环己醇电解氧化制备己二酸  

Synthesis of Adipic Acid by Electro-oxidation of Cyclohexanol

作　　者：章晶晶[1] 黄武[2] 易清风[2] 周伟[2] 李晓虎[2] 刘小平[2] 

机构地区：[1]湛江师范学院化学科学与技术学院,湛江524048 [2]湖南科技大学化学化工学院,湘潭411201

出　　处：《应用化学》2008年第10期1171-1175,共5页Chinese Journal of Applied Chemistry

基　　金：湖南省教育厅重点项目(07A019);教育部留学回国人员科研启动基金([2007]1108)资助项目

摘　　要：研究了在1 mol/L NaOH溶液中环己醇电解氧化为己二酸。电解前,镍电极首先活化从而在其表面形成三价氢氧化镍(NiOOH),后者将环己醇氧化为环己酮,并进一步氧化为己二酸等产物。正交实验结果表明,在电流密度6×10-3A/cm2,反应温度60℃,反应时间16 F/mol(F为Faraday常数),NaOH浓度1.0 mol/L的条件下,己二酸产率为42.59%。电解动力学实验表明,反应具有典型连串反应的特征,各步骤的反应速率常数表明,环己醇电解氧化到环己酮是快反应,而环己酮进一步电解氧化到己二酸和戊二酸等产物是慢反应,是整个电解过程的控制步骤。Electro-synthesis of adipic acid from cyclohexanol in alkaline solution was investigated.Before electrolysis,the Ni electrode was activated by voltammetric technique to form NiOOH on its surface.Cyclo-hexanol was first oxidized to cyclohexanone and then to adipic acid on the activated Ni electrode.Orthogonal tests showed that the maximum yield of adipic acid was 42.59% under the optimum conditions of current density of 6×10^-3 A/cm^2,reaction temperature of 60 ℃,reaction time of 16 F/mol,and c（NaOH）=1.0 mol/L.Results of the kinetic study on the cyclohexanol oxidation show that the reaction obeys the consecutive reaction mechanism,and the formation of cyclohexanone is a fast step and the formation of adipic acid is a slower and rate-determining step.The corresponding kinetic equations of cycylohexanol oxidation were derived.The proposed kinetic model gave a satisfactory description for the electro-oxidation of cyclohe-xanol in 1 mol/L NaOH.

关 键 词：环己醇 镍电极 电氧化 己二酸 环己酮 

分 类 号：O646[理学—物理化学]