金属卟啉催化空气氧化环己烷反应的工艺优化

Optimization of aerobic oxidation of cyclohexane catalyzed by metalloporphyrins

简单铁、钴、铜、锰四苯基卟啉用于催化空气氧化环己烷联产KA油(环己醇和环己酮)和己二酸的反应,利用正交实验方法考察了锰四苯基卟啉催化下环己烷氧化反应中反应温度、压力、空气流速、时间、催化剂用量对反应转化率和产物选择性的影响,并获得了优化的工艺条件。以醇酮酸(环己醇、环己酮和己二酸)总产率作为评价指数进行极差分析得到温度、空气流速、反应时间、压力、催化剂量的极差值分别为6.17、3.12、2.25、1.81、1.53,表明温度是影响环己烷氧化的关键因素。锰四苯基卟啉催化环己烷空气氧化反应的优化工艺条件为温度150℃、压力1.2MPa、空气流速0.13m3.h-1、催化剂用量7mg、反应时间3.5h。验证实验表明,在上述优化条件下,环己烷转化率达20.0%,醇酮酸总选择性可达90.0%,己二酸选择性达到21.0%。

The simple metalloporphyrins TPPMC1 （M=Fe, Mn） and TPPM （M=Co, Cu） are generally used to catalyze the aerobic oxidation of cyclohexane to KA oil （cyclohexanol and cyclohexanone） and adipic acid. By using orthogonal design, the influence of reaction temperature, the air flow rate, the reaction time, amount of catalyst and pressure on the cyclohexane aerobic oxidation over TPPMnCl was studied, and the optimized conditions for the cyclohexane oxidation with air catalyzed by TPPMnC1 were obtained. Range analysis results of the above five factors were 6.17, 3.12, 2.25, 1.81, 1.53 respectively by taking the total yield （including cyclohexanol, cyclohexanone and adipic acid） as the evaluation index, indicating that reaction temperature was the key factor. Under the optimized conditions of reaction temperature 150℃, pressure 1.2 MPa, air flow rate 0. 13 m^3 · h^-1 , 7 mg of TPPMnCl , and reaction time 3.5 h, the conversion of cyclohexane was 20.0%, the total selectivity was 90.0%, and the selectivity of adipic acid could go up to 21.0%.