环戊烯选择氧化合成戊二酸绿色催化过程

Green Catalytic Process for Synthesis of Glutaric Acid by Selective Oxidation of Cyclopentene

研究了以环戊烯为原料、草酸为有机络合剂、H2O2为氧化剂,在催化剂钨酸(H2WO4)的作用下一步合成戊二酸的绿色新过程,考察了氧化剂的含量、反应物配比、催化剂用量、反应温度、反应时间等对反应的影响。确定了最佳反应条件:选用50%(质量分数)的H2O2为氧化剂、反应物配比n(H2O2)∶n(环戊烯)=4.4、n(H2WO4)∶n(草酸)=1、催化剂用量(H2WO4占环戊烯的摩尔分数)1.5%、反应温度85℃、反应时间6h。在最佳反应条件下,戊二酸的收率高达92.3%。该方法洁净、高效,产物戊二酸的纯度高,符合绿色化学的要求。实验结果表明,强酸性环境有利于戊二酸的生成,表明此反应为酸催化的选择氧化反应。

A novel one-step green process for synthesis of glutaric acid by selective oxidation of cyclopentene was investigated. Hydrogen peroxide （H2O2）was used as oxidant, oxalic acid as complexing agent and tungstic acid（ H2WO4 ）as catalyst. Glutadc acid can be used as starting material for synthesizing plasticizers and disinfectants. Under optimal reaction conditions：50% （mass fraction） hydrogen peroxide as oxidant, n （ H2O2 ） ： n （cyclopentene） = 4.4, n （ H2WO4 ） ： n （ oxalic acid） = 1, catalyst content 1.5 % （ mole fraction in cyclopentene）, reaction temperature 85℃ and reaction time 6 h, yield of glutaric acid could reach 92.3 %. Since H2O2 was used as oxidant, the process, without any phase-transfer catalyst and organic solvent, was clean and non-toxic, and could meet requirement of environmental protection. It was found that strong acidity was favorable to the process therefore tungstic acid was a very suitable catalyst for the reaction.