Ti-TUD-1 Applied To The Catalytic Oxidation Of Cyclohexanone And Cyclohexene

Ti-TUD-1 possesses a three-dimensional pore structure, large surface area, and pore-size tunable mesoporous molecular sieve. In addition, the synthesis of Ti-TUD-1 is rather simple and the cost of Ti-TUD-1 is relatively cheap. Owing to its three-dimensional pore structure, large molecules can freely diffuse in the mesopores of Ti-TUD-1. Therefore, it is expected that Ti-TUD-1 as catalyst could be applied in catalytic reactions with diffusion limitations.In this thesis, Ti-TUD-1 was synthesized via a sol-gel method, and the synthesized samples were characterized with various techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (UV-DRS), Raman spectroscopy, infrared spectroscopy (IR), N2 adsorption-desorption. Additionally, the effects of crystallization time during synthesis and post-acid treatment on the textural properties of Ti-TUD-1 were systematically investigated. Then the systematical investigation was carried out on the application of Ti-TUD-1 as catalyst to the ammoximation of cyclohexanone to cyclohexanone oxime and to the oxidation of cyclohexene, including the effects of the reaction conditions, way of adding reagents, and Ti-content in the catalysts, in order to optimize the reaction performance.The results show that in the catalytic ammoximation of cyclohexanone, the optimized reaction conditions are as follows:a reaction temperature of 80℃, a molar ammonia/cyclohexanone ratio of 1.5, and t-butanol as a solvent, and in the oxidation of cyclohexene, the optimized reaction conditions are as follows:a reaction temperature of 70℃, a molar cyclohexene/hydrogen peroxide ratio of 1, a reaction time of 8 h, and acetonitrile as a solvent, Moreover, due to the decomposition of hydrogen peroxide during the reaction, the way of continuously adding hydrogen peroxide can reduce its decomposition rate, resulting in enhancing its utilization for the objective reactions. In conclusion, Ti-TUD-1 shows some remarkable catalytic properties in the ammoximation of cyclohexanone to cyclohexanone oxime and the oxidation of cyclohexene, implying some industrial applicability of Ti-TUD-1 in the conducted reactions.