连续流选择性加氢技术研究进展

doi:10.6023/cjoc202310006

摘要/Abstract

流动氢化技术是合成制备精细化学品的重要手段, 在制备药物中间体及生产高值化学品方面占比极大. 非均相催化氢化法具有优良的经济环保性, 通过使用负载型催化剂能有效减少污染物排放, 提高底物转化率以及选择性. 详细介绍了按催化剂负载方式分类的微反应器类型以及常用的固体催化剂, 阐述了连续流技术在不同官能团催化氢化领域中取得的进展. 在此基础上概述了作为十大新兴化学技术之一的流动化学, 在催化加氢应用上具有极大远景, 连续、自动化和智能化技术是制药和化学工业的未来.

关键词: 氢化, 多相催化, 流动化学, 微反应器

Flow hydrogenation technology is an important means of synthesizing and preparing fine chemicals, accounting for a significant proportion of the preparation of pharmaceutical intermediates and the production of high-value chemicals. The heterogeneous catalytic hydrogenation method has excellent economic and environmental protection properties. By using loaded catalysts, pollutant emissions can be effectively reduced, and substrate conversion rate and selectivity can be improved. This article provides a detailed introduction to the types of microreactors classified by catalyst loading methods and commonly used solid catalysts and elaborates on the progress made by continuous flow technology in the field of catalytic hydrogenation of different functional groups. On this basis, flow chemistry, as one of the top ten emerging chemical technologies, has great prospects in catalytic hydrogenation applications. Continuous, automated, and intelligent technologies are the future of the pharmaceutical and chemical industries.

Key words: hydrogenation, heterogeneous catalysis, flow chemistry, microreactor

引用此文

密思怡, 马隆龙, 刘建国. 连续流选择性加氢技术研究进展[J]. 有机化学, 2024, 44(5): 1445-1457.

Siyi Mi, Longlong Ma, Jianguo Liu. Research Progress of Continuous Flow Selective Hydrogenation Technology[J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1445-1457.

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图/表 15

图1. 三种微反应器示意图

Figure 1. Schematic representation of microchannel in three types (a) Packed-bed, (b) monolithic and (c) wall-coated

图2. 基于微填充床反应器内进行的流动氢化系统示意图[13]

Figure 2. Schematic representation of flow hydrogenation system based on micro-packed bed reactor

图3. 连续流氢化反应中催化静态混合器简化装置示意图[19]

Figure 3. Simplified device diagram of the tubular flow reactor set-up for continuous flow hydrogenation reaction

图4. 负载型催化剂制备工艺示意图[33]

Figure 4. Schematic representation of the supported catalyst preparation process

图5. 碳碳双键的连续加氢

Figure 5. Continuous hydrogenation of carbon-carbon double

图6. 涡流流体装置图[40]

Figure 6. Schematic representation of the vortex fluidic device

图7. 炔烃的连续加氢

Figure 7. Continuous hydrogenation of alkynes

图8. 由MOF-74(Ni)合成的Ni@C用于苯乙炔半氢化示意图

Figure 8. Diagram of Ni@C synthesis from MOF-74(Ni) for semi hydrogenation of phenylacetylene

图9. 羰基的连续加氢

Figure 9. Continuous hydrogenation of carbonyl groups

图10. H-Cube? Mini Plus系统示意图[61]

Figure 10. Diagram of H-Cube ? Mini Plus

图11. 硝基的连续加氢

Figure 11. Continuous hydrogenation of nitro groups

Operation mode	Conversion/%	Selectivity/%
Batch	100	61.8
Continuous flow	100	99.7

表1. 间歇与连续流中转换率和选择性比较

Table 1. Comparison of conversion rate and selectivity between batch and continuous flow mode

图12. 氰基的连续加氢

Figure 12. Continuous hydrogenation of cyanide groups

图13. 连续流中苄基脱保护反应

Figure 13. Deprotection reaction of benzyl groups

图14. 苄氧羰基的脱保护反应

Figure 14. Deprotection reaction of benzyloxy carbonyl groups

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