Cu-H_4SiW_(12)O_(40)/SiO_2催化甘油氢解合成1,3-丙二醇反应研究

Synthesis of 1,3-propanediol through glycerol hydrogenolysis catalyzed by Cu-H_4SiW_(12)O_(40)/SiO_2

甘油氢解制备1,3-丙二醇是一条绿色反应途径.首先评价了一系列SiO2负载Cu-杂多酸的催化性能,发现Cu-H4SiW12O40/SiO2的催化活性最好.然后,分别考察了溶剂和反应条件对该反应的影响.结果表明:适宜的溶剂为正丙醇;在催化剂用量为甘油质量的11.0%、甘油溶液浓度50%、反应温度180℃、H2初压9.0 MPa、反应时间16h条件下,甘油转化率为28.3%,1,3-丙二醇的收率和选择性分别达到6.3%和22.3%.在此基础上,采用GC-MS对反应体系进行了定性分析,并对可能发生的副反应进行了合理的推测.

Hydrogenolysis of glycerol to 1,3- propanediol is a green route. The catalytic performance of some silica-supported copper-heteropoly acid catalysts was evaluated and Cu-H4 SiW12 O40 /SiO2 showed the highest catalytic activity. Then the effects of solvent and reaction conditions were studied. 1-Propanol was selected as the suitable solvent. Under the reaction conditions of weight ratio of Cu-H4 SiW12 O40 /SiO2 to glycerol = 11∶100, 50% of glycerol solution, reaction temperature of 180 ℃, H2 initial pressure of 9.0 MPa and reaction time of 16 h, the conversion of glycerol was 28.3%, the yield and selectivity of 1,3-propanediol reached 6.3% and 22.3%, respectively. Furthermore, GC-MS was used for qualitative analysis of the reaction system and the formation of byproducts was proposed reasonably.