The Study On The Phase Equilibrium Of Biomimetic Catalytic Oxidation Of Cyclohexanone And The Production Of Metalloporphyrins

As a kind of important chemical product and intermediate in organic synthesis, which was widely used in manufactured fields of plasticizer, fiber, food additive and nylon-66, the demand of adipic acid increased every year. At present, it mainly adopted the oxidant nitric acid to react with the mixtures of cyclohexanone and cyclohexanol in order to obtain adipic acid in industry. However, there were too many processes and the equipment was easily to corrosion in the practical production. Moreover, it would emit a large number of greenhouse gases NOx.These shortcomings limited the further production of adipic acid.In view of the above problems, the oxidation of cyclohexanone, the O2 as oxygen source and the metalloporphyrin as catalyst, was researched and a set of feasible analysis method was established in this work. Moreover, it was explored the suitable catalyst and solvent and the optimized process condition was obtained. Meanwhile, the solubilities of dicarboxylic acid (adipic acid, glutaric acid, and succinic acid) in solvent mixtures were measured and the corresponding thermodynamic model of solid-liquid equilibrium (SLE) was established to provide the basic data for the oxidation reaction. In additional, the solubilities of several metalporphyrins in the process were measured and the corresponding thermodynamic model of SLE was established to provide the basic data for the production of metalloporphyrins. The detail works were as follows:The influence of metalporphyrins and reaction solvents to the oxidation of cyclohexanone was studied respectively; By using the orthogonal experiment, it was studied the influence of the dosage of catalyst, temperature, reaction time and the ratio of acetic acid and cyclohexanone to the oxidation of cyclohexanone; By an intuitive analysis of the experimental result, the optimization condition was obtained. Under the optimum reaction condition, the convention rate of cyclohexanone was 93.10%, while the yield of adipic acid could reach up to 51.92%.Under experimental temperature ranged from 305.55 to 343.15 K, the solubility of dicarboxylic acid (adipic acid, glutaric acid and succinic acid) in ?-caprolactone/ cyclohexanone/acetic acid mixtures were determined respectively. Meanwhile, the experimental data were correlated by NRTL, Apelblat and ?h model equations and the corresponding parameters of model equations were obtained. The results showed that the three models can correlate the solubility of dicarboxylic acid in ?-caprolactone/ cyclohexanone/acetic acid mixtures well.At the temperature ranged from 303.15-353.15 K, the solubilities of tetra-4-methoxyphenylporphyrin and 5,10,15,20-tetra(p-tolyl)porphine in propionic acid/water solvent mixtures and tetra-4-methoxyphenylporphyrin, 5,10,15,20-tetra(p-tolyl)porphine,5,10,15,20-tetrakis(4-chlorophenyl)-porphyrin and ?-oxo-bis(5,10,15,20-tetrakis(4-chlorophenyl)porphinato iron) in DMF solvent were determined by the static equilibrium method. Meanwhile, the Apelblat model equation was taken to correlate the experimental data and the parameters of model equation were obtained. The results showed that the average relative deviation ARD is less than 7%, Apelblat equation model could correlate the solubility of metalporphyrin in various solvents well.