Research progress in the synthesis of olefins by selective hydrodechlorination

doi:10.11949/0438-1157.20240701

Abstract

Abstract:

In recent years, with the increasing consumption of aliphatic unsaturated compounds such as ethylene and propylene in modern society, the transformation of halogenated compounds to above high-value chemicals via the selective hydrodechlorination technology has attracted much attention in both of academia and industry. The core is the design and preparation of high-performance catalysts. This paper first reviews the research progress of catalysts for hydrodechlorination to olefins, focusing on summarizing the influence of the geometric structure, electronic structure, catalytic promoter, and preparation method of the active components of the catalysts such as Pd and Pt on the formation of olefins. Then, the progress of mechanism in the synthesis of olefins via catalytic selective hydrodechlorination is summarized from dynamics and theoretical calculations. Furthermore, four main reasons of catalyst deactivation are summarized. Finally, based on the structural stability of metal fluoride under high temperature and strong corrosive atmosphere such as HCl, and easily achieving interaction between supports and active components, the development of Pd-based and Pt-based supported metal fluoride catalysts is a significant rote to synthesizing olefins via the selective hydrodechlorination.

Key words: catalyst support, selectivity, reactivity, hydrodechlorination, olefin, noble metal catalyst

摘要：

近年来，随着乙烯、丙烯等脂肪族不饱和化合物用量日益剧增，利用选择性加氢脱氯技术将多氯代烃转化为这类高附加值化学品受到学术界和工业界的广泛关注，其核心在于高性能催化剂的设计与制备。首先综述了加氢脱氯合成烯烃用催化剂的研究进展，重点归纳总结了催化剂活性组分如Pd、Pt的几何结构、电子结构以及催化助剂、制备方法等对烯烃生成的影响规律。其次，从动力学、理论计算等方面对催化选择性加氢脱氯合成烯烃反应机理进行了概述。此外，总结了造成催化剂失活的四个主要因素。最后指出，基于金属氟化物在高温强腐蚀性HCl气氛下结构保持稳定、易于实现调控载体与活性组分之间相互作用等特点，设计制备金属氟化物负载型Pd、Pt催化剂，是实现温和条件下选择性加氢脱氯合成烯烃的一个重要途径。

关键词: 催化剂载体, 选择性, 活性, 加氢脱氯, 烯烃, 贵金属催化剂

CLC Number:

TQ 203.2

Chen YANG, Wei MAO, Xingzong DONG, Song TIAN, Fengwei ZHAO, Jian LYU. Research progress in the synthesis of olefins by selective hydrodechlorination[J]. CIESC Journal, 2025, 76(1): 53-70.

杨晨, 毛伟, 董兴宗, 田松, 赵锋伟, 吕剑. 选择性加氢脱氯合成烯烃研究进展[J]. 化工学报, 2025, 76(1): 53-70.

Figures/Tables 20

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载体	底物	活性组分	反应温度/℃	原料转化率/%	目标烯烃产物	烯烃选择性/%	文献
SiO₂	1,2-DCE	Pt₁₆Cu₈₄	350	<15	C₂H₄	91	[25]
	1,2-DCE	Pd_1.5Ag_3.0	300	—	C₂H₄	100	[35]
	1,2-DCE	Pt₁Sn₃	200	1.0	C₂H₄	96	[36]
γ-Al₂O₃	1,2-DCE	Pd_0.13Ag_0.84	250	8.9	C₂H₄	94.6	[15]
	1,2-DCE	Rh、Ni	300	37	C₂H₄	>95	[20]
	1,2-DCE	Pd₁Cu₃	250	5.5	C₂H₄	>80	[14]
BEA	1,2-DCE	Ni_2.0Ag_2.0	250	—	C₂H₄	100	[38]
SBA-15	1,2-DCE	Ni	300	38.1	C₂H₄	>95	[33]
HMS	1,2-DCE	Ni	300	39.2	C₂H₄	>95	[33]
MCM-41	1,2-DCE	Ni	300	40.2	C₂H₄	>95	[33]
TiO₂	1,2-DCE	AgPd_0.35	170	0.21	C₂H₄	97.3	[8]
CeO₂	TCE	Pt	300	12	C₂H₄	40	[37]
Ce_0.5Zr_0.5O₂	1,2-DCE	Ni	300	64.2	C₂H₄	>90	[33]
活性炭	1,2-DCE	AgPd_0.6	170	0.05	C₂H₄	82	[8]
	CFC-113	Ru	200	33.5	CTFE	96.1	[22]
	CF₃OCFClCF₂Cl	Ru	250	29	CF₃OCF=CF₂	97	[13]
	CF₃OCFClCF₂Cl	Ni	300	6	CF₃OCF=CF₂	86	[13]
	CF₃OCFClCF₂Cl	Pd₁Ru₈	250	73	CF₃OCF=CF₂	89	[13]
	1,2-DCE	Ni	230	—	C₂H₄	97	[31]
	1,2-DCE	Pd₀₅Ni₉₅	260	<2	C₂H₄	100	[39]
	CTFE	Pd	250	76	TrFE	80	[40]
	CTFE	Pd-K	250	90	TrFE	85	[41]

载体	底物	活性组分	反应温度/℃	原料转化率/%	目标烯烃产物	烯烃选择性/%	文献
SiO₂	1,2-DCE	Pt₁₆Cu₈₄	350	<15	C₂H₄	91	[25]
	1,2-DCE	Pd_1.5Ag_3.0	300	—	C₂H₄	100	[35]
	1,2-DCE	Pt₁Sn₃	200	1.0	C₂H₄	96	[36]
γ-Al₂O₃	1,2-DCE	Pd_0.13Ag_0.84	250	8.9	C₂H₄	94.6	[15]
	1,2-DCE	Rh、Ni	300	37	C₂H₄	>95	[20]
	1,2-DCE	Pd₁Cu₃	250	5.5	C₂H₄	>80	[14]
BEA	1,2-DCE	Ni_2.0Ag_2.0	250	—	C₂H₄	100	[38]
SBA-15	1,2-DCE	Ni	300	38.1	C₂H₄	>95	[33]
HMS	1,2-DCE	Ni	300	39.2	C₂H₄	>95	[33]
MCM-41	1,2-DCE	Ni	300	40.2	C₂H₄	>95	[33]
TiO₂	1,2-DCE	AgPd_0.35	170	0.21	C₂H₄	97.3	[8]
CeO₂	TCE	Pt	300	12	C₂H₄	40	[37]
Ce_0.5Zr_0.5O₂	1,2-DCE	Ni	300	64.2	C₂H₄	>90	[33]
活性炭	1,2-DCE	AgPd_0.6	170	0.05	C₂H₄	82	[8]
	CFC-113	Ru	200	33.5	CTFE	96.1	[22]
	CF₃OCFClCF₂Cl	Ru	250	29	CF₃OCF=CF₂	97	[13]
	CF₃OCFClCF₂Cl	Ni	300	6	CF₃OCF=CF₂	86	[13]
	CF₃OCFClCF₂Cl	Pd₁Ru₈	250	73	CF₃OCF=CF₂	89	[13]
	1,2-DCE	Ni	230	—	C₂H₄	97	[31]
	1,2-DCE	Pd₀₅Ni₉₅	260	<2	C₂H₄	100	[39]
	CTFE	Pd	250	76	TrFE	80	[40]
	CTFE	Pd-K	250	90	TrFE	85	[41]

活性组分	助剂	催化剂制备方法	反应温度/℃	反应底物	转化率/%	目标烯烃产物	乙烯选择性/%	文献
Pd	Ag	光沉积法	250	1,2-DCE	1.2	C₂H₄	90	[17]
Pd	Ag	浸渍法	250	1,2-DCE	<2	C₂H₄	68	[17]
Pt	—	热熔法	300	TCE	10	C₂H₄	48	[37]
Pt	—	浸渍法	300	TCE	12	C₂H₄	40	[37]
Pt	Sn	表面还原法	200	1,2-DCE	0.6	C₂H₄	75	[58]
Pt	Sn	浸渍法	200	1,2-DCE	0.7	C₂H₄	91	[58]
Pt	Cu	表面还原法	350	1,2-DCE	29	C₂H₄	91	[25]
Pt	Cu	浸渍法	350	1,2-DCE	20	C₂H₄	60	[25]
Pd	Cu	沉淀-还原法	250	1,2-DCE	11.3	C₂H₄	96	[14]
Pd	Cu	浸渍法	250	1,2-DCE	5.3	C₂H₄	80	[14]

活性组分	助剂	催化剂制备方法	反应温度/℃	反应底物	转化率/%	目标烯烃产物	乙烯选择性/%	文献
Pd	Ag	光沉积法	250	1,2-DCE	1.2	C₂H₄	90	[17]
Pd	Ag	浸渍法	250	1,2-DCE	<2	C₂H₄	68	[17]
Pt	—	热熔法	300	TCE	10	C₂H₄	48	[37]
Pt	—	浸渍法	300	TCE	12	C₂H₄	40	[37]
Pt	Sn	表面还原法	200	1,2-DCE	0.6	C₂H₄	75	[58]
Pt	Sn	浸渍法	200	1,2-DCE	0.7	C₂H₄	91	[58]
Pt	Cu	表面还原法	350	1,2-DCE	29	C₂H₄	91	[25]
Pt	Cu	浸渍法	350	1,2-DCE	20	C₂H₄	60	[25]
Pd	Cu	沉淀-还原法	250	1,2-DCE	11.3	C₂H₄	96	[14]
Pd	Cu	浸渍法	250	1,2-DCE	5.3	C₂H₄	80	[14]

离子态/金属态	电极电势/V
Cu²⁺/Cu	0.34
Ag⁺/Ag	0.80
Pd²⁺/Pd	0.99
Ru³⁺/Ru	0.38
Pt²⁺/Pt	1.19
Au⁺/Au	1.52
Ir³⁺/Ir	1.16