高选择性和稳定性的CsPW/Nb2O5催化剂用于甘油脱水制备丙烯醛

doi:10.1016/S1872-2067(12)60666-4

催化学报 ›› 2013, Vol. 34 ›› Issue (12): 2174-2182.DOI: 10.1016/S1872-2067(12)60666-4

高选择性和稳定性的CsPW/Nb₂O₅催化剂用于甘油脱水制备丙烯醛

刘蓉, 王铁峰, 刘畅, 金涌

清华大学化学工程系, 绿色反应工程与工艺北京市重点实验室, 北京100084

收稿日期:2013-06-22 修回日期:2013-07-18 出版日期:2013-11-25 发布日期:2013-11-25
通讯作者: 王铁峰
基金资助:
教育部新世纪优秀人才支持计划(NCET-12-0297).

Highly selective and stable CsPW/Nb₂O₅ catalysts for dehydration of glycerol to acrolein

Rong Liu, Tiefeng Wang, Chang Liu, Yong Jin

Beijing Key Laboratory of Green Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Received:2013-06-22 Revised:2013-07-18 Online:2013-11-25 Published:2013-11-25
Contact: Tiefeng Wang
Supported by:
This work was supported by the Program for New Century Excellent Talents in University (NCET-12-0297).

摘要/Abstract

摘要：

以磷钨酸铯盐Cs_2.5H_0.5PW₁₂O₄₀(CsPW)为活性组分, 负载到Nb₂O₅载体上, 并用于甘油脱水制备丙烯醛的反应中. 通过调节焙烧温度(400–700 ℃)以及活性组分负载量(5-60 wt%), 对催化剂酸性进行调节. CsPW负载量为20 wt%, 500 ℃焙烧的CsPW/Nb₂O₅催化剂性能最佳, 甘油转化率为96%, 丙烯醛选择性为80%, 反应10 h内没有失活现象, 并且该催化剂具有良好的热稳定性, 可通过烧炭进行再生.

关键词: 甘油脱水, 丙烯醛, 五氧化二铌, 磷钨酸铯盐

Abstract:

Acrolein production by gas-phase dehydration of glycerol at 300 ℃, catalyzed by a Cs⁺-substituted Keggin-type phosphotungstate, Cs_2.5H_0.5PW₁₂O₄₀ (CsPW), supported on Nb₂O₅ was investigated. The catalysts were characterized using N₂ adsorption-desorption, X-ray diffraction, Fourier-transform infrared and Raman spectroscopies, and NH₃ temperature-programmed desorption. It was demonstrated that Lewis acid sites were responsible for byproduct formation, and that Brönsted acid sites of medium strength were the active sites for acrolein production by glycerol dehydration. The acidity of the supported CsPW was affected by the calcination temperature and CsPW loading. The CsPW was well dispersed on Nb₂O₅ at loadings ≤20 wt%, and the strong acid sites of bulk CsPW were converted to selective medium acid sites. The CsPW catalyst with 20% of CsPW loading calcined at 500 ℃ gave 96% of glycerol conversion and 80% of acrolein selectivity, and there was no significant deactivation in 10 h. The catalyst with a 20% decrease in activity was regenerated by simple coke burning with air at 500 ℃.

Key words: Glycerol dehydration, Acrolein, Niobium(Ⅴ) oxide, Cesium heteropoly salt, Cs_2.5H_0.5PW₁₂O₄₀

刘蓉, 王铁峰, 刘畅, 金涌. 高选择性和稳定性的CsPW/Nb₂O₅催化剂用于甘油脱水制备丙烯醛[J]. 催化学报, 2013, 34(12): 2174-2182.

Rong Liu, Tiefeng Wang, Chang Liu, Yong Jin. Highly selective and stable CsPW/Nb₂O₅ catalysts for dehydration of glycerol to acrolein[J]. Chinese Journal of Catalysis, 2013, 34(12): 2174-2182.

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高选择性和稳定性的CsPW/Nb₂O₅催化剂用于甘油脱水制备丙烯醛

Highly selective and stable CsPW/Nb₂O₅ catalysts for dehydration of glycerol to acrolein

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