乙炔选择性加氢催化剂研究进展

doi:10.16085/j.issn.1000-6613.2021-2568

摘要/Abstract

摘要：

乙烯是石化工业中最重要的工业原料之一，然而乙烯产品中少量乙炔杂质的存在会直接影响乙烯的下一步应用。乙炔选择性催化加氢被认为是脱除乙炔杂质最有效的方法之一。本文综述了乙炔选择性加氢催化剂近年来的研究进展，介绍了乙炔选择加氢的反应机理，归纳总结了活性组分、助剂、载体以及结构对乙炔加氢催化剂性能的影响。鉴于Pd基催化剂仍然是工业应用的主流催化剂，文中综述了Pd基催化剂的研究现状和目前存在的一些挑战，同时提出了催化性能优化的建议。最后，就如何进一步提高乙炔选择性加氢催化剂性能的发展趋势进行了归纳，主要从单原子合金催化剂、催化剂微观调控以及电化学炔烃加氢方面进行论述，为未来提高乙炔加氢催化剂的性能提供了指导方向。

关键词: 乙炔加氢, 催化剂载体, 活性, 优化, 微观调控, 单原子合金, 电化学炔烃加氢

Abstract:

Ethylene is one of the most important industrial raw materials in petrochemical industry, however, the presence of a small amount of acetylene impurities in ethylene products will directly affect the subsequent application of ethylene. Selective catalytic hydrogenation of acetylene is considered to be one of the most effective methods for removing acetylene impurities. In this paper, the research progress of acetylene selective hydrogenation catalysts in recent years is reviewed, including the reaction mechanism, and the effects of active components, promoters, supports and structures on the catalyst performance. In view of the fact that the Pd-based catalysts are still the mainstream catalysts used in industry, the research status and current challenges of Pd-based catalysts are reviewed, and suggestions for the optimization of catalytic performance are proposed. Finally, the development trends to further improve the catalytic performance of acetylene hydrogenation catalysts are summarized, mainly from the aspects of single-atom alloy catalyst, catalyst micro-control, and electrochemical olefin hydrogenation.

Key words: acetylene hydrogenation, catalyst support, reactivity, optimization, micro-control, single-atom alloy, electrochemical alkynes hydrogenation

中图分类号:

O643.3

陈志强, 车春霞, 吴登峰, 温翯, 韩伟, 张峰, 许昊翔, 程道建. 乙炔选择性加氢催化剂研究进展[J]. 化工进展, 2022, 41(10): 5390-5405.

CHEN Zhiqiang, CHE Chunxia, WU Dengfeng, WEN He, HAN Wei, ZHANG Feng, XU Haoxiang, CHENG Daojian. Advances in catalysts for selective hydrogenation of acetylene[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5390-5405.

图/表 8

图1 乙炔加氢反应机理[13-14]

表1 不同载体种类对乙炔选择性加氢性能的影响

载体	活性组分	助剂	制备方法	反应温度/℃	反应时间/h	乙炔转化率/%	乙烯选择性/%
θ-Al₂O₃，δ-Al₂O₃^［74］	Pd	Ag，Ni	浸渍法	60	—	20~80	-60~80
α-Al₂O₃^［75］	Pd	Ag	浸渍法	60	80	80	90
γ-Al₂O₃^［76］	Pd	—	浸渍法	30	—	100	60
β-Al₂O₃^［77］	Pd	—	—	60~100	—	90	95
SiO₂^［38］	Pd	Au，Ag	化学沉积	65	—	20~60	55~80
TiO₂^［78］	Pd	Ag	浸渍法	40	—	5~60	10~57
C^［79］	Pd	Zn	浸渍法	120	—	100	82
多金属氧酸盐的金属-有机骨架（MOF）^［80］	Pd	—	原位还原	120	12	100	92.6
氮掺杂石墨烯（N-Gr）^［81］	Pd	—	冷冻干燥辅助法	125	24	99	93.5
氮掺杂碳纳米球^［82］	Pd	—	模板路易斯酸掺杂法	110	20	83	82
氮掺杂碳纳米管（N-CNTs）^［83］	Pd	—	化学气相沉积法	80	35	80以上	40左右
ZnO-Al₂O₃^［84］	Pd	Ag	共沉淀法	90	3	90~100	77.6
MgO ^［85］	Pd	—	球磨	140	50	100	70以上
金刚石/石墨烯^［28］	Pd	—	退火处理、溶液合成	180	30	100	90
金刚石/石墨烯^［86］	Cu	—	退火处理、溶液合成	200	60	95	98

图2 CO漫反射傅里叶变换红外光谱（DRIFTS）以及X射线吸收光谱（XAS）图[100]（1Å=0.1nm）

表2 Pd1Au(111)、Pd1Ag(111)、Pd1Cu(111)和Pd(111)表面乙烯吸附能[100-102]

金属表面	d（C $̿$ C）/Å	ΔE（C₂H₄）/eV
Pd(111)	1.45	-0.91
Pd₁Au(111)	1.39	-0.53
Pd₁Ag(111)	1.39	-0.46
Pd₁Cu(111)	1.39	-0.51

表2 Pd1Au(111)、Pd1Ag(111)、Pd1Cu(111)和Pd(111)表面乙烯吸附能[100-102]

金属表面	d（C $̿$ C）/Å	ΔE（C₂H₄）/eV
Pd(111)	1.45	-0.91
Pd₁Au(111)	1.39	-0.53
Pd₁Ag(111)	1.39	-0.46
Pd₁Cu(111)	1.39	-0.51

图3 MOF限制的共还原策略示意图以及催化剂尺寸表征图[106]

图4 海胆状以及八面体PdAuAg催化剂的表征图[108]

图5 Cu催化剂、阴极示意图以及催化剂性能图[112]

图6 传统热催化及电催化乙炔加氢过程[113]

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