Cr2O3气相催化1,1,2-三氯乙烷脱HCl性能

doi:10.11944/j.issn.1000-0518.2019.05.180245

摘要/Abstract

摘要：

采用沉淀法制备了不同焙烧温度的Cr₂O₃催化剂,用于1,1,2-三氯乙烷(TCE)气相脱氯化氢制备二氯乙烯的反应。采用X射线衍射(XRD)、氢气程序升温还原(H₂-TPR)、氨气程序升温脱附(NH₃-TPD)、X射线光电子能谱(XPS)表征手段,研究了Cr₂O₃催化剂气相催化裂解TCE脱氯化氢反应及其反应机理。结果表明,Cr₂O₃催化剂上TCE气相脱氯化氢反应的转化率随着催化剂焙烧温度的升高逐渐降低,然而顺-1,2-二氯乙烯(cis-DCE)的选择性先增大后减小。 400 ℃焙烧的Cr₂O₃催化剂催化性能最好,TCE转化率为70.8%,顺-1,2-二氯乙烯的选择性为90.0%。然而,催化剂的单位面积反应速率随着焙烧温度升高先提高后下降,400 ℃焙烧催化剂的单位面积反应速率为0.801×10^-2 μmol/(s·m²)。催化剂的单位面积反应速率和顺-1,2-二氯乙烯(cis-DCE)的选择性与催化剂表面Cr₂O₃物种具有很好的对应关系,表明催化剂表面Cr₂O₃物种有利于脱氯化氢反应。以酸中心为活性中心计算得到的转换频率(TOF)变化趋势与单位面积反应速率相一致,400 ℃焙烧的催化剂的TOF为2.82×10^-5 s^-1,表明Cr₂O₃催化剂Cr物种合适的平均价态(~3.20)有利于脱氯化氢反应。

关键词: Cr₂O₃催化剂, 1,1,2-三氯乙烷, 脱氯化氢, 顺-1,2-二氯乙烯, 表面Cr₂O₃物种

Abstract:

A series of Cr₂O₃ catalysts was prepared by a precipitation method and tested for the gas phase dehydrochlorination of 1,1,2-trichloroethane(TCE) to synthesize cis-1,2-dichloroethylene(cis-DCE). X-ray diffraction(XRD), hydrogen temperature-programmed reduction(H₂-TPR), ammonia temperature-programmed desorption(NH₃-TPD) and X-ray photoelectron spectroscopy(XPS) were used to study the dehydrochlorination of TCE on Cr₂O₃ catalyst and its reaction mechanism. It is found that the conversion ratio of TCE on the catalysts decreases with the increase of the calcination temperature, while the selectivity to cis-DCE first increases and then decreases. The best performance is obtained on the catalyst calcined at 400 ℃, with a TCE conversion ratio of 70.8% and a cis-DCE selectivity of 90.0%. In addition, the areal specific reaction rate also first increases and then decreases with the increase of the calcination temperature, with the highest value being obtained on the catalysts calcined at 400 ℃(0.801×10^-2 μmol/(s·m²). The catalytic behaviors of the catalysts are well related to their surface Cr₂O₃ species. Turnover frequencies(TOFs) calculated based on the surface acidity and the highest value being obtained on the catalysts calcined at 400 ℃(2.82×10^-5 s^-1) show that the oxidation states of the surface Cr species are important for the reaction and the Cr species with an average valence of 3.2 are appropriate for the reaction.

Key words: Cr₂O₃ catalysts, 1,1,2-trichloroethane, dehydrochlorination, cis-1,2-dichloroethylene, surface Cr₂O₃ species

董朝霞,宋通洋,鲁继青,谢冠群,罗孟飞. Cr₂O₃气相催化1,1,2-三氯乙烷脱HCl性能[J]. 应用化学, 2019, 36(5): 515-523.

DONG Zhaoxia,SONG Tongyang,LU Jiqing,XIE Guanqun,LUO Mengfei. Gas Phase Dehydrochlorination of 1,1,2-Trichloroethane over Cr₂O₃ Catalysts[J]. Chinese Journal of Applied Chemistry, 2019, 36(5): 515-523.

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Cr₂O₃气相催化1,1,2-三氯乙烷脱HCl性能

Gas Phase Dehydrochlorination of 1,1,2-Trichloroethane over Cr₂O₃ Catalysts

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