丙二酸二乙酯加氢合成1,3-丙二醇反应的研究

Hydrogenation of diethyl malonate to 1,3-propanediol

对丙二酸二乙酯(DEM)加氢还原合成1,3-丙二醇反应体系进行了热力学分析和实验研究,考察了铜基催化剂体系的优化工艺条件。结果表明,主反应为放热反应,不可自发向右进行,提高压力和降低温度对主反应有利。对该反应,铜基催化剂优于银基和镍基催化剂,其最佳反应条件为:200℃、2MPa、原料液(DEM乙醇溶液)w(DEM)为10%、n(H_2)/n(DEM)为440。在此条件和液时空速1.2h^(-1)下,DEM转化率达到69.83%,1,3-丙二醇的选择性和收率分别为21.19%和14.80%。

Thermodynamics and process feasibility of hydrogenation of diethyl malonate（DEM） to 1,3-propanediol were studied,and the synthesis conditions over the copper-based catalyst were optimized. Results showed that the main reaction was an exothermic reaction and could not occur spontaneously, but could be promoted by increasing pressure and decreasing temperature. The copperbased catalyst was better than the Ag-based and Ni-based catalysts for this reaction, and the opitimum reaction conditions for it were determined as follows： 200℃, 2MPa, diethyl malonate mass fraction of 10% in the feed ethanol solution and H2/DEM mole ratio of440. Under above conditions and LHSV of 1.2h^-1, the conversion of diethyl malonate reached 69.83% and the selectivity and yield of1,3-propanediol were 21.19% and 14.8%, respectively.