Heterogeneous Catalytic Synthesis Of Cumene Hydrogen Peroxide And Dicumyl Peroxide

Cumene hydroperoxide（CHP）and dicumyl peroxide（DCP）are important chemical products,which play an important role in the fields of polymer materials,fine chemicals and organic synthesis.In the traditional production process,sulfuric acid is usually used as catalyst for homogeneous preparation,which not only causes equipment corrosion,but also has some problems as serious equipment corrosion,catalyst not easy to be recovered,large amount of waste acid produced,serious environmental pollution.Therefore,preparation of organic peroxides by heterogeneous catalysis can effectively solve the problems of equipment corrosion,complex post-treatment and safety risks.In this study,on the basis of reviewing the application of heterogeneous catalysts in the preparation of organic peroxides,multicomponent oxides and molecular sieves supported superacid were selected as catalysts to prepare cumene hydroperoxide and dicumyl peroxide respectively.The main research contents of this paper were as follows:1.Cu O-Zn O-Ti O₂ complex oxides were prepared by coprecipitation method,and was characterized by XRD,SEM,TEM,O₂-TPD and XPS.Its catalytic activity for liquid phase oxidation of cumene was studied,and the reaction mechanism was discussed.When the reaction temperature is 95℃,the reaction time is 10 h,and the amount of catalyst is0.9 wt%of the total raw material,the content of active oxygen is 4.61%.Cu O-Zn O-Ti O₂contains a large amount of lattice oxygen and reactive oxygen species.The generated O₂^-interacts with hydrogen atoms of cumene tertiary carbon,which reduces the energy required for the formation of free radicals and promotes the formation of free radicals,which is beneficial to the synthesis of CHP.2.The CHP synthesized in the first part andα-methylstyrene（α-MS）were used as raw materials.Dicumyl peroxide（DCP）was prepared by using p-toluene sulfonic acid（PTSA）supported on MCM-41 and SBA-15 molecular sieves prepared by impregnation method as catalyst.The structures was characterized by XRD,SEM,NH₃-TPD and N₂adsorption/desorption.When the feed ratio of n（α-MS）:n（CHP）is 2.0,the reaction temperature is 44℃,the amount of SBA-15 loaded p-toluenesulfonic acid（PTSA/MCM-41）is 0.2 wt%of the amount of CHP,and the reaction time is 3.0 h,the yield of DCP is55.7%,while it is 62.1%when the amount of loaded p-toluene sulfonic acid（PTSA/SBA-15）is 0.15%of the amount of CHP and the reaction time is 2.5 h.Through Gaussian calculation,the whole reaction is completed through two transition states of TS1 and TS2.3.According to the above experimental results,a process with an annual output of1500 tons of DCP was designed usingα-MS and CHP as raw materials.The main design tasks include material balance,process design,reactor design,crystallization kettle design,vacuum distillation column design and other equipment selection.