Study On Synthesis Of ε-caprolactone Over Solid Acid Catalysts

ε-Caprolactone(ε-CL), an important intermediate of organic synthesis, is mainly (?)sed to produce PCL and polyesters.Those polymers have good thermosplasticity and ormation workability, its biocompatibility, nontoxicity, medicine permeability and biological degradability prepossess them great application prospect in the material, the environmental protection and the medical aspect's, which result in research on the synthesis of the epsilon caprolactone monomer to be more and more important.ε-CL can be synthesized in various ways, of which the oxidizing cyclohexanone method has been paid more attention in the world.The solid acid catalyst acts as one kind of emerging special purpose fine c(?)emical, has the characteristics as following:easy separated from the liquid phase reacting system, does not corrode the equipment, simple post-processing, possible of d(?)plicate uses, less pollution to the environment, high selectivity, and high atomic use.when it's used in the synthesis of epsilon caprolactone by catalyzing the oxidation of cyclohexanone,it's able to enhance the yield and the selectivity of epsilon caprolactone greatly.The research primary coverage includes:(1) Having prepared six solid acid catalysts, and characterization of the crystal structure,specific surface area and suface morphology of those catalysts with XRD, nitrogen adsorption-desorption, SEM, TEM test analysis methods and so on. (2) Having carried out the active aporaisal experiments, and selected the catalyst of best catalyzed effect. (3) Having taken 30% hydrogen peroxide as the oxidant, inspected the factors that influence the catalysis effect such as the pressure, the temperature, the time, the catalyst amount, the material ratio and so on, and the process condition of synthesis ofε-CL have been optimized as well. (4) Having simulated the rectificating separation process of crude product through the ASPEN software, with the aim of obtaining the practical data, then conducting the industrialization production of the epsilon caprolactone with high purity.The result indicated:The best catalyst is B2O3/γ-Al2O3, finally, the optimal process condition parameter have been determined through experiments. That is:In the first step, the reaction vacuum degree is the 400mmHg column, n (propionic acid): n (hydrogen peroxide)=4:1, the catalyst is 0.8g, the reaction time is 3h, then the yield and selectivity ofε-caprolactone can reach 87.721% and 95.07% respectively; In the second step, the reaction temperature is 50℃, and the reaction time is 3h.I carried out the industrialization simulation of epsilon caprolactone separation process using ASPEN software,then obtained the material balance and the energy balance results of the separation process,the operation parameter of the rectifying tower, the column internals parameter, the column tray parameter distribution map, the hydraulic parameter list and so on,they are the industrialization data with extremely value.