Acta Chimica Sinica ›› 2020, Vol. 78 ›› Issue (10): 1111-1119.DOI: 10.6023/A20060246 Previous Articles     Next Articles



姚旭婷, 黄鑫, 林玉霞, 刘月明   

  1. 华东师范大学化学与分子工程学院 上海市绿色化学与化工过程绿色化重点实验室 上海 200062
  • 投稿日期:2020-06-18 发布日期:2020-09-04
  • 通讯作者: 刘月明
  • 基金资助:

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

Yao Xuting, Huang Xin, Lin Yuxia, Liu Yueming   

  1. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China
  • Received:2020-06-18 Published:2020-09-04
  • Supported by:
    Project supported by the National key Research and Development Program of China (No. 2016YFB0701100).

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.

Key words: deactivated TS-1, cyclohexanol, cyclohexene, hydration reaction, Brønsted acid site