炔烃选择性加氢制烯烃反应的研究进展

doi:10.16085/j.issn.1000-6613.2023-1181

摘要/Abstract

摘要：

炔烃选择性加氢制烯烃是石油化工领域重要的反应过程。传统的热催化方法在过去的几十年中被广泛研究，而新兴光/电催化方法的研究仍处于初级阶段。得益于催化剂合成方法、结构表征技术和理论计算等的快速发展，逐步揭示了炔烃选择性加氢过程中的催化剂活性位点和反应机理。本文介绍了近年来各类催化剂在炔烃选择性加氢方面的研究进展，总结了设计高性能催化剂的相应调控策略。对比了传统热催化加氢与光/电催化选择性加氢技术路线的不同特点，重点分析了不同类型的催化加氢反应出现的问题及解决策略。最后，对该领域的研究现状进行了简要的概述，提出了该领域面临的主要挑战和未来发展趋势，并展望了未来催化剂设计和调控目标产物选择性等方向。

关键词: 炔烃选择性加氢, 热催化, 光催化, 电催化

Abstract:

Selective hydrogenation of alkynes to produce alkenes is a crucial reaction process in petroleum and chemical engineering. Traditional thermal catalytic methods have been extensively studied over the past few decades, while the research on emerging photo-/electrocatalytic methods is still in its preliminary stage and designing highly efficient catalysts remains a significant challenge. The rapid progress in catalyst synthesis methods, structural characterization techniques, and theoretical calculations has gradually revealed the reaction mechanisms and the mechanisms of catalytic active sites involved in the selective hydrogenation of alkynes. This review provides an overview of recent advancements in various catalysts for selective hydrogenation of alkynes and summarizes the corresponding strategies for designing high-performance catalysts. A comparison between traditional thermal catalytic hydrogenation and photo-/electrocatalytic selective hydrogenation routes is made, with a focus on the different characteristics and analysis of the problems and their possible solutions in various types of catalytic hydrogenation reactions. Furthermore, a concise overview of the current research status in this field is provided, along with the major challenges and future development trends. Additionally, the review highlights the potential directions in catalyst design and modulation of target product selectivity for future research.

Key words: selective catalytic hydrogenation of alkynes, thermocatalytic, photocatalysis, electrocatalytic

中图分类号:

TQ211

吴泽亮, 管琦卉, 陈世霞, 王珺. 炔烃选择性加氢制烯烃反应的研究进展[J]. 化工进展, 2024, 43(8): 4366-4381.

WU Zeliang, GUAN Qihui, CHEN Shixia, WANG Jun. Advances in selective hydrogenation of alkynes to alkenes[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4366-4381.

图/表 17

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气体组成	催化剂	反应温度/℃	反应压力/MPa	空速/mL·g_cat^-1·h^-1	转化率/%	选择性/%	参考文献
C₃H₄∶H₂ = 2.5∶7.5	Cu_2.75Ni_0.25Fe	250	0.1	1.68 × 10⁴	100	97	[4]
C₂H₂∶C₂H₄∶H₂ = 0.5∶25∶1	Pd₁/g-C₃N₄	110	0.1	3 × 10⁴	80	92	[33]
C₃H₄∶H₂ = 1∶3	Cu-Al HT	250	0.1	1.68 × 10⁴	100	—	[42]
C₂H₂∶H₂ = 1∶30	In₂O₃	350	0.1	—	100	85	[44]
C₂H₂∶C₂H₄∶H₂ = 1∶9∶1.8	Pd₄S/CNFs	250	0.1	6 × 10⁴	100	95	[47]
C₂H₂∶C₂H₄∶H₂ = 1∶99∶2	Ti-Pd/PHSNs	45	0.1	7200	70	69	[48]
C₂H₂∶C₂H₄∶H₂ = 1∶9∶1.2	Pd₄S/CNFs	250	1.8	2.16 × 10⁶	46.6	96	[49]
C₂H₂∶C₂H₄∶H₂ = 0.5∶20∶3	Pd@C/CNT	150	0.1	6 × 10⁴	93	70	[50]
C₂H₂∶C₂H₄∶H₂ = 1∶20∶20	AuPd_0.01/SiO₂	160	0.1	6 × 10⁴	86	56.4	[51]
C₂H₂∶C₂H₄∶H₂ = 0.8∶83.2∶16	Au/SiO₂	175	0.1	9.2 × 10⁴	94	47	[52]
C₃H₄∶H₂ = 1∶30	CeO₂	250	0.1	—	96	91	[53]
C₂H₂∶C₂H₄∶H₂ = 0.5∶50∶5	Al₁₃Fe₄	200	0.1	9× 10⁴	80	82	[54]
C₂H₂∶H₂ = 1∶5	Ni₆In/SiO₂	180	0.1	3.6× 10⁴	63	100	[55]
C₂H₂∶H₂ = 0.475∶9.25	CrO _x /(110)γ-Al₂O₃	140	0.1	2.166 × 10⁴	100	98.5	[56]

气体组成	催化剂	反应温度/℃	反应压力/MPa	空速/mL·g_cat^-1·h^-1	转化率/%	选择性/%	参考文献
C₃H₄∶H₂ = 2.5∶7.5	Cu_2.75Ni_0.25Fe	250	0.1	1.68 × 10⁴	100	97	[4]
C₂H₂∶C₂H₄∶H₂ = 0.5∶25∶1	Pd₁/g-C₃N₄	110	0.1	3 × 10⁴	80	92	[33]
C₃H₄∶H₂ = 1∶3	Cu-Al HT	250	0.1	1.68 × 10⁴	100	—	[42]
C₂H₂∶H₂ = 1∶30	In₂O₃	350	0.1	—	100	85	[44]
C₂H₂∶C₂H₄∶H₂ = 1∶9∶1.8	Pd₄S/CNFs	250	0.1	6 × 10⁴	100	95	[47]
C₂H₂∶C₂H₄∶H₂ = 1∶99∶2	Ti-Pd/PHSNs	45	0.1	7200	70	69	[48]
C₂H₂∶C₂H₄∶H₂ = 1∶9∶1.2	Pd₄S/CNFs	250	1.8	2.16 × 10⁶	46.6	96	[49]
C₂H₂∶C₂H₄∶H₂ = 0.5∶20∶3	Pd@C/CNT	150	0.1	6 × 10⁴	93	70	[50]
C₂H₂∶C₂H₄∶H₂ = 1∶20∶20	AuPd_0.01/SiO₂	160	0.1	6 × 10⁴	86	56.4	[51]
C₂H₂∶C₂H₄∶H₂ = 0.8∶83.2∶16	Au/SiO₂	175	0.1	9.2 × 10⁴	94	47	[52]
C₃H₄∶H₂ = 1∶30	CeO₂	250	0.1	—	96	91	[53]
C₂H₂∶C₂H₄∶H₂ = 0.5∶50∶5	Al₁₃Fe₄	200	0.1	9× 10⁴	80	82	[54]
C₂H₂∶H₂ = 1∶5	Ni₆In/SiO₂	180	0.1	3.6× 10⁴	63	100	[55]
C₂H₂∶H₂ = 0.475∶9.25	CrO _x /(110)γ-Al₂O₃	140	0.1	2.166 × 10⁴	100	98.5	[56]

底物	催化剂	反应温度/℃	反应压力/MPa	转化率/%	选择性/%	参考文献
苯乙炔	Ag/SiO₂	100	10	30	100	[60]
苯乙炔	Au/CeO₂	25	3	99	99	[61]
苯乙炔	Pd₁/NC-PHF	60	0.5	93.1	93.5	[62]
苯丙炔	Meso-PdP	60	0.1	100	97.4	[63]
二苯乙炔	Pd-Pb NCs	25	0.1	96	96	[64]
2-甲基-3-丁炔-2-醇	Pd₃S/C₃N₄	30	0.1	—	100	[65]
1-戊炔	Pd/ZnO	100	0.1	41	87	[66]
1-辛炔	Pd@Ag/HAP	25	0.1	99	99	[67]
苯乙炔	H₃₅₀Ni/COF	100	1	>99	85	[68]
苯乙炔	Ni₂P@C-PPS/CNFs	100	0.5	100	94.6	[69]
苯乙炔	Ni@NC-800	110	1	97	94	[70]

底物	催化剂	反应温度/℃	反应压力/MPa	转化率/%	选择性/%	参考文献
苯乙炔	Ag/SiO₂	100	10	30	100	[60]
苯乙炔	Au/CeO₂	25	3	99	99	[61]
苯乙炔	Pd₁/NC-PHF	60	0.5	93.1	93.5	[62]
苯丙炔	Meso-PdP	60	0.1	100	97.4	[63]
二苯乙炔	Pd-Pb NCs	25	0.1	96	96	[64]
2-甲基-3-丁炔-2-醇	Pd₃S/C₃N₄	30	0.1	—	100	[65]
1-戊炔	Pd/ZnO	100	0.1	41	87	[66]
1-辛炔	Pd@Ag/HAP	25	0.1	99	99	[67]
苯乙炔	H₃₅₀Ni/COF	100	1	>99	85	[68]
苯乙炔	Ni₂P@C-PPS/CNFs	100	0.5	100	94.6	[69]
苯乙炔	Ni@NC-800	110	1	97	94	[70]

气体组成	催化剂	反应温度/℃	转化率/%	选择性/%	参考文献
C₂H₂∶C₂H₄:∶H₂=20∶20∶1	Pd₁/N-graphene	125	99	93.5	[77]
C₃H₄∶H₂=1∶5	Pt-SA/CsPbBr₃	5	—	86.6	[78]
C₂H₂=5%（体积分数）	[Ru(bpy)₃]²⁺/CoTPPS	室温	—	99	[79]
C₂H₂∶C₂H₄=1∶30	[Ru(bpy)₃]²⁺/CoTPPS	室温	100	98.9	[79]
C₃H₄=5%（体积分数）	[Ru(bpy)₃]²⁺/CoTPPS	—		99	[79]
C₂H₂∶C₂H₄∶H₂=1∶20∶10	Pd₁/TiO₂ SACs	120	100	>50	[80]