甘油直接制备丙烯醇的催化剂和反应工艺研究进展

doi:10.16085/j.issn.1000-6613.2019-1738

摘要/Abstract

摘要：

丙烯醇是一种十分重要的中间体和化学原料。近年来，以甘油为原料直接制备丙烯醇的研究引起了许多科学家的关注。本文参考了最近十年来发表的文献，详细介绍了均相甲酸诱导的甘油脱氧脱水反应、催化剂作用下的甘油脱氧脱水反应、液固相甘油氢解反应和气固相甘油氢转移反应等过程制备丙烯醇的相关工艺、反应机理和催化剂的研究进展及发展趋势，并对比了上述工艺的优缺点。其中，均相甲酸诱导的甘油脱氧脱水工艺比较成熟，已经在实验室中得到验证和应用，但是甲酸的消耗量大，整个过程的原子经济性很差。甘油脱氧脱水反应和液固相甘油氢解反应不仅需要采用价格昂贵的铼基催化剂，而且丙烯醇的选择性较低。铁基催化剂作用下的气固相甘油氢转移反应制备丙烯醇，由于催化剂的价格低廉、制备工艺简单、产品分离容易等优势而备受关注，是最近五年的研究热点。在文献基础上，认为今后研究应该重点关注催化剂的酸碱性、氢转移能力及其与速率控制步骤的匹配，并有针对性地对催化剂进行优化和改进。

关键词: 丙烯醇, 甘油, 催化剂, 反应机理

Abstract:

Allyl alcohol is a pivotal intermediate. Production of allyl alcohol by renewable glycerol is of great importance and has attracted the attentions of many scientists. On the base of published works, this review discussed the recent progresses of catalytic synthesis of allyl alcohol from glycerol. The reaction conditions, catalysts and mechanism of formic acid-mediated homogenous deoxydehydration (DODH) of glycerol, Re catalyzed DODH of glycerol, direct hydrogenolysis of glycerol in liquid phase, and catalytic transferred hydrogenation (CTH) of glycerol in vapor-phase were summarized. Among of which, formic acid-mediated homogenous DODH reaction had been applied in the laboratory, but the atomic economy of the whole process was poor due to the high consumption of formic acid. The selectivity of allyl alcohol in Re catalyzed DODH of glycerol and direct hydrogenolysis of glycerol in liquid phase was low. The continuous CTH of glycerol over Fe-based catalyst in vapor-phase was the hot topics for its simple preparation process, low price of catalyst and easiness in product separation. At last, it was suggested that the acidity/basicity and the activity of hydrogen transfer of the catalyst, and its matching with the rate determining step should be focused in the future research.

Key words: allyl alcohol, glycerol, catalyst, reaction mechanism

中图分类号:

O643.32

侯珏, 李春虎. 甘油直接制备丙烯醇的催化剂和反应工艺研究进展[J]. 化工进展, 2020, 39(7): 2648-2655.

Jue HOU, Chunhu LI. Catalysts and technology for the synthesis of allyl alcohol from glycerol[J]. Chemical Industry and Engineering Progress, 2020, 39(7): 2648-2655.

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