乙炔氢氯化反应无汞贵金属催化剂的研究进展

doi:10.16085/j.issn.1000-6613.2020-0687

摘要/Abstract

摘要：

受“水俣公约”和环境保护政策约束，研究和开发新型无汞催化剂是保障我国乙炔法制备聚氯乙烯未来发展的核心环节。无汞催化剂包括贵金属催化剂、非贵金属催化剂和非金属催化剂，其中贵金属催化剂被认为是最具有工业化应用前景的催化剂。本文概述了近年来国内外乙炔氢氯化贵金属Au、Ru、Pd和Pt催化剂的研究进展，重点综述了不同催化剂的活性组分、催化机理及催化剂的改性方法等方面的研究，分析了不同改性方法的作用机制及不同催化剂改性的研究方向。研究表明，添加助剂或多金属复配、配体和离子液体的使用及载体改性均使贵金属催化剂的催化活性和稳定性得到一定程度提高，从而进一步增加了贵金属催化剂工业化应用的可能性。

关键词: 乙炔氢氯化, 催化剂, 贵金属, 活性, 离子液体

Abstract:

According to the “Minamata Convention” and environmental protection policy, the development of mercury-free catalysts for acetylene hydrochlorination is indispensable and exigent in China. Among all kinds of mercury-free catalysts including noble metal, non-noble metal and non-metallic catalysts, noble metal catalyst is considered to be the most promising catalyst for industrial application. The research progress of Au, Ru, Pd and Pt based catalysts for acetylene hydrochlorination in recent years was reviewed, with the emphasis on the active components, catalyst mechanism and modification methods of different catalysts. The effects of different modification methods and the research direction of each catalyst were also analyzed. The use of promoters, ligands and ionic liquids, as well as the modification of supports, can improve the activity and stability of catalysts, and increase their industrial application possibility.

Key words: acetylene hydrochlorination, catalysts, noble metal, activity, ionic liquid

中图分类号:

TQ426

代元元, 李杰, 王志文, 赵长森, 解荣永. 乙炔氢氯化反应无汞贵金属催化剂的研究进展[J]. 化工进展, 2021, 40(2): 813-823.

Yuanyuan DAI, Jie LI, Zhiwen WANG, Changsen ZHAO, Rongyong XIE. Research progress of mercury-free noble metal catalysts for acetylene hydrochlorination[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 813-823.

图/表 12

图1 金属氯化物的乙炔氢氯化反应活性与标准电极电势的关系[8]

图2 Au/C催化剂上乙炔氢氯化反应模型和反应能量分布[9]

图3 添加不同金属氧化物助剂的Au基催化剂的乙炔转化率(180℃,720h-1)和Au基催化剂的稳定性测试(180℃，60h-1)[17]

表1 不同助金属对Au基催化剂的催化性能影响

催化剂	温度 /℃	空速 /h^-1	运行时间 /h	转化率 /%	选择性 /%	参考文献
Au(0.5%)-Cu/AC	160	50	200	99.5	99.5	[21]
Au(1%)-Sn/AC	170	720	48	95	99	[22]
Au(0.3%)-Bi/AC	180	600	5	85	—	[23]
Au(1%)-Cs/AC	180	50	500	99.5	99.9	[24]
Au(0.2%)-Cu-K/AC	165	40	1600	89	99.7	[25]
Au(0.25%)-Cu-Cs/AC	180	50	600	98.5	99.9	[26]
Au(1%)-In-Cs/AC	180	1480	50	89.1	99.9	[13]
Au(1%)-Li/AC	180	600	48	91.3	99.9	[27]
Au(1%)-Ba/AC	200	360	86	92.3	99.9	[28]
1Au(1.5%)-Ni/CSs	170	900	46	97	99.9	[29]

表2 不同配体对Au基催化剂的催化性能影响[30]

Au前体配合物	Au负载量/%	转化率/%
Au[CS(NH₂)₂]₂	0.1	95
Na₃Au(S₂O₃)₂	0.1	86
KAu(CN)₂	0.1	85
(NH₄)₃Au(S₂O₃)₂	0.1	75
KAu(SCN)₄	0.1	74
Ca₃[Au(S₂O₃)₂]₂	0.1	74
KAu(CN)₄	0.1	69
Au(NCNH₂)₂	0.1	55
HAuCl₄+Aqua regia	1	52
HAu(C₃Cl₃N₃O₃)₃Cl	1	52
[Au(P(NCH₂CH₂OCH₂CH₂)₃)₂]NO₃	1	33
[(AuCl)₂dppe]	1	14
[Au(en)₂]Cl₃	1	14
HAuCl₄+H₂O	1	11
炭黑挤出物(无Au)	0	7

图4 不同配体对于0.25% Au催化剂性能的影响和反应机理(180℃，600h-1)[31]

图5 不同原料气对Au/AC和Au-IL/AC催化剂催化性能的影响(180℃，180h-1)[34]

图6 基于Ru5Cl7乙炔氢氯化的反应能量分布[39]

图7 Ru@IL/AC催化剂乙炔氢氯化的催化机理[45]

图8 体系2(M=Pt)和体系3(M=Pd)乙炔氢氯化的分步机理[47]

图9 离子液体改性的Pd催化剂的乙炔转化率及与Au基催化剂时空收率对比(160℃，1000h-1)[53]

图10 不同催化剂的时空收率随着反应时间的变化及反应50h后的STEM图[54]

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