Citation: WANG Yun, LIANG Yan, HE Jun, ZHANG Wen-Xia, LUO Jian-Wei, LU Ji-Qing, LUO Meng-Fei. Catalytic Behaviors of Cr₂O₃ and CrO₃/Cr₂O₃ Catalysts for Gas Phase Fluorination of 2-Chloro-1,1,1-trifluoroethane:Active Species and Catalyst Deactivation[J]. Chinese Journal of Inorganic Chemistry, ;2017, 33(1): 123-133. doi: 10.11862/CJIC.2016.281 shu

Catalytic Behaviors of Cr₂O₃ and CrO₃/Cr₂O₃ Catalysts for Gas Phase Fluorination of 2-Chloro-1,1,1-trifluoroethane:Active Species and Catalyst Deactivation

WANG Yun ¹ ,
LIANG Yan ¹ ,
HE Jun ² ,
ZHANG Wen-Xia ¹ ,
LUO Jian-Wei ¹ ,
LU Ji-Qing ¹ ,
LUO Meng-Fei ^1,*,,

1.
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, China
2.
Taizhou Entry-Exit Inspection and Quarantine Bureau, Taizhou, Zhejiang 318000, China

Corresponding author: LUO Meng-Fei, mengfeiluo@zjnu.cn
Received Date: 23 June 2016
Revised Date: 28 October 2016

Figures(9)

Two Cr-based model catalysts (Cr₂O₃ and CrO₃/Cr₂O₃) were prepared respectively by precipitation and impregnation method and tested for gas phase fluorination of 2-chloro-1,1,1-trifluoroethane to synthesize 1,1,1,2-tetrafluoroethane. It was found that the Cr₂O₃ catalyst containing low valent Cr species (Cr³⁺) was stable during the reaction with a steady state conversion of 18.5%. On the contrary, the CrO₃/Cr₂O₃ catalyst containing both high valent Cr species (Cr⁶⁺) and low valent Cr species (Cr³⁺) had higher initial activity (30.6%) but it deactivated rapidly, with the same activity as the Cr₂O₃ catalyst at steady state. Moreover, quantitative analyses showed that the Cr⁶⁺ species in the CrO₃/Cr₂O₃ catalyst had an initial turnover frequency of 1.71×10^-4 mol_HCFC-133a·mol_Cr(Ⅵ)^-1·s^-1, which was much higher than that of the Cr³⁺ species (4.16×10^-5 mol_HCFC-133a·mol_Cr(Ⅲ)^-1·s^-1) in the Cr₂O₃ catalyst. In addition, the characterization results revealed that the Cr₂O₃ remained its structure while the high valent Cr species in the CrO₃/Cr₂O₃ reacted with HF to form catalytically active CrO_xF_y species. However, such CrO_xF_y species could either volatilize during the reaction or transformed to stable but inactive CrF₃, which accounted for the catalyst deactivation.
- Cr₂O₃,
- CrO₃/Cr₂O₃,
- fluorination,
- HCFC-133a,
- HFC-134a,
- catalyst deactivation
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Catalytic Behaviors of Cr2O3 and CrO3/Cr2O3 Catalysts for Gas Phase Fluorination of 2-Chloro-1,1,1-trifluoroethane:Active Species and Catalyst Deactivation

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通讯作者: 陈斌, bchen63@163.com

Catalytic Behaviors of Cr₂O₃ and CrO₃/Cr₂O₃ Catalysts for Gas Phase Fluorination of 2-Chloro-1,1,1-trifluoroethane:Active Species and Catalyst Deactivation