The Industrial Applied Research On Cyclohexane Oxidation With Biomimetic 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 single continuous reactor, three stir-reactors in series as well as continuous experiments in small and pilot scales have been carried out. The industrial plant to produce cobaltoporphyrin catalyst has been built and run successfully. 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 biomimetic catalytic oxidation experiment on the plant with the capacity of 70kt/a of cyclohexanone and the design of the plant with the capacity of 125kt/a have been completed. The main research works and results are as follows:1. The plant to produce cobaltoporphyrin catalyst has been designed and installed. Porphyrin was produced by using traditional Adler method. The results are: the yield of porphyrin can reach 20.3% while the concentration of the reactants is 0.45mol/L and the reaction time is 35min.The recovery ratio of propyl acid can reach 95% which results in decreasing the production cost of porphyrin, so it can meet the industrial application requirements of metalloporphyrin.2. The single continuous experimental device of cyclohexane oxidation with biomimetic catalyst has been designed and erected. The experiment results are: the fully mixed stir-reactor is better than other types; the optimal reaction temperature is 143~145癈 and reaction pressure is 0.85+0.05MPa(G)3. The pilot device of three stir-reactors in series for cyclohexane oxidation with biomimetic catalyst. The research results are: the best catalyst is cobaltoporphyrin and its concentration is 3mg/L.4. The mathematic reaction model for cyclohexane oxidation with biomimetic catalyst is established as per small-pilot scale experiments and related references. This model has been used to simulate the industrial experiments.5. The cyclohexane oxidation with biomimetic 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 small -model scales.6. The research on industrial design was done by using the above mentionedmodel 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.7. 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 of atom reaction and in line with green chemistry. The selective oxidation of inert hydrocarbon is developed under relatively mild conditions due to the successful application of biomimetic technology in industrial plant, which is very important to pertinent process such as the synthesis of bebzylalcohoh benzaldehydes 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.