Progress on the synthesis of 1,1,2-trifluoroethene and the catalysts

doi:10.16085/j.issn.1000-6613.2022-1084

Abstract

Abstract:

Hydrofluoroolefins (HFOs) have great potential in many applications due to their superior properties of zero ozone depletion potential (ODP) and low global warming potential (GWP). 1,1,2-Trifluoroethene (TrFE), a novel HFO compound, is considered as a promising candidate of a heat pump working fluid in the air-conditioning system for the new energy vehicles or being used to synthesize the fluoropolymers which are further used as piezoelectric and electrocaloric cooling materials and to synthesize the high value-added alkenyl halides for microchips. In this review, we categorized the existing approaches for TrFE synthesis. The technical challenges of each method were elaborated and the potential solutions were discussed. For the most commonly used methods that use 1,1,1,2-tetrafluoroethane (HFC-134a) and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) as starting materials, the low selectivity to 1,1,2-trifluoroethene and the deactivation of the catalysts are the most critical challenges, which also limit the scaling-up and the commercialization of the technologies.

Key words: catalyst, synthesis, hydrogenation, stability, olefin, fluorine

摘要：

含氟烯烃（HFOs）具有ODP为零、GWP值极低的优点，其中1,1,2-三氟乙烯（TrFE）可作为新能源汽车热泵工质、含氟高聚材料的合成单体、高附加值卤代烯烃制备的关键原料，有望实现在新能源汽车空调系统、压电材料与电卡制冷材料、高端芯片蚀刻等领域的广泛应用。本文对TrFE合成工艺进行分类，并详述各路线的技术难点与解决策略；针对主要合成路线即1,1,1,2-四氟乙烷（HFC-134a）脱氟化氢、1,1,2-三氯-1,2,2-三氟乙烷（CFC-113）催化加氢制备TrFE路线，对催化剂进行总结与归纳，讨论催化剂配方、制备方法、结构等因素对反应的影响。如何提高1,1,2-三氟乙烯选择性与催化剂稳定性是该研究的重点与难点，也是制约其产业化与商品化的决定因素。

关键词: 催化剂, 合成, 加氢, 稳定性, 烯烃, 氟

CLC Number:

LI Ling, MA Chaofeng, LU Chunshan, YU Wanjin, SHI Nengfu, JIN Jiamin, ZHANG Jianjun, LIU Wucan, LI Xiaonian. Progress on the synthesis of 1,1,2-trifluoroethene and the catalysts[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1822-1831.

李玲, 马超峰, 卢春山, 于万金, 石能富, 金佳敏, 张建君, 刘武灿, 李小年. 新型含氟替代品1,1,2-三氟乙烯的合成工艺与催化剂研究进展[J]. 化工进展, 2023, 42(4): 1822-1831.

Figures/Tables 11

References 59

1	SICARD A J, BAKER R T. Fluorocarbon refrigerants and their syntheses: Past to present[J]. Chemical Reviews, 2020, 120(17): 9164-9303.
2	ALBÀ C G, ALKHATIB I I I, LLOVELL F, et al. Assessment of low global warming potential refrigerants for drop-in replacement by connecting their molecular features to their performance[J]. ACS Sustainable Chemistry & Engineering, 2021, 9(50): 17034-17048.
3	UDDIN K, ARAKAKI S, SAHA B B. Thermodynamic analysis of low-GWP blends to replace R410A for residential building air conditioning applications[J]. Environmental Science and Pollution Research, 2021, 28(3): 2934-2947.
4	YU Binbin, OUYANG Hongsheng, SHI Junye, et al. Evaluation of low-GWP and mildly flammable mixtures as new alternatives for R410A in air-conditioning and heat pump system[J]. International Journal of Refrigeration, 2021, 121: 95-104.
5	SHI Junye, HAN Donglin, LI Zichao, et al. Electrocaloric cooling materials and devices for zero-global-warming-potential, high-efficiency refrigeration[J]. Joule, 2019, 3(5): 1200-1225.
6	NEESE B, CHU Baojin, LU Shengguo, et al. Large electrocaloric effect in ferroelectric polymers near room temperature[J]. Science, 2008, 321(5890): 821-823.
7	陈岩飞, 王聪海, 肖晓明. 一种催化制备六氟‐ 1,3‐丁二烯的方法: CN106495982B[P]. 2018-09-18.
	CHEN Yanfei, WANG Conghai, XIAO Xiaoming. Method for preparing hexafluoro-1, 3-butadiene: CN106495982B[P]. 2018-09-18.
8	张奎, 黄天梁, 黄荣保. 一种六氟丁二烯的制备方法: CN110590495A[P]. 2019-12-20.
	ZHANG Kui, HUANG Tianliang, HUANG Rongbao. Method for preparing hexafluorobutadiene and its application in plasma medium etching: CN110590495A[P]. 2019-12-20.
9	刘敏洋, 于万金, 林胜达, 等. 一种卤代丙烯的制备方法: CN113527040A[P]. 2021-10-22.
	LIU Minyang, YU Wanjin, LIN Shengda, et al. Preparation method of halogenated propylene: CN113527040A[P]. 2021-10-22.
10	GUILLET Dominique, DEVIC Michel, GUILPAIN Gerard, et al. Procede de preparation de trifluoroethylene: FR2961203[P]. 2011-12-16.
11	GUILLET Dominique, DEVIC Michel, GUILPAIN Gerard, et al. Method for preparing trifluoroethylene:. WO2011157907A1[P]. 2011-12-22.
12	LIZUKA A, ISHIZAKI H, MIZUKOSHI A, et al. Simultaneous decomposition and fixation of F-gases using waste concrete[J]. Industrial & Engineering Chemistry Research, 2011, 50(21): 11808-11814.
13	LEE Sprague, DANIEL Graham, LOUIS Ferstandig. Production of aliphatic fluorocarbons: WO0107384A1[P]. 2001-02-01.
14	罗孟飞, 蔚辰刚, 贾文志, 等. 一种三氟乙烯和四氟甲烷的制备方法: CN102267866B[P]. 2013-11-27.
	LUO Mengfei, WEI Chengang, JIA Wenzhi, et al. Method for preparing trifluoroethylene and tetrafluoromethane simultaneously: CN102267866B[P]. 2013-11-27.
15	朱志荣, 贾文志, 魏建华. 一种生产三氟乙烯联产氟化氢的方法: CN103288589A[P]. 2013-09-11.
	ZHU Zhirong, JIA Wenzhi, WEI Jianhua. Preparation of hydrofluoric acid during production of trifluoroethylene: CN102267866B[P]. 2013-11-27.
16	NAKAMURA M, OKAMOTO H. Method for producing trifluoroethylene: WO2015147063A1[P]. 2015-10-01.
17	NAKAMURA M, OKAMOTO H. Method for producing trifluoroethylene: WO2015115548A1[P]. 2015-08-06.
18	张万宏, 韩文峰, 李宏峰, 等. 一种三氟乙烯的制备方法: CN103044190B[P]. 2014-12-24.
	ZHANG Wanhong, HAN Wenfeng, LI Hongfeng, et al. Process for preparation of trifluoroethylene from pyrolysis of 1,1,1,2-tetrafluoroethane: CN103044190B[P]. 2014-12-24.
19	TOMIYORI Y, NAKAMURA M. Process for producing hydrofluoroolefin: WO2016163522A1[P]. 2016-10-13.
20	TOMIYORI Y, NAKAMURA M. Method for producing hydrofluoroolefin: WO2017104829A1[P]. 2017-06-22.
21	TOMIYORI Y, NAKAMURA M. Method for producing hydrofluoroolefin: WO2017104828A1[P]. 2017-06-22.
22	富依勇佑, 中村允彦. 氢氟烯烃的制造方法: CN108368011B[P]. 2021-09-17.
	TOMIYORI Y, NAKAMURA M. Method for producing hydrofluoroolefin: CN108368011B[P]. 2021-09-17.
23	TOMOAKI Taniguchi, SHOJI Furuta. Method for producing trifluoroethylene: JP2016124847A[P]. 2016-07-11.
24	ERCAN Uenveren, ERHARD Kemnitz, STEPHAN Ruediger, et al. Preparation of halogenated alkenes over amorphous metal fluoride catalysts: WO2009010472A1[P]. 2009-01-22.
25	刘武灿, 徐卫国, 张建君. 三氟乙烯制备方法研究进展[J]. 有机氟工业, 2010(3): 13-15.
	LIU Wucan, XU Weiguo, ZHANG Jianjun. Study progress on the preparation of trifluoroethylene[J]. Organo-Fluorine Industry, 2010(3): 13-15.
26	TAKITA Yusaku, YAMADA Hiroshi, ISHIHARA Tatsumi, et al. Catalytic hydrodechlorination of CFC 113 (CCl₂FCClF₂)[J]. Nippon Kagaku Kaishi, 1991(5): 584-590.
27	LUC Lerot, VINCENT Wilmet, JOSEPH Pirotton. A 1,1,2 -trichloro-1,2,2-trifluoroethane hydrogenation process: EP0355907A1[P]. 1990-02-28.
28	MORI T, YASUOKA T, MORIKAWA Y. Hydrodechlorination of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) over supported ruthenium and other noble metal catalysts[J]. Catalysis Today, 2004, 88(3/4): 111-120.
29	OKAZAKI S, HABUTSU H. Hydrodechlorination of CCl₂FCClF₂ over NiO-Cr₂O₃ catalysts[J]. Journal of Fluorine Chemistry, 1992, 57(1/2/3): 191-201.
30	STEPANOV A A, DELYAGINA N I, CHERSTKOV V F. Catalytic synthesis of polyfluoroolefins[J]. Russian Journal of Organic Chemistry, 2010, 46(9): 1290-1295.
31	MENG Baochuan, SUN Zhaoyang, MA Jinpeng, et al. Selective liquid-phase hydrodechlorination of chlorotrifluoroethylene over palladium-supported catalysts: activity and deactivation[J]. Catalysis Letters, 2010, 138(1/2): 68-75.
32	曹贵平, 粟小理, 孟保川, 等. 催化氢解三氟氯乙烯制备三氟乙烯的工艺方法及专用设备: CN101402548B[P]. 2011-06-22.
	CAO Guiping, LI Xiaoli, MENG Baochuan, et al. Process for preparation of trifluoroethylene by hydrogenolysis of trifluorochloroethylene: CN101402548B[P]. 2011-06-22.
33	胡昌明, 涂明虎. 催化氢解三氟氯乙烯制备三氟乙烯的方法: CN1080277[P]. 1994-01-05.
	HU Changming, TU Minghu. preparation of trifluoroethylene by catalytic hydrogenolysis of trifluorochloroethylene: CN1080277[P]. 1994-01-05.
34	王益, 王其明, 沈德新, 等. 一种制备三氟乙烯的方法: CN102372593A[P]. 2012-03-14.
	WANG Yi, WANG Qiming, SHEN Dexin, et al. A process for preparing trifluoroethylene: CN102372593A[P]. 2012-03-14.
35	赵卫娟, 徐卫国, 方小青. 一种制备三氟乙烯的方法: CN101851146B[P]. 2013-09-25.
	ZHAO Weijuan, XU Weiguo, FANG Xiaoqing. Preparation of trifluoroethylene: CN101851146B[P]. 2013-09-25.
36	林韦康, 朱海, 陈东辉, 等. 4,4-二氟-3-氧代-2-哌啶-1-基亚甲基丁酸乙酯的合成方法: CN112279821A[P]. 2021-01-29.
	LIN Weikang, ZHU Hai, CHEN Donghui, et al. Synthesis method of 4,4-difluoro-3-oxo-2-piperidin-1-yl methylene butyrate ethyl ester: CN112279821A[P]. 2021-01-29.
37	YUUSUKE Etou, KENJI Adachi, SENSUKE Ogoshi. Method for producing 1,1,2-trifluoroethylene, hexafluoro-1,3-butadiene, or 1,2-dichlorohexafluorocyclobutane: WO2021029420A1[P]. 2021-02-18.
38	KAMIGUCHI S, WATANABE M, KONDO K, et al. Catalytic dehydrohalogenation of alkyl halides by Nb, Mo, Ta, and W halide clusters with an octahedral metal framework and by a Re chloride cluster with a triangular metal framework[J]. Journal of Molecular Catalysis A: Chemical, 2003, 203(1/2): 153-163.
39	赵洋, 蔚辰刚, 周强, 等. Y-Mg-Al-F催化剂用于1,1,1,2-四氟乙烷裂解制备三氟乙烯[J]. 应用化学, 2014, 31(4): 400-405.
	ZHAO Yang, YU Chengang, ZHOU Qiang, et al. Performance of Y-Mg-Al-F catalysts for catalytic pyrolysis of 1,1,1,2-tetrafluoroethane to trifluoroethylene[J]. Chinese Journal of Applied Chemistry, 2014, 31(4): 400-405.
40	贾文志, 刘行, 董正曦, 等. CF₃CFH₂脱HF反应Lewis酸催化剂失活的研究[J]. 化学世界, 2017, 58(9): 513-518.
	JIA Wenzhi, LIU Xing, DONG Zhengxi, et al. Study on deactivation of lewis catalysts for dehydrofluorination of 1,1,1,2-tetrafluoroethane[J]. Chemical World, 2017, 58(9): 513-518.
41	白彦波, 马洋博, 毛伟, 等. 气相催化脱氟化氢制备含氟烯烃催化剂的研究进展[J]. 化工进展, 2013, 32(10): 2387-2391, 2452.
	BAI Yanbo, MA Yangbo, MAO Wei, et al. Advances in catalysts of gas-phase catalytic dehydrofluorination to prepare fluorinated olefins[J]. Chemical Industry and Engineering Progress, 2013, 32(10): 2387-2391, 2452.
42	POWELL R L, SHARRATT A P. Process for the production of fluorine containing olefins: US5856593A[P]. 1999-01-05.
43	KÖNIG R, SCHOLZ G, SCHEURELL K, et al. Spectroscopic characterization of crystalline AlF₃ phases[J]. Journal of Fluorine Chemistry, 2010, 131(1): 91-97.
44	白彦波, 毛伟, 秦越, 等. 制备条件对AlF₃催化1,1,1,2-四氟乙烷脱氟化氢性能的影响[J]. 化学反应工程与工艺, 2014, 30(5): 458-462.
	BAI Yanbo, MAO Wei, QIN Yue, et al. Effect of preparation conditions on catalytic performance of AlF₃ used for dehydrofluoration of 1,1,1,2-tetrafluoroethane[J]. Chemical Reaction Engineering and Technology, 2014, 30(5): 458-462.
45	HAN T U, YOO B S, KIM Y M, et al. Catalytic conversion of 1,1,1,2-tetrafluoroethane (HFC-134a)[J]. Korean Journal of Chemical Engineering, 2018, 35(8): 1611-1619.
46	HAN Wenfeng, WANG Haili, LIU Bing, et al. PVDF mediated fabrication of freestanding AlF₃ sub-microspheres: Facile and controllable synthesis of α, β and θ-AlF₃ [J]. Materials Chemistry and Physics, 2020, 240: 122287.
47	YANG Hong, WU Sen, CHEN Zhengfei, et al. Catalytic performance for the conversion of potent fluorinated greenhouse gases by aluminium fluorides with different morphology[J]. Catalysis Letters, 2021, 151(7): 2065-2074.
48	WANG Fang, ZHANG Wenxia, LIANG Yan, et al. Pd/AlF₃catalysts for catalytic dehydrofluorination of 1,1,1,3,3-pentafluoropropane[J]. Chemical Research in Chinese Universities, 2015, 31(6): 1003-1006.
49	唐浩东, 孙慧, 韩文锋, 等. 一种 1,1,1,2-四氟乙烷催化裂解生成三氟乙烯的催化剂及原位再生方法: CN106000428B[P]. 2018-11-13.
	TANG Haodong, SUN Hui, HAN Wenfeng, et al. Catalyst for catalytic cracking of 1,1,1,2-tetrafluoroethane to generate trifluoroethylene and in situ regeneration method: CN106000428B[P]. 2018-11-13.
50	陈焱锋, 朱志荣, 贾文志, 等. 用于合成三氟乙烯的催化剂及其制备方法: CN107243352B[P]. 2019-12-20.
	CHEN Yanfeng, ZHU Zhirong, JIA Wenzhi, et al. Catalyst for synthesizing trifluoroethylene and preparation method thereof: CN107243352B[P]. 2019-12-20.
51	XI Zhiwen, LIU Xing, LI Junhui, et al. A novel Ni/NiF₂-AlF₃ catalyst with mild-strength lewis acid sites for dehydrofluorination of 1,1,1,2-tetrafluoroethane to synthesize trifluoroethylene[J]. ChemistrySelect, 2019, 4(15): 4506-4511.
52	OHNISHI R, SUZUKI I, ICHIKAWA M. Bi-Pd catalyst for selective hydrodechlorination of 1,1,2-trichlorotrifluoroethane to trifluoroethene, a key intermediate to 1,1,1,2-tetrafluoroethane as a CFC replacement for refrigeration[J]. Chemistry Letters, 1991, 20(5): 841-844.
53	OHNISHI R, SUZUKI H, WANG W L, et al. Promoting role of metal additives in modified Pd catalysts for selective hydrodechlorination of CFC-113[J]. Studies in Surface Science and Catalysis, 1993, 77: 429-432.
54	SAIKI T, SUMIDA M, NAKANO S, et al. Method for producing trifluoroethylene: EP0471320A1[P]. 1992-02-19.
55	LUC Lerot, VINCENT Wilmet, JOSEPH Pirotton. Catalytic compositions, process for obtaining them and process for hydrogenation of 1,1,2-trichloro-1,2,2-trifluoroethane by means of these compositions: US5053377A[P]. 1991-10-01.
56	LUC Lerot, VINCENT Wilmet, JOSEPH Pirotton. Process for the preparation of chlorotrifluoroethylene and of trifluoroethylene from 1,1,2-trichloro-1,2,2-trifluoroethane and catalytic composition used in this process: EP0496446A1[P]. 1992-07-29.
57	L·莱罗, V·维尔梅, J·皮罗敦. 制备一氯三氟乙烯和三氟乙烯的方法以及用于该方法的催化剂组合物: CN1065261[P]. 1992-10-14.
	LEROT L, WILMET, PIROTTON J. Process for the preparation of chlorotrifluoroethylene and of trifluoroethylene from 1,1,2-trichloro-1,2,2-trifluoroethane and catalytic composition used in this process: CN1065261[P]. 1992-10-14.
58	廖湘洲, 粟小理, 陆子薇, 等. 加氢脱卤催化剂和三氟氯乙烯与三氟乙烯的制备方法: CN113649030A[P]. 2021-11-16.
	LIAO Xiangzhou, LI Xiaoli, LU Ziwei, et al. Hydrodehalogenation catalyst and preparation method of trifluorochloroethylene and trifluoroethylene: CN113649030A[P]. 2021-11-16.
59	MORIKAWA Y, IKAWA T, WATARU U. Production of trifluoroethylene: JP05009138[P]. 1993-01-19.

[1]	ZHANG Mingyan, LIU Yan, ZHANG Xueting, LIU Yake, LI Congju, ZHANG Xiuling. Research progress of non-noble metal bifunctional catalysts in zinc-air batteries [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 276-286.
[2]	SHI Yongxing, LIN Gang, SUN Xiaohang, JIANG Weigeng, QIAO Dawei, YAN Binhang. Research progress on active sites in Cu-based catalysts for CO₂ hydrogenation to methanol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 287-298.
[3]	XIE Luyao, CHEN Songzhe, WANG Laijun, ZHANG Ping. Platinum-based catalysts for SO₂ depolarized electrolysis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 299-309.
[4]	YANG Xiazhen, PENG Yifan, LIU Huazhang, HUO Chao. Regulation of active phase of fused iron catalyst and its catalytic performance of Fischer-Tropsch synthesis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 310-318.
[5]	ZHAO Wei, ZHAO Deyin, LI Shihan, LIU Hongda, SUN Jin, GUO Yanqiu. Synthesis and application of triazine drag reducing agent for nature gas pipeline [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 391-399.
[6]	WANG Zhengkun, LI Sifang. Green synthesis of gemini surfactant decyne diol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 400-410.
[7]	WANG Lele, YANG Wanrong, YAO Yan, LIU Tao, HE Chuan, LIU Xiao, SU Sheng, KONG Fanhai, ZHU Canghai, XIANG Jun. Influence of spent SCR catalyst blending on the characteristics and deNO _x performance for new SCR catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 489-497.
[8]	DENG Liping, SHI Haoyu, LIU Xiaolong, CHEN Yaoji, YAN Jingying. Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 542-548.
[9]	XU Youhao, WANG Wei, LU Bona, XU Hui, HE Mingyuan. China’s oil refining innovation: MIP development strategy and enlightenment [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4465-4470.
[10]	CHENG Tao, CUI Ruili, SONG Junnan, ZHANG Tianqi, ZHANG Yunhe, LIANG Shijie, PU Shi. Analysis of impurity deposition and pressure drop increase mechanisms in residue hydrotreating unit [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4616-4627.
[11]	WANG Peng, SHI Huibing, ZHAO Deming, FENG Baolin, CHEN Qian, YANG Da. Recent advances on transition metal catalyzed carbonylation of chlorinated compounds [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4649-4666.
[12]	ZHANG Qi, ZHAO Hong, RONG Junfeng. Research progress of anti-toxicity electrocatalysts for oxygen reduction reaction in PEMFC [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4677-4691.
[13]	GE Quanqian, XU Mai, LIANG Xian, WANG Fengwu. Research progress on the application of MOFs in photoelectrocatalysis [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4692-4705.
[14]	WANG Weitao, BAO Tingyu, JIANG Xulu, HE Zhenhong, WANG Kuan, YANG Yang, LIU Zhaotie. Oxidation of benzene to phenol over aldehyde-ketone resin based metal-free catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4706-4715.
[15]	GE Yafen, SUN Yu, XIAO Peng, LIU Qi, LIU Bo, SUN Chengying, GONG Yanjun. Research progress of zeolite for VOCs removal [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4716-4730.