The Industrial Applied Research On Cyclohexane Oxidation With Metalloporphyrin Catalyst

The industrial process of cyclohexane oxidation with air in the presence of metalloporphyrin catalyst to produce cyclohexanone has been studied in this paper. The design and installation of three stir-reactors in series as well as continuous experiments in medium-sized have been carried out. The mathematic model of cyclohexane oxidation with air in the presence of metalloporphyrin catalyst has been set up and process simulation has been executed. Guided by the simulation results, the metalloporphyrin catalytic oxidation experiment on the plant with the capacity of 45 kt/a and 70kt/a of cyclohexanone and the design of the plant with the capacity of 124kt/a have been completed. The main research works and results are as follows: 1.The medium-sized of three stir-reactors in series for cyclohexane oxidation with metalloporphyrin catalyst. The research results are: the fully mixed stir-reactor is better than other types; the optimal reaction temperature is 143～145℃ and reaction pressure is 0.85±0.05MPa(G)。the best catalyst is cobaltoporphyrin and its concentration is 3mg/L. 2. The mathematic reaction model for cyclohexane oxidation with metalloporphyrin catalyst is established as medium-sized experiments and related references. This model has been used to simulate the industrial experiments. 3. The cyclohexane oxidation with metalloporphyrin catalyst was carried out on the industrial plant with five stir-reactor in series producing cyclohexanone in non-catalyst oxidation way. The applicability of mathematic model has been verified by the results of continuous experiments in medium-sized experiments. 4. The research on industrial design was done by using the above mentioned model and ASPEN PLUS. All those industrial researches and experiment indicate that the technology of metalloporphyrin can be directly applied to existing plant to expand the capacity, provided that the heat balance issue could be solved by adding heat-exchange equipments. The investment will yield high return by the new technology with excellent perspective. 5. Preparation of cyclohexanone by cyclohexane oxidation is firstly realized using metalloporphyrin as catalyst, the research results showed that the selectivity and conversion of C-H bond oxidation reaction with metalloporphyrin catalyst is high under relatively mild conditions, the conversion is twice and the selectivity is increased by 5% than existing process. The process is in line with green chemistry. The selective oxidation of inert hydrocarbon is developed under relatively mild conditions due to the successful application of metalloporphyrin catalyst in industrial plant, which is very important to pertinent process such as the synthesis of bebzylalcohol,benzaldehyde,benzoicacid based on toluene and of PTA based on dimethylbenzene,etc.The application and "radiation" of the new technology will prompt the development of trade and technology.