丙二酸二乙酯加氢制备1,3-丙二醇反应动力学研究

Kinetic study of diethyl malonate hydrogenation over copper-based catalyst

铜基催化剂催化丙二酸二乙酯加氢一条绿色制备1,3-丙二醇的路线。在消除内外扩散的基础上,根据丙二酸二乙酯加氢反应体系建立本征动力学反应模型,得到了在实验条件下适定的动力学模型、反应物的吸附方式和速率控制步骤。进一步通过该模型的活化能、吸附焓和指前因子计算,说明了提高选择性催化酯基能力和抑制副产物丙酸乙酯的生成是以后提高丙二酸二乙酯加氢制备1,3-丙二醇的关键。为以后合理设计催化丙二酸二乙酯加氢制备1,3-丙二醇的铜基催化剂提供了基础。

The synthesis of 1,3-propanediol through diethyl malonate hydrogenation have received considerable attention due to its low-cost and eco-friendly advantages.The intrinsic kinetic models were proposed based on different rate-determining and adsorption steps including dissociative and molecular ways.Besides,the parameters in obtained appropriate kinetic model was carefully calculated and were further examined with the criterions.The reaction rate constants and adsorption equilibrium constants suggest the improvement of 1,3-propanediol yield lies on enhancement of selectively active C=O groups and inhibition of ethyl propionate products.The available information in this study provides a direction to rationally design copper-based catalyst for diethyl malonate hydrogenation process.