Research progress of catalysts for gas-phase dehydrofluorination to synthesize C2 hydrofluoroolefins

doi:10.16085/j.issn.1000-6613.2024-0732

Abstract

Abstract:

The gas-phase catalytic dehydrofluorination to synthesize C₂ fluoroalkenes is an economically efficient process that enables continuous large scale production. The key lies in the development of highly efficient and stable dehydrofluorination catalysts. The research progress of gas-phase dehydrofluorination catalysts for C₂ hydrofluoroolefin synthesis has been summarized. Firstly, this review introduces the E1 and E2 mechanisms of gas-phase dehydrofluorination reaction, followed by a discussion on the impacts of acidity, fluoride ion affinity, and synergy of multi-active sites on the catalyst activity and stability. Then, the applications of dehydrofluorination catalysts in the synthesis of important C₂ hydrofluoroolefins such as vinyl fluoride, vinylidene fluoride, 1,2-difluoroethylene, and trifluoroethylene have been summarized. Although research suggests that catalysts with appropriate Lewis acid site strength and multiple active sites can significantly enhance reaction efficiency and catalyst lifetime, challenges remain in overcoming issues such as high-temperature sintering and carbon deposition. Future efforts should focus on optimizing catalyst design under process conditions and improving catalyst regeneration capabilities, which thereby promote the sustainable production of fluorinated compounds.

Key words: catalyst, hydrofluoroolefins, alkane, dehydrofluorination, activity, stability

摘要：

气相催化脱氟化氢合成C₂氢氟烯烃是一种经济高效、可实现连续化放大生产的工艺路线，其核心技术是开发高效稳定脱氟化氢催化剂。本文总结了国内外C₂氢氟烯烃合成用气相脱氟化氢催化剂的研究进展。首先，介绍了气相脱氟化氢反应的E1机制和E2机制，在此基础上探讨了酸性、氟离子亲和力以及多活性位点协同对催化剂活性与稳定性的影响。接着，归纳了脱氟化氢催化剂在氟乙烯、偏氟乙烯、1,2-二氟乙烯、三氟乙烯等重要C₂氢氟烯烃合成中的应用情况。虽然已有研究表明，开发Lewis酸位点强度适宜且具有多活性位点的催化剂可以显著提升脱氟化氢反应效率和催化剂寿命，但仍需克服高温烧结和积炭等挑战。未来需结合工艺条件优化催化剂设计，提高催化剂再生能力，推动含氟化合物的可持续生产。

关键词: 催化剂, 氢氟烯烃, 烷烃, 脱氟化氢, 活性, 稳定性

CLC Number:

TQ213

LU Peng, ZHANG Di, LIU Yaoyao, YU Wanjin, LIU Wucan, ZHANG Jianjun. Research progress of catalysts for gas-phase dehydrofluorination to synthesize C₂ hydrofluoroolefins[J]. Chemical Industry and Engineering Progress, 2025, 44(7): 3907-3916.

卢朋, 张迪, 刘瑶瑶, 于万金, 刘武灿, 张建君. 气相脱氟化氢合成C₂氢氟烯烃催化剂的研究进展[J]. 化工进展, 2025, 44(7): 3907-3916.

Figures/Tables 7

序号	化学反应式	反应活化能/kJ·mol^–1
1	$C H 3 C H F 2 → C H 2 ̿ C H F + H F$	259^[18]
2	$C H 3 C F 3 → C H 2 ̿ C F 2 + H F$	310~311^[19-20]
3	$C H 2 F C F 3 → C H F ̿ C F 2 + H F$	296^[21]

序号	化学反应式	反应活化能/kJ·mol^–1
1	$C H 3 C H F 2 → C H 2 ̿ C H F + H F$	259^[18]
2	$C H 3 C F 3 → C H 2 ̿ C F 2 + H F$	310~311^[19-20]
3	$C H 2 F C F 3 → C H F ̿ C F 2 + H F$	296^[21]

硬酸		交界酸		软酸
离子	η/eV	离子	η/eV	离子	η/eV
Li⁺	35.1	Fe²⁺	7.2	Cu⁺	6.3
Na⁺	21.1	Co²⁺	8.2	Ag⁺	7.0
K⁺	13.6	Ni²⁺	8.5	Au⁺	5.6
Mg²⁺	32.6	Cu²⁺	8.3	Hg²⁺	7.7
Ca²⁺	19.5	Zn²⁺	10.9	Cs⁺	10.6
Al³⁺	45.8	Ba²⁺	12.8
B³⁺	110.7
Zr⁴⁺	17.4

硬碱		交界碱		软碱
离子	η/eV	离子	η/eV	离子	η/eV
F^-	7.0	NO₂^-	4.5	I^-	3.7
OH^-	5.6	Br^-	4.2	CN^-	5.3
Cl^-	4.7			H^-	6.8

催化剂	反应温度/℃	反应空速/h^-1	物料比（HFC-152a∶N₂）	反应时长/h	HFC-152a转化率/%	VF选择性/%	参考文献
氟化α-Cr₂O₃	350	600	—	—	78.9	95.6	[57]
立方晶型CrF₃	300	300	—	—	42	92.2	[58]
六棱柱形Cr₂O₃	300	300	1∶9	70	80	100	[59]
纳米级Cr₂O₃	300	300	1∶9	110	>83	—	[60]
MgF₂/β-AlF₃	300	600	—	48	56.6	100	[61]
ZnF₂/β-AlF₃	300	600	—	48	56.5	100	[61]
Al-Y-Ni	300	600	1∶1	48	75.6	99.2	[62]
Cr₂O₃-α-AlF₃	380	3000	—	8	84.4	—	[63]
Cr-Al	400	1200	1∶1	60	92	—	[64]
Al-F(p-BDC)	300	1200	1∶1	10	79.8	100	[65]
TiF₃@C-AlF _x	300	600	—	48	>81	—	[32]
MIL-53-Al-X-F	300	1200	1∶1	25	>55	—	[66]
MgF₂	300	300	5∶4	25	56	99.5	[67-68]
Fe _x Mg _y F₂	300	750	—	初始	60	99.5	[69]
TiOF₂	300	600	1∶1	33	53	100	[70]
5%AlF₃/SiC	300	300	1∶1	35	45	—	[71]
SiC（球磨2h）	300	300	1∶1	30	42	100	[72]
5%Al₂O₃@SiC	300	300	1∶1	35	40	—	[73]

催化剂	反应温度/℃	反应空速/h^-1	物料比	反应时长/h	HFC-143a转化率/%	VDF选择性/%	来源
Mg₂P₂O₇	450	895	HFC-143a∶H₂∶N₂=2∶15∶83	100	50	90	[76]
纳米纤维MgF₂	450	1200	HFC-143a∶N₂=1∶1	10	16mmol/(h·g_催化剂)	>99.5	[77]
粉煤灰	500	1890	HFC-143a∶N₂=5∶95	1/3	28	99	[78]

反应温度/℃	接触时间/g·s·cm^-3	物料比	反应时长/h	HFC-143转化率/%	HFO-1132选择性/%
350	40	—	1	68	94
400	40	—	1	89	90
400	40	—	10	52	98
400	40	HFC-143∶O₂=85∶15	10	88	91

催化剂	反应温度/℃	反应空速/h^-1	物料比（HFC-134a∶N₂）	反应时长/h	HFC-134a转化率/%	HFO-1123选择性/%	参考文献
3%Zn/Cr₂O₃	400	—	6.5∶93.5	—	2.2	93.4	[87]
Al₂O₃	450	225	1∶9	—	23.4	98.5	[84]
γ-Al₂O₃	400	—	1∶4（添加水）	24	32	—	[85]
HS-AlF₃/γ-Al₂O₃	300	—	1∶4	—	12.2	83.7	[86]
HS-α-AlF₃	400	679	1∶9	0.33	28.3	99	[37]
Mg/AlF₃	450	700	1∶9	—	33.4	99	[89]
CrCl₃/AlF₃	380	300	—	400	66	98.2	[90]
Fe/AlF₃	500	—	6.5∶93.5	4.85	24.1	99.6	[91]
Fe/Al₂O_1.2F_3.6	410	600	—	300	66.5	98.4	[92]
Y-Mg-Al-F	400	700	1∶9	100	30.8	>99	[93]
NiF _x /AlF₃	400	700	1∶9	20	21.4	99.7	[94]
NiAlF-12.8	430	675	1∶10	100	20.1	99	[88]
AlNiF（Al∶Ni=2∶1）	500	—	1∶2	20	21.3	99	[42]
NiAlF-5	450	675	1∶10	300	>20	99	[95]
NiAlF(H)	500	—	1∶2	10	29.2	99	[96]

References 96

[1]	ZAPSAS George, PATIL Yogesh, GNANOU Yves, et al. Poly(vinylidene fluoride)-based complex macromolecular architectures: From synthesis to properties and applications[J]. Progress in Polymer Science, 2020, 104: 101231.
[2]	MATHER Brian D, REINARTZ Nicole M, SHIFLETT Mark B. Polymerization of vinyl fluoride in ionic liquid and ionic solutions[J]. Polymer, 2016, 82: 295-304.
[3]	SOULESTIN Thibaut, LADMIRAL Vincent, DOS SANTOS Fabrice Domingues, et al. Vinylidene fluoride- and trifluoroethylene-containing fluorinated electroactive copolymers. How does chemistry impact properties?[J]. Progress in Polymer Science, 2017, 72: 16-60.
[4]	SAKODA Naoya, PERERA Uthpala A, Kyaw THU, et al. Measurements of PvT properties, saturated densities, and critical parameters of R1132(E)[J]. International Journal of Refrigeration, 2022, 140: 166-171.
[5]	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.
[6]	HASHIMOTO Mai, OTSUKA Tetsuo, FUKUSHIMA Masato, et al. Development of new low-GWP refrigerants–refrigerant mixtures including HFO-1123[J]. Science and Technology for the Built Environment, 2019, 25(6): 776-783.
[7]	MIYAMOTO H, NISHIDA M, SAITO T. Measurement of the vapour–liquid equilibrium properties of binary mixtures of the low-GWP refrigerants R1123 and R1234yf[J]. The Journal of Chemical Thermodynamics, 2021, 158: 106456.
[8]	SICARD Alexandre J, BAKER R TOM. Fluorocarbon refrigerants and their syntheses: Past to present[J]. Chemical Reviews, 2020, 120(17): 9164-9303.
[9]	李玲, 马超峰, 卢春山, 等. 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.
	LI Ling, MA Chaofeng, LU Chunshan, et al. Progress on the synthesis of 1,1,2-trifluoroethene and the catalysts[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1822-1831.
[10]	卢朋, 张迪, 刘瑶瑶, 等. 低GWP制冷剂HFO-1132的制备及应用研究概述[J]. 浙江化工, 2022, 53(3): 1-6.
	LU Peng, ZHANG Di, LIU Yaoyao, et al. Overview of preparation and application of low GWP refrigerant HFO-1132[J]. Zhejiang Chemical Industry, 2022, 53(3): 1-6.
[11]	张呈平, 郭勤, 权恒道. 氯氟烃替代物的过去、现在和未来[J]. 精细化工, 2023, 40(5): 941-952.
	ZHANG Chengping, GUO Qin, QUAN Hengdao. Past, present and future of chlorofluorocarbons substitutes[J]. Fine Chemicals, 2023, 40(5): 941-952.
[12]	郑治文, 张荣慧, 王来来, 等. 合成偏氟乙烯和含氟丙烯的催化剂及应用研究进展[J]. 分子催化, 2019, 33(3): 285-295.
	ZHENG Zhiwen, ZHANG Ronghui, WANG Lailai, et al. Research progress in catalysts and applications for the synthesis of vinylidene fluoride and fluoropropylene[J]. Journal of Molecular Catalysis (China), 2019, 33(3): 285-295.
[13]	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.
[14]	王海丽. 氟化铝的可控制备及催化含氟烷烃脱氟化氢性能研究[D]. 杭州: 浙江工业大学, 2019.
	WANG Haili. Controllable preparation of aluminum fluoride and its catalytic performance for dehydrofluorination of fluorinated alkanes[D]. Hangzhou: Zhejiang University of Technology, 2019.
[15]	秦越, 张伟, 王博, 等. 脱卤化氢合成氢氟烯烃催化剂的研究进展[J]. 化工新型材料, 2011, 39(12): 34-37.
	QIN Yue, ZHANG Wei, WANG Bo, et al. Research advance on catalysts for the synthesis of hydrofluoroolefins by dehydrohalogenation reaction[J]. New Chemical Materials, 2011, 39(12): 34-37.
[16]	李小娟. Cr₂O₃催化剂的制备及HFC-152a脱HF合成氟乙烯反应催化性能[D]. 杭州: 浙江工业大学, 2016.
	LI Xiaojuan. Preparation of Cr₂O₃ catalyst and its catalytic performance for synthesis of vinyl fluoride by dehydrofluorination of HFC-152a[D]. Hangzhou: Zhejiang University of Technology, 2016.
[17]	KUSHIDA Megumi, TAKAHASHI Kazuhiro, NAKAUE Tsubasa. Method for manufacturing 2-chloro-1,1-difluoroethane (HCFC-142), 1,1,2-trifluoroethane (HFC-143), and (E)-1,2-difluoroethylene (HFO-1132(E)) and/or (Z)-1,2-difluoroethylene (HFO-1132(Z)): US20230138340[P]. 2023-05-04.
[18]	Eugene TSCHUIKOW-ROUX, QUIRING W J, SIMMIE J M. Kinetics of the thermal decomposition of 1,1-difluoroethane in shock waves. Consecutive first-order reaction[J]. The Journal of Physical Chemistry, 1970, 74(12): 2449-2455.
[19]	TSANG Wing, LIFSHITZ Assa. Kinetic stability of 1,1,1-trifluoroethane[J]. International Journal of Chemical Kinetics, 1998, 30(9): 621-628.
[20]	MATSUGI Akira, YASUNAGA Kenji, SHIINA Hiroumi. Thermal decomposition of 1,1,1-trifluoroethane revisited[J]. The Journal of Physical Chemistry A, 2014, 118(50): 11688-11695.
[21]	MILLWARD G E, TSCHUIKOW-ROUX E. Kinetic analysis of the shock wave decomposition of 1,1,1,2-tetrafluoroethane[J]. The Journal of Physical Chemistry, 1972, 76(3): 292-298.
[22]	TEINZ Katharina, WUTTKE Stefan, Fabian BÖRNO, et al. Highly selective metal fluoride catalysts for the dehydrohalogenation of 3-chloro-1,1,1,3-tetrafluorobutane[J]. Journal of Catalysis, 2011, 282(1): 175-182.
[23]	TEINZ Katharina, MANUEL Saul Robles, CHEN Benjamin Bin, et al. Catalytic formation of 2,3,3,3-tetrafluoropropene from 2-chloro-3,3,3-trifluoropropene at fluorinated chromia: A study of reaction pathways[J]. Applied Catalysis B: Environmental, 2015, 165: 200-208.
[24]	KERVAREC Maëva-Charlotte, MARSHALL Clara Patricia, BRAUN Thomas, et al. Selective dehydrofluorination of 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) to 2-chloro-3,3,3-trifluoropropene (HFO-1233xf) using nanoscopic aluminium fluoride catalysts at mild conditions[J]. Journal of Fluorine Chemistry, 2019, 221: 61-65.
[25]	KAMIGUCHI Satoshi, WATANABE Masaki, KONDO Kunihiko, 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.
[26]	SHIROUDI Abolfazl, ZAHEDI Ehsan. Theoretical study of HF elimination kinetics of ethane fluorides and derivatives [C₂H_6- _n F _n (n=1—4)] [J]. Indian Journal of Chemistry, 2010, 49A: 1579-85.
[27]	LUO Yuran. Handbook of bond dissociation energies in organic compounds[M]. Boca Raton, Fla.: CRC Press, 2003: 65-98.
[28]	STAHL Timo, KLARE Hendrik F T, OESTREICH Martin. Main-group lewis acids for C—F bond activation[J]. ACS Catalysis, 2013, 3(7): 1578-1587.
[29]	VELA Javier, SMITH Jeremy M, YU Ying, et al. Synthesis and reactivity of low-coordinate iron(Ⅱ) fluoride complexes and their use in the catalytic hydrodefluorination of fluorocarbons[J]. Journal of the American Chemical Society, 2005, 127(21): 7857-7870.
[30]	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.
[31]	HAN Wenfeng, LIU Bing, KANG Yikun, et al. Experimental and DFT mechanistic study of dehydrohalogenation of 1-chloro-1,1-difluoroethane over metal fluorides[J]. Industrial & Engineering Chemistry Research, 2019, 58(39): 18149-18159.
[32]	HAN Wenfeng, YANG Hong, WANG Linzhe, et al. Confined aluminum fluoride layers derived from the in situ etching of Ti₃AlC₂ as the robust catalyst for dehydrofluorination reaction[J]. Applied Surface Science, 2021, 538: 148022.
[33]	GAO Yanzhao, MENG Xianglei, HUANG Shiqi, et al. Effects of MgO doping in Pd/γ-Al₂O₃ catalysts for the hydrogenation of perfluoro olefin[J]. Molecular Catalysis, 2024, 552: 113652.
[34]	DAMBOURNET Damien, ELTANAMY Gehan, VIMONT Alexandre, et al. Coupling sol-gel synthesis and microwave-assisted techniques: A new route from amorphous to crystalline high-surface-area aluminium fluoride[J]. Chemistry—A European Journal, 2008, 14(20): 6205-6212.
[35]	KEMNITZ Erhard. Nanoscale metal fluorides: A new class of heterogeneous catalysts[J]. Catalysis Science & Technology, 2015, 5(2): 786-806.
[36]	KRAHL Thoralf, KEMNITZ Erhard. Aluminium fluoride—The strongest solid Lewis acid: Structure and reactivity[J]. Catalysis Science & Technology, 2017, 7(4): 773-796.
[37]	MAO Wei, BAI Yanbo, WANG Bo, et al. A facile Sol-gel synthesis of highly active nano α-aluminum fluoride catalyst for dehydrofluorination of hydrofluorocarbons[J]. Applied Catalysis B: Environmental, 2017, 206: 65-73.
[38]	MAO Wei, BAI Yanbo, JIA Zhaohua, et al. Highly efficient gas-phase dehydrofluorination of 1,1,1,3,3-pentafluoropropane to 1,3,3,3-tetrafluoropropene over mesoporous nano-aluminum fluoride prepared from a polyol mediated sol-gel process[J]. Applied Catalysis A: General, 2018, 564: 147-156.
[39]	WANG Haili, HAN Wenfeng, LI Xiliang, et al. Solution combustion synthesis of Cr₂O₃ nanoparticles and the catalytic performance for dehydrofluorination of 1,1,1,3,3-pentafluoropropane to 1,3,3,3-tetrafluoropropene[J]. Molecules, 2019, 24(2): 361.
[40]	LIU Bing, HAN Wenfeng, CHEN Aimin, et al. Confinement of AlF₃ in MOF derived structures for the formation of 4-fold coordinated Al and significantly improved dehydrofluorination activity[J]. Chemical Engineering Journal, 2020, 394: 124946.
[41]	WANG Fang, ZHANG Wenxia, LIANG Yan, et al. Pd/AlF₃ catalysts for catalytic dehydrofluorination of 1,1,1,3,3-pentafluoropropane[J]. Chemical Research in Chinese Universities, 2015, 31(6): 1003-1006.
[42]	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.
[43]	LUO Jianwei, SONG Jiandong, JIA Wenzhi, et al. Catalytic dehydrofluorination of 1,1,1,3,3-pentafluoropropane to 1,3,3,3-tetrafluoropropene over fluorinated NiO/Cr₂O₃ catalysts[J]. Applied Surface Science, 2018, 433: 904-913.
[44]	JIA Wenzhi, FANG Xiuxiu, FANG Chentao, et al. Selective dehydrofluorination of 1,1,1,3,3-pentafluoropropane to synthesize tetrafluoropropylene and trifluoropropyne over the ZnO/Cr₂O₃ catalysts[J]. ChemistrySelect, 2020, 5(42): 13027-13032.
[45]	FANG Xiuxiu, WANG Yun, JIA Wenzhi, et al. Dehydrofluorination of 1,1,1,3,3-pentafluoropropane over C-AlF₃ composite catalysts: Improved catalyst stability by the presence of pre-deposited carbon[J]. Applied Catalysis A: General, 2019, 576: 39-46.
[46]	HESS A, KEMNITZ E, LIPPITZ A, et al. ESCA, XRD, and IR characterization of aluminum oxide, hydroxyfluoride, and fluoride surfaces in correlation with their catalytic activity in heterogeneous halogen exchange reactions[J]. Journal of Catalysis, 1994, 148(1): 270-280.
[47]	BAILEY C L, WANDER A, MUKHOPADHYAY S, et al. Adsorption of HF and HCl on the β-AlF₃ (100) surface[J]. Physical Chemistry Chemical Physics, 2008, 10(20): 2918-2924.
[48]	PEARSON Ralph G. Hard and soft acids and bases[J]. Journal of the American Chemical Society, 1963, 85(22): 3533-3539.
[49]	KLOPMAN Gilles. Chemical reactivity and the concept of charge- and frontier-controlled reactions[J]. Journal of the American Chemical Society, 1968, 90(2): 223-234.
[50]	PARR Robert G, PEARSON Ralph G. Absolute hardness: Companion parameter to absolute electronegativity[J]. Journal of the American Chemical Society, 1983, 105(26): 7512-7516.
[51]	KOCH Ernst-Christian. Acid-base interactions in energetic materials: Ⅰ. The hard and soft acids and bases (HSAB) principle-insights to reactivity and sensitivity of energetic materials[J]. Propellants, Explosives, Pyrotechnics, 2005, 30(2): 164.
[52]	贾兆华, 毛伟, 白彦波, 等. 氟化镁基催化剂催化2-氯-1,1,1,2-四氟丙烷气相脱卤化氢反应性能研究[J]. 现代化工, 2018, 38(3): 105-109.
	JIA Zhaohua, MAO Wei, BAI Yanbo, et al. Gas-phase dehydrohalogenation of 2-chloro-1,1,1,2-tetrafluoropropene over magnesium fluoride-based catalysts[J]. Modern Chemical Industry, 2018, 38(3): 105-109.
[53]	MAO Wei, BAI Yanbo, WANG Wei, et al. Highly selective dehydrochlorination of 1,1,1,2-tetrafluoro-2-chloropropane to 2,3,3,3-tetrafluoropropene over alkali metal fluoride modified MgO catalysts[J]. ChemCatChem, 2017, 9(5): 824-832.
[54]	JIA Wenzhi, CAI Xia, ZHANG Yong, et al. Catalytic dehydrofluorination of hydrofluoroalkanes to fluorinated olifein over Ni/AlF₃ catalysts[J]. MATEC Web of Conferences, 2018, 238: 03004.
[55]	NAWAZ Zeeshan. Light alkane dehydrogenation to light olefin technologies: A comprehensive review[J]. Reviews in Chemical Engineering, 2015, 31(5): 413-436.
[56]	王术成, 张迪, 林胜达, 等. 1,1-二氟乙烷气相脱氟化氢制备氟乙烯催化剂研究进展[J]. 化工生产与技术, 2014, 20(6): 12-15, 9.
	WANG Shucheng, ZHANG Di, LIN Shengda, et al. Research on the catalysts for synthesis of vinyl fluoride by vapor phase dehydrofluorination of R152a[J]. Chemical Production and Technology, 2014, 20(6): 12-15, 9.
[57]	CHRISTOPH Frank J, COULSTON George W, RAO Velliyur Nott Mallikarjuna. Chromium catalyst and manufacture of vinyl fluoride by catalytic dehydrofluorination of 1,1-difluoroethane: WO9641679A1[P]. 1996-12-27.
[58]	MALLIKARJUNA Rao V, SUBRAMANIAN Munirpallam A. Dehydrofluorination process and catalyst for the manufacture of fluoroalkenes from hydrofluorocarbon: US6031141A[P]. 2000-02-29.
[59]	HAN Wenfeng, LI Xiaojuan, TANG Haodong, et al. Preparation of fluorinated Cr₂O₃ hexagonal prism and catalytic performance for the dehydrofluorination of 1,1-difluoroethane to vinyl fluoride[J]. Journal of Nanoparticle Research, 2015, 17(9): 365.
[60]	HAN Wenfeng, WANG Zhikun, LI Xiaojuan, et al. Solution combustion synthesis of nano-chromia as catalyst for the dehydrofluorination of 1,1-difluoroethane[J]. Journal of Materials Science, 2016, 51(24): 11002-11013.
[61]	RAO Vn Mallikarjuna, SUBRAMANIAN Munirpallam A. Catalytic manufacture of vinyl fluoride by dehydrofluorination of 1,1-difluoroethane: US5880315A[P]. 1999-03-09.
[62]	王术成, 张迪, 林胜达, 等. 一种用于由 1,1-二氟乙烷制备氟乙烯的铝基催化剂、其制备方法及应用: CN104841413B[P]. 2020-06-16.
	WANG Shucheng, ZHANG Di, LIN Shengda, et al. An aluminum based catalyst for the preparation of fluoroethylene from 1,1-difluoroethane, its preparation method, and application: CN104841413B[P]. 2020-06-16.
[63]	于洪波, 贾文志, 普志英, 等. 高比表面积Cr₂O₃-α-AlF₃催化剂的制备和应用[J]. 物理化学学报, 2011, 27(11): 2677-2681.
	YU Hongbo, JIA Wenzhi, PU Zhiying, et al. Preparation and application of a Cr₂O₃-α-AlF₃ catalyst with a high specific surface area[J]. Acta Physico-Chimica Sinica, 2011, 27(11): 2677-2681.
[64]	HAN Wenfeng, LIU Bing, LI Xiliang, et al. Combustion synthesis of amorphous Al and Cr composite as the catalyst for dehydrofluorination of 1,1-difluoroethane[J]. Industrial & Engineering Chemistry Research, 2018, 57(38): 12774-12783.
[65]	韩文锋, 贾忠盛, 余厚霖, 等. 一种Al-F(p-BDC)催化剂及其制备方法和应用: CN112521414B[P]. 2022-07-08.
	HAN Wenfeng, JIA Zhongsheng, YU Houlin, et al. Al-F(p-BDC) catalyst as well as preparation method and application thereof: CN112521414B[P]. 2020-12-08.
[66]	WEI Xiaoli, JIA Zhongsheng, WANG Chuanzhao, et al. Under-coordinated AlF₃ clusters confined in carbon matrix with robust sintering resistance for dehydrofluorination of hydrofluorocarbons[J]. Chemical Engineering Journal, 2022, 431: 134178.
[67]	丁珊珊, 陈鑫鑫, 李雨臻, 等. 模板法制备高比表面积的氟化镁及其在HFC-152a脱HF反应中的应用[J]. 无机材料学报, 2018, 33(11): 1186-1192.
	DING Shanshan, CHEN Xinxin, LI Yuzhen, et al. High-surface-area magnesium fluoride: Preparation by template method and catalytic activity for the dehydrofluorination of HFC-152a[J]. Journal of Inorganic Materials, 2018, 33(11): 1186-1192.
[68]	TANG Haodong, DANG Mingming, LI Yuzhen, et al. Rational design of MgF₂ catalysts with long-term stability for the dehydrofluorination of 1,1-difluoroethane (HFC-152a)[J]. RSC Advances, 2019, 9(41): 23744-23751.
[69]	张蕾, 李雨臻, 李利春, 等. 溶胶-凝胶法制备Fe掺杂MgF₂催化剂及其催化1,1-二氟乙烷(R152a)脱HF反应的性能[J]. 无机化学学报, 2021, 37(1): 39-46.
	ZHANG Lei, LI Yuzhen, LI Lichun, et al. Fe-doped MgF₂ catalyst: Preparation by sol-gel method and performance in dehydrogenation of 1,1-difluoroalkane(R152a)[J]. Chinese Journal of Inorganic Chemistry, 2021, 37(1): 39-46.
[70]	WEI Xiaoli, YANG Hong, LIU Bing, et al. Synthesis of titanium oxyfluoride with oxygen vacancy as novel catalysts for pyrolysis of fluorinated greenhouse gasses to hydrofluoroolefins[J]. Journal of the Taiwan Institute of Chemical Engineers, 2021, 129: 189-196.
[71]	LU Jiaqin, HAN Wenfeng, YU Wei, et al. Thermally conductive SiC as support of aluminum fluoride for the catalytic dehydrofluorination reaction[J]. Catalysis Communications, 2020, 142: 106033.
[72]	WEI Xiaoli, WEI Yifan, LU Jiaqin, et al. Evolution of Lewis acidity by mechanochemical and fluorination treatment of silicon carbide as novel catalyst for dehydrofluorination reactions[J]. Molecular Catalysis, 2023, 537: 112948.
[73]	WEI Xiaoli, SUN Yiwei, JIANG Jianhai, et al. Stabilizing F-Al-O active center via confinement of Al₂O₃ in SiC framework for conversion of 1,1-difluoroethane greenhouse gas[J]. Journal of Fluorine Chemistry, 2024, 274: 110257.
[74]	郑海峰, 尹红, 袁慎峰, 等. 1-氯-1,1-二氟乙烷裂解制备偏氟乙烯的研究进展[J]. 化工进展, 2014, 33(1): 16-20, 49.
	ZHENG Haifeng, YIN Hong, YUAN Shenfeng, et al. Research progress in the pyrolysis of 1-chloro-1,1-difluoroethane to vinylidene fluoride[J]. Chemical Industry and Engineering Progress, 2014, 33(1): 16-20, 49.
[75]	张万宏, 桑益, 吴伟震. 1,1-二氟-1-氯乙烷合成研究进展[J]. 化工生产与技术, 2011, 18(2): 1-5, 37.
	ZHANG Wanhong, SANG Yi, WU Weizhen. Research development of HFCFC-142b synthesis[J]. Chemical Production and Technology, 2011, 18(2): 1-5, 37.
[76]	LI Gongliang, NISHIGUCHI Hiroyasu, ISHIHARA Tatsumi, et al. Catalytic dehydrofluorination of CF₃CH₃(HFC143a) into CF₂CH₂(HFC1132a)[J]. Applied Catalysis B: Environmental, 1998, 16(4): 309-317.
[77]	HAN Wenfeng, ZHANG Chunpeng, WANG Haili, et al. Sub-nano MgF₂ embedded in carbon nanofibers and electrospun MgF₂ nanofibers by one-step electrospinning as highly efficient catalysts for 1,1,1-trifluoroethane dehydrofluorination[J]. Catalysis Science & Technology, 2017, 7(24): 6000-6012.
[78]	ETOU Yuusuke, NAKAMURA Shingo. Methods for producing halogenated alkene compound and fluorinated alkyne compound: US11655199[P]. 2023-05-23.
[79]	USUI Takashi, NAKAUE Tsubasa, CHAKI Takehiro, et al. Method for producing fluoroolefin： US11236030[P]. 2022-02-01.
[80]	KOMATSU Yuzo. Method for preparing 1,2-difluoroethylene and/or 1,1,2-trifluoroethane: US11332423[P]. 2022-05-17.
[81]	USUI Takashi, NAKAUE Tsubasa, KOMATSU Yuzo, et al. The method for manufacturing of cis/trans-1,2-difluoroethylene: WO2019240233A1[P]. 2019-12-19.
[82]	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. Research progress on preparation methods of trifluoroethylene[J]. Organo-Fluorine Industry, 2010(3): 13-15.
[83]	赵洋. HFC-134a裂解制备三氟乙烯催化剂的研究[D]. 金华: 浙江师范大学, 2014.
	ZHAO Yang. Study on catalyst for preparing trifluoroethylene by cracking HFC-134a[D]. Jinhua: Zhejiang Normal University, 2014.
[84]	JIA Wenzhi, WU Qian, LANG Xuewei, et al. Influence of lewis acidity on catalytic activity of the porous alumina for dehydrofluorination of 1,1,1,2-tetrafluoroethane to trifluoroethylene[J]. Catalysis Letters, 2015, 145(2): 654-661.
[85]	HAN Tae Uk, YOO Beom-Sik, KIM Young-Min, et al. Catalytic conversion of 1,1,1,2-tetrafluoroethane (HFC-134a)[J]. Korean Journal of Chemical Engineering, 2018, 35(8): 1611-1619.
[86]	UENVEREN Ercan, KEMNITZ Erhard, RUEDIGER Stephan, et al. Preparation of halogenated alkenes over amorphous metal fluoride catalysts: WO2009010472A1[P]. 2009-01-22.
[87]	POWELL Richard Llewellyn, SHARRATT Andrew Paul. Process for the production of fluorine containing olefins： US5856593[P]. 1999-01-05.
[88]	JIA Wenzhi, LIU Min, LANG Xuewei, et al. Catalytic dehydrofluorination of 1,1,1,2-tetrafluoroethane to synthesize trifluoroethylene over a modified NiO/Al₂O₃ catalyst[J]. Catalysis Science & Technology, 2015, 5(6): 3103-3107.
[89]	蔚辰刚, 谢冠群, 周强, 等. MgF₂-AlF₃催化剂用于四氟乙烷裂解制备三氟乙烯[J]. 工业催化, 2012, 20(4): 56-59.
	YU Chengang, XIE Guanqun, ZHOU Qiang, et al. Catalytic pyrolysis performance of MgF₂-AlF₃ catalysts for tetrafluoroethane to trifluoroethylene[J]. Industrial Catalysis, 2012, 20(4): 56-59.
[90]	白彦波, 吕剑, 毛伟, 等. 一种 1,1,1,2-四氟乙烷制备三氟乙烯用催化剂: CN106902850B[P]. 2019-08-27.
	BAI Yanbo, Jian LYU, MAO Wei, et al. Catalyst for preparing trifluoroethylene from 1,1,1,2-tetrafluoroethane: CN106902850B[P]. 2019-08-27.
[91]	秦越, 吕剑, 张伟, 等. 一种三氟乙烯的制备方法: CN104710273B[P]. 2013-12-12.
	QIN Yue, Jian LYU, ZHANG Wei, et al. A process for the preparation of trifluoroethylene: CN104710273B[P]. 2013-12-12.
[92]	白彦波, 吕剑, 毛伟, 等. 一种 1,1,1,2-四氟乙烷制备三氟乙烯用催化剂: CN105251518A[P]. 2015-11-02.
	BAI Yanbo, Jian LYU, MAO Wei, et al. A kind of catalyst for preparing trifluoroethylene from 1,1,1,2-tetrafluoroethane and its preparation method: CN105251518A [P]. 2015-11-02.
[93]	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.
[94]	赵洋, 章轩语, 周强, 等. MO _x /Al₂O₃(M=Ni、Mg、Co、Ce)催化剂氟化预处理过程的物相转变和HFC-134a裂解制三氟乙烯性能[J]. 化工进展, 2014, 33(8): 2050-2054.
	ZHAO Yang, ZHANG Xuanyu, ZHOU Qiang, et al. Catalysts phase transition in pre-fluorination of MO _x /Al₂O₃(M=Ni, Mg, Co, Ce) and catalytic pyrolysis performance of HFC-134a to trifluoroethylene[J]. Chemical Industry and Engineering Progress, 2014, 33(8): 2050-2054.
[95]	JIA Wenzhi, CHEN Yanfeng, LIU Min, et al. Effect of calcination temperature and fluorination treatment on NiF₂-AlF₃ catalysts for dehydrofluorination of 1,1,1,2-tetrafluoroethane to synthesize trifluoroethylene[J]. Applied Catalysis A: General, 2019, 571: 150-157.
[96]	JIA Wenzhi, HUANG Xiaodan, YANG Xinhui, et al. Synergistic roles of surface acidity and Ni species in NiF₂/AlF₃ catalysts for pyrolysis of 1,1,1,2-tetrafluoroethane[J]. Molecular Catalysis, 2022, 527: 112433.

Research progress of catalysts for gas-phase dehydrofluorination to synthesize C₂ hydrofluoroolefins

气相脱氟化氢合成C₂氢氟烯烃催化剂的研究进展

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 7

References 96

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	ZHANG Wei, LIANG Yaocheng, WU Qiao, FU Yehao, YIN Yanshan, CHENG Shan, RUAN Min, LIU Tao, ZHOU Zhaoyi, ZHANG Kaikai, LI Dancong. Metal ion modified Cu-SSZ-13 catalyst for NH₃-selective catalytic reduction of NO _x [J]. Chemical Industry and Engineering Progress, 2025, 44(7): 3879-3891.
[2]	WANG Hui, LIU Jiaxu. Research progress on the synthesis of SSZ-39 zeolite and NH₃-SCR application [J]. Chemical Industry and Engineering Progress, 2025, 44(7): 3892-3906.
[3]	LI Hongwei, XU Hanqiao, ZHAO Yan, LIU Yaozong, TENG Zhijun, JI Dong, LI Guixian. Research progress and prospect of platinum-based catalysts for electrocatalytic methanol oxidation [J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3443-3456.
[4]	KONG Xiaoyang, LIU Zhentao, ZOU Yutong, WANG Dandan, DUAN Aijun, XU Chunming, WANG Xilong. Development in catalysts for hydrocracking of polycyclic aromatic hydrocarbons to BTX [J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3468-3485.
[5]	LIU Shizhe. Advances in catalytic system for methylcyclohexane dehydrogenation [J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3486-3496.
[6]	FU Yuanpeng, DONG Xianshu, MA Xiaomin, FAN Yuping. Mechanism study on preparation of LiNi_1/3Co_1/3Mn_1/3O₂ ternary electrode material precursor by liquid sol-gel method [J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3561-3569.
[7]	YAO Ruwei, SONG Yueyin, NIU Qinqin, LI Congming. Na-S co-modified iron catalysts for CO₂ hydrogenation to C₂₊ alcohols [J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3154-3162.
[8]	CHEN Shaowei, CHEN Yi, NIU Jiangqi, LIU Tianqi, HUANG Jianguo, CHEN Huanhao, FAN Xiaolei. Research progress and application prospects of dielectric barrier discharge plasma catalytic reactors [J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3175-3189.
[9]	WANG Jiahui, LI Peiya, YANG Fusheng, WANG Bin, FANG Tao. Research progress on the dehydrogenation of methylcyclohexane as a liquid organic hydrogen carrier [J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3208-3223.
[10]	ZHANG Ying, ZHENG Xuemei, MA Aiyuan, TIAN Shihong. Research progress based on conventional and microwave pyrolysis behavior of polyethylene [J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3224-3237.
[11]	SHI Xiuding, WANG Yongquan, ZENG Jing, SU Chang, HONG Junming. Nanotubular Co-N-C activated percarbonate for tetracycline degradation [J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3041-3052.
[12]	DING Ajing, ZHOU Qiaoqiao, GU Xuehong. Catalytic gasification of poplar wood in a membrane reactor to produce clean syngas [J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2716-2723.
[13]	HE Zhiyong. Catalyst evolved by stepwise dehydroxylation/decarbonization method achieves efficient methanol decomposition to produce hydrogen [J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2724-2732.
[14]	TANG Zequn, WANG Zishuai, XIAO Gang, SU Haijia. Research advances in catalytic solvolysis to convert plastic waste [J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2746-2757.
[15]	FAN Xiaoya, ZHAO Zhen, PENG Qiang. Review on electrocatalytic co-reduction of carbon dioxide and nitrate for urea synthesis [J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2856-2869.