Hydrodechlorination of trifluoro-trichloroethane to chlorotrifluoroethylene: Revealing the deactivation mechanism and regeneration strategy of Pd-Cu/AC catalyst

doi:10.1016/j.cjche.2024.02.006

中国化学工程学报 ›› 2024, Vol. 70 ›› Issue (6): 261-268.DOI: 10.1016/j.cjche.2024.02.006

Hydrodechlorination of trifluoro-trichloroethane to chlorotrifluoroethylene: Revealing the deactivation mechanism and regeneration strategy of Pd-Cu/AC catalyst

Song Tian², Yicheng Chen¹, Xiaoyu Wen¹, Bingcheng Li¹, Jian Lu², Zile Li¹, Feng Feng¹, Qingtao Wang¹, Qunfeng Zhang¹, Xiaonian Li¹

1. State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Institute of Industrial Catalysis of Zhejiang University of Technology, Hangzhou 310014, China;
2. State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi'an Modern Chemistry Research Institute, Xi'an 710065, China

收稿日期:2023-09-28 修回日期:2024-02-14 出版日期:2024-06-28 发布日期:2024-08-05
通讯作者: Qingtao Wang,E-mail:qtwang@zjut.edu.cn;Qunfeng Zhang,E-mail:zhangqf@zjut.edu.cn;Xiaonian Li,E-mail:xnli@zjut.edu.cn
基金资助:
We are grateful to be financially supported by the National Natural Science Foundation of China (22008212, 22078292, 21902124), Natural Science Basic Research Planning Shaanxi Province of China (2017ZDJC-29), Key Research and Development Project of Shaanxi Province (2018ZDXM-GY-173), China Postdoctoral Science Foundation (2019 M663848) and Open cooperative innovation fund of Xi'an Institute of modern chemistry (SYJJ48).

Hydrodechlorination of trifluoro-trichloroethane to chlorotrifluoroethylene: Revealing the deactivation mechanism and regeneration strategy of Pd-Cu/AC catalyst

Song Tian², Yicheng Chen¹, Xiaoyu Wen¹, Bingcheng Li¹, Jian Lu², Zile Li¹, Feng Feng¹, Qingtao Wang¹, Qunfeng Zhang¹, Xiaonian Li¹

1. State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Institute of Industrial Catalysis of Zhejiang University of Technology, Hangzhou 310014, China;
2. State Key Laboratory of Fluorine & Nitrogen Chemicals, Xi'an Modern Chemistry Research Institute, Xi'an 710065, China

Received:2023-09-28 Revised:2024-02-14 Online:2024-06-28 Published:2024-08-05
Contact: Qingtao Wang,E-mail:qtwang@zjut.edu.cn;Qunfeng Zhang,E-mail:zhangqf@zjut.edu.cn;Xiaonian Li,E-mail:xnli@zjut.edu.cn
Supported by:
We are grateful to be financially supported by the National Natural Science Foundation of China (22008212, 22078292, 21902124), Natural Science Basic Research Planning Shaanxi Province of China (2017ZDJC-29), Key Research and Development Project of Shaanxi Province (2018ZDXM-GY-173), China Postdoctoral Science Foundation (2019 M663848) and Open cooperative innovation fund of Xi'an Institute of modern chemistry (SYJJ48).

摘要/Abstract

摘要： Chlorotrifluoroethylene (CTFE) is a vital fluorinated olefinic monomer produced through the catalytic hydrodechlorination of trichlorotrifluoroethane (CFC-113), an eco-friendly process. However, hydrodechlorination catalysts for olefin production often suffer from poor stability. The Pd/AC catalyst and Pd-Cu/AC catalyst prepared by co-impregnation method exhibited poor stability, Pd-Cu/AC catalyst with CFC-113 conversion dropping to around 37% after 50 h of hydrodechlorination reaction. Brunauer-Emmett-Teller, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction of fresh and deactivated Pd/AC catalysts indicate that the deactivation of Pd/AC catalysts is due to high-temperature agglomeration of Pd. Comparative analysis of fresh and deactivated Pd-Cu/AC catalysts using Brunauer-Emmett-Teller, transmission electron microscopy, and thermogravimetric analysis techniques revealed decreased dispersion of active sites, reduced surface area, catalyst aggregation deactivation, and a significant decrease in Cu content. Furthermore, the results of NH₃-TPD revealed that the acid sites of the catalyst increased significantly. X-ray diffraction spectra indicated the formation of new species, basic copper chloride (Cu₂(OH)₃Cl), during the reaction. As the reaction progressed, these new species agglomerated, leading to a gradual loss of catalyst activity. Moreover, the deactivated catalyst was successfully reactivated using a simple alkaline washing method.

关键词: CFC-113, Hydrodechlorination, Chlorotrifluoroethylene, Catalyst deactivation

Abstract: Chlorotrifluoroethylene (CTFE) is a vital fluorinated olefinic monomer produced through the catalytic hydrodechlorination of trichlorotrifluoroethane (CFC-113), an eco-friendly process. However, hydrodechlorination catalysts for olefin production often suffer from poor stability. The Pd/AC catalyst and Pd-Cu/AC catalyst prepared by co-impregnation method exhibited poor stability, Pd-Cu/AC catalyst with CFC-113 conversion dropping to around 37% after 50 h of hydrodechlorination reaction. Brunauer-Emmett-Teller, transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction of fresh and deactivated Pd/AC catalysts indicate that the deactivation of Pd/AC catalysts is due to high-temperature agglomeration of Pd. Comparative analysis of fresh and deactivated Pd-Cu/AC catalysts using Brunauer-Emmett-Teller, transmission electron microscopy, and thermogravimetric analysis techniques revealed decreased dispersion of active sites, reduced surface area, catalyst aggregation deactivation, and a significant decrease in Cu content. Furthermore, the results of NH₃-TPD revealed that the acid sites of the catalyst increased significantly. X-ray diffraction spectra indicated the formation of new species, basic copper chloride (Cu₂(OH)₃Cl), during the reaction. As the reaction progressed, these new species agglomerated, leading to a gradual loss of catalyst activity. Moreover, the deactivated catalyst was successfully reactivated using a simple alkaline washing method.

Key words: CFC-113, Hydrodechlorination, Chlorotrifluoroethylene, Catalyst deactivation

Song Tian, Yicheng Chen, Xiaoyu Wen, Bingcheng Li, Jian Lu, Zile Li, Feng Feng, Qingtao Wang, Qunfeng Zhang, Xiaonian Li. Hydrodechlorination of trifluoro-trichloroethane to chlorotrifluoroethylene: Revealing the deactivation mechanism and regeneration strategy of Pd-Cu/AC catalyst[J]. 中国化学工程学报, 2024, 70(6): 261-268.

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Hydrodechlorination of trifluoro-trichloroethane to chlorotrifluoroethylene: Revealing the deactivation mechanism and regeneration strategy of Pd-Cu/AC catalyst

Hydrodechlorination of trifluoro-trichloroethane to chlorotrifluoroethylene: Revealing the deactivation mechanism and regeneration strategy of Pd-Cu/AC catalyst

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