The Research On Metalloporphyrins Catalyzed H₂O₂ Oxidation Of Cyclohexanone

Adipic acid, is the most valuable diacid among the alkyl diacids as well as the most important industrial product and intermediates. With the development of the economy, the demand of adipic acid becomes larger. The oxidation system of cyclohexane mainly adopted nitric acid oxidation process in the past time. This oxidation process is complex. It is difficult to achieve high convers ion of cyclohexane and high selectivity of adipic acid at the same time. Meanwhile, a large number of NOx?N2O are produced in this process. Nowadays, under the premise of increasingly serious environmental problems, the research on the green synthesis process of adipic acid have an important significance.Based on this, The research is focused on the absence of a solvent and in the case of no aid to metalloporphyrins as catalyst. Under atmospheric pressure and low temperature conditions, cheaper 30% hydrogen peroxide as oxidant oxidation of cyclohexanone, the main product of butyric acid and adipic acid with high selectivity is obtained.In order to research and analysis the process about hydrogen peroxide oxidation of cyclohexanone catalyzed by metalloporphyrins, firstly, we reviewed the supply and demand situation of monobasic acid and binary acid, the different technology of the synthesis of adipic acid and the catalyst system of oxidation of cyclohexanone were summarized.Secondly, according to the demand of our research, the reaction liquid of metalloporphyrins catalyzed H₂O₂ oxidation of cyclohexanone were analyzed by GC-MS. The methods of qualitative and quantitative analysis of the products about oxidation of cyclohexanone have been established. These analysis methods were repeatable and accurate.Then, to understand the law of cyclohexanone oxidation reaction, we were investigated the influence of different metalloporphyrin catalyst, at different temperatures and at different times of the metalloporphyrins catalyzed oxidation of cyclohexanone reaction product conversion, selectivity and yield effect. And by using the orthogonal experiment researched the effects of the variety of solvent, reaction temperature, reaction time, type of catalyst, the material ratio of the reaction. The aim to reference the selectivity of adipic acid, the optimized reaction conditions show as follow:(T_p-ClPPFe)₂Cl as catalyst, the reaction temperature was 80 ?, the mole ratio of hydrogen peroxide and cyclohexanone was 1:5, and the reaction time was 4 h.Finally, we analysised the reaction of(T_p-ClPPFe)₂Cl catalyzed H₂O₂ oxidation of cyclohexanone by the methods of thermodynamics and dynamics. The study found that the reaction of(T_p-ClPPFe)₂Cl catalyzed H₂O₂ oxidation of cyclohexanone was a dynamic controlled process. The reaction of(T_p-ClPPFe)₂Cl catalyzed H₂O₂ oxidation of cyclohexanone were considered at the same time the concentration of components changed over time in different temperatures which were determined by using othermal method from 353 K to 338 K, The kinetics model of the reaction of(T_p-ClPPFe)₂Cl catalyzed H₂O₂ oxidation of cyclohexanone were established in combination with allenuzi formula. The data was processed by the ode45?F? function in the integration of the matlab software. The calcula ted data matched experimental data. kinetic constant various equations were obtained. The influence of temperature on the reaction rate constant of(T_p-ClPPFe)₂Cl catalyzed H₂O₂ oxidation of cyclohexanone have been analysed. The dynamics preliminary analys is of cyclohexanone oxidation reaction will provide data information for later industrialization.