微反应器中连续还原胺化反应的研究进展

doi:10.16085/j.issn.1000-6613.2023-1479

摘要/Abstract

摘要：

还原胺化反应是一种把醛（酮）转化为胺类物质的有效方法。还原胺化反应路径复杂，影响因素众多，合适的反应条件能够提升反应效率和选择性。本文总结了还原胺化反应常见的催化体系及催化剂、溶剂、温度、底物性质以及氨/水/酸的加入对反应的影响。基于这些影响因素，进一步介绍了连续微反应器技术在还原胺化过程中的应用，总结了以伯胺/仲胺/叔胺为目标产物的连续还原胺化过程、以硝基化合物为原料的连续还原胺化过程、酶催化及无催化剂的连续还原胺化过程。微反应器中的温度控制、传质强化和停留时间分布能进一步实现反应强化和选择性提升。基于微反应器的连续还原胺化技术及该技术与新型催化材料的结合有望在胺类物质的生产领域扮演越来越重要的角色。

关键词: 还原胺化, 多相反应, 微反应器, 连续合成, 催化剂

Abstract:

Reductive amination is a convenient way to transform aldehydes (ketones) into amines. Reductive amination has a complex reaction pathway and numerous influencing factors. The implementation of appropriate reaction conditions can significantly enhance reaction efficiency and selectivity. This article summarizes prevalent catalytic systems and the impacts of catalysts, solvents, temperatures, substrate properties, as well as the addition of ammonia/water/acid on the reductive amination. Subsequently, the utilization of microreactors in reductive amination is further discussed. The discussion encompasses continuous reductive amination process with primary, secondary, and tertiary amines as the target product, continuous reductive amination processes utilizing nitro compounds as starting materials, enzyme-catalyzed, and catalyst-free continuous reductive amination processes. Temperature control, mass transfer enhancement, and residence time distribution within microreactors can further intensify the reaction and improve the selectivity. The continuous reductive amination technology, coupled with novel catalytic materials, is expected to play an increasingly pivotal role in the production of amine compounds.

Key words: reductive amination, multiphase reaction, microreactors, continuous synthesis, catalyst

中图分类号:

TQ032.4

张家昊, 李盈盈, 徐彦琳, 尹佳滨, 张吉松. 微反应器中连续还原胺化反应的研究进展[J]. 化工进展, 2024, 43(1): 186-197.

ZHANG Jiahao, LI Yingying, XU Yanlin, YIN Jiabin, ZHANG Jisong. Research advancement of continuous reductive amination in microreactors[J]. Chemical Industry and Engineering Progress, 2024, 43(1): 186-197.

图/表 11

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催化剂	反应条件	收率/%	参考文献
Ru/C^ox	90℃，4MPa	98	[27]
Ru₁/NC	100℃，2MPa	97	[16]
Ru/TiP	30℃，1.4MPa	97	[32]
[Rh(cod)Cl]₂	135℃，6.5MPa	86	[33]
Rh/Al₂O₃	80℃，2MPa	92	[34]
Ni/Al₂O₃	80℃，1MPa	99	[15]
Ni _y AlO _x	100℃，0.1MPa	99	[37]
Ni/SiO₂	70℃，1MPa	99	[38]
Fe/SiC	140℃，6.5MPa	99	[39]
Co/SiC	50℃，1MPa	99	[40]
Pd/C	80℃，3.5MPa	100	[41]
Pd/NiO	25℃，0.1MPa	98	[42]
Pt/Al₂O₃	25℃，0.5MPa	99	[43]
Au/CeO₂/TiO₂	100℃，3MPa	79	[46]
Ru(DMP)₂Cl₂	60℃，1.2MPa	98	[47]
Co/NC	110℃，1MPa	98	[48]
[Rh(COD)Cl]₂	100℃，1.4MPa	86	[49]
Cu/AlO _x	80℃，1MPa	99	[50]
Cu/SiO₂TiO₃	100℃，0.1MPa	97	[51]
Pt nanowire	80℃，0.1MPa	93.3	[52]
PtMo nanowire	100℃，0.1MPa	96.1	[18]
Pd/Fe₂O₃	0℃，0.1MPa	96.6	[39]

催化剂	反应条件	收率/%	参考文献
Ru/C^ox	90℃，4MPa	98	[27]
Ru₁/NC	100℃，2MPa	97	[16]
Ru/TiP	30℃，1.4MPa	97	[32]
[Rh(cod)Cl]₂	135℃，6.5MPa	86	[33]
Rh/Al₂O₃	80℃，2MPa	92	[34]
Ni/Al₂O₃	80℃，1MPa	99	[15]
Ni _y AlO _x	100℃，0.1MPa	99	[37]
Ni/SiO₂	70℃，1MPa	99	[38]
Fe/SiC	140℃，6.5MPa	99	[39]
Co/SiC	50℃，1MPa	99	[40]
Pd/C	80℃，3.5MPa	100	[41]
Pd/NiO	25℃，0.1MPa	98	[42]
Pt/Al₂O₃	25℃，0.5MPa	99	[43]
Au/CeO₂/TiO₂	100℃，3MPa	79	[46]
Ru(DMP)₂Cl₂	60℃，1.2MPa	98	[47]
Co/NC	110℃，1MPa	98	[48]
[Rh(COD)Cl]₂	100℃，1.4MPa	86	[49]
Cu/AlO _x	80℃，1MPa	99	[50]
Cu/SiO₂TiO₃	100℃，0.1MPa	97	[51]
Pt nanowire	80℃，0.1MPa	93.3	[52]
PtMo nanowire	100℃，0.1MPa	96.1	[18]
Pd/Fe₂O₃	0℃，0.1MPa	96.6	[39]

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