乙醇介质中生物质基糠醛一锅三步法制备γ-戊内酯的研究

Furfural is an important biomass-derived platform compound, recently, much effort has been devoted to convert furfural into liquid fuels and organic bulk chemicals. The conversion of furfural into γ-valerolactone is very important pathway for the utilization of biomass. According to the current research advances and existing problems for the conversion of furfural into γ-valerolactone, a series of studies persisted in the concept of green chemical engineering will be carried out in this project. Firstly, the reaction system will be developed for the transfer hydrogenation of furfural to furfuryl alcohol using ethanol as H-doner in the presence of ethanol and catalysts. Secondly, the reaction system will be established for the alcoholysis of furfuryl alcohol to ethyl levulinate in ethanol medium, and the possible reaction mechanism will be presented. Eventually, the reaction system will be built for the transfer hydrogenation of ethyl levulinate to γ-valerolactone, and γ-valerolactone wil be separated and purified from the crude mixture. Furthermore, the technology roadmap for the conversion of furfural into γ-valerolactone will be drafted to provide theoretical reference and technical support for the commercial production of γ-valerolactone in the future.

糠醛是一种重要的生物质基平台化合物，将其转化为具有广泛用途的能源化学品γ-戊内酯是深度开发利用生物质资源的重要途径之一，但是制备过程中存在生产成本较高，反应条件苛刻的问题。本项目秉承绿色化工的理念，拟研究开发在乙醇介质中糠醛一锅三步法制备γ-戊内酯的新途径。具体内容包括：糠醛转移加氢制备糠醇反应体系的建立；糠醇醇解制备乙酰丙酸乙酯反应体系的建立及反应机理探索；乙酰丙酸乙酯转移加氢制备γ-戊内酯反应体系的建立、反应机理探索及产物分离纯化。本项目拟通过制备绿色高效催化剂；优化反应过程；探索糠醇醇解和乙酰丙酸乙酯转移加氢的反应机理等研究，为生物质基糠醛制备γ-戊内酯提供理论基础和技术支持。

将生物质基平台化合物糠醛通过一锅三步法制备新型能源化学品γ-戊内酯，是深度开发利用生物质资源的重要途径之一，也是生物质化工领域的研究热点，但是，在整个制备过程中存在着副产物较多，生产成本较高，反应条件苛刻的问题。在课题组前期研究的基础上，本项目首先制备了廉价的金属氢氧化物催化剂Al(OH)3，以乙醇作为原位氢供体并通过MPV反应将糠醛选择性加氢转化为糠醇；然后，制备了碳基固体酸催化剂GCC，在乙醇介质中，催化糠醇醇解制备乙酰丙酸乙酯，并对反应条件进行了调控和优化；接着，我们使用另一种廉价的金属氢氧化物催化剂Ni(OH)2，以乙醇作为原位氢供体并通过MPV反应将乙酰丙酸乙酯选择性加氢转化为γ-戊内酯；最后，通过结合催化剂表征、反应条件优化和理论模拟结果，揭示了催化剂组成-结构-性能之间的关系，阐明了选择性加氢制备糠醇和γ-戊内酯以及醇解制备乙酰丙酸乙酯的反应机理，进而为生物质基糠醛制备γ-戊内酯提供了理论基础和技术支持。