025, 36(1): 109842-. doi: 10.1016/j.cclet.2024.109842
15. [15]
  Ruolin CHENG , Haoran WANG , Jing REN , Yingying MA , Huagen LIANG . Efficient photocatalytic CO₂ cycloaddition over W₁₈O₄₉/NH₂-UiO-66 composite catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 523-532. doi: 10.11862/CJIC.20230349
16. [16]
  Jianjun LI , Mingjie REN , Lili ZHANG , Lingling ZENG , Huiling WANG , Xiangwu MENG . UV-assisted degradation of tetracycline hydrochloride by MnFe₂O₄@activated carbon activated persulfate. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1869-1880. doi: 10.11862/CJIC.20240187
17. [17]
  Junjie Zhang , Yue Wang , Qiuhan Wu , Ruquan Shen , Han Liu , Xinhua Duan . Preparation and Selective Separation of Lightweight Magnetic Molecularly Imprinted Polymers for Trace Tetracycline Detection in Milk. University Chemistry, 2024, 39(5): 251-257. doi: 10.3866/PKU.DXHX202311084
18. [18]
  Shengyan Yang , Xiangzhen Meng , Xin Wang , Yang Zhang . Construction and Exploration of an Online-Offline Blended “Eight-Link” Teaching Method for Physical Chemistry Experiments Based on OBE Concept. University Chemistry, 2024, 39(11): 28-37. doi: 10.3866/PKU.DXHX202402019
19. [19]
  Hong RAO , Yang HU , Yicong MA , Chunxin LÜ , Wei ZHONG , Lihua DU . Synthesis and in vitro anticancer activity of phenanthroline-functionalized nitrogen heterocyclic carbene homo- and heterobimetallic silver/gold complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(12): 2429-2437. doi: 10.11862/CJIC.20240275
20. [20]
  Jiahui YU , Jixian DONG , Yutong ZHAO , Fuping ZHAO , Bo GE , Xipeng PU , Dafeng ZHANG . The morphology control and full-spectrum photodegradation tetracycline performance of microwave-hydrothermal synthesized BiVO₄:Yb³⁺,Er³⁺ photocatalyst. Journal of Fuel Chemistry and Technology, 2025, 53(3): 348-359. doi: 10.1016/S1872-5813(24)60514-1

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(1510)
HTML views(329)

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