Synthesis Of Methyl Ethyl Ketone Peroxide Catalyzed By Zirconium(Titanium) Modified HZSM-5 Zeolites And UiO-66

Methyl ethyl ketone peroxide?MEKP?is mainly used for the curing of unsaturated resins at room temperature.It is also used as initiator,bleaching agent and fungicide for organic synthesis.Industrial production process,methyl ethyl ketone peroxide is synthesized by oxidation of methyl ethyl ketone?MEK?with hydrogen peroxide?H₂O₂?,and then neutralization,separation,dehydration,filtering to obtain the finished product.In the traditional process sulfuric acid is used as the catalyst,which causes corrosion to the equipment,and produce the waste acid.The preparation of methyl ethyl ketone peroxide by heterogeneous synthesis is of great practical significance.In this thesis,HZSM-5 zeolite,zirconium?titanium?modified HZSM-5 zeolite,and organic framework material UiO-66 used as catalysts to catalytic synthesis methyl ethyl ketone peroxide.The main tasks are as follows:1.HZSM-5 zeolite with different silicon-aluminum ratios were prepared by hydrothermal method.The effects of silica-alumina ratio on the synthesis of methyl ethyl ketone peroxide were investigated.It was characterized by the methods of XRD,FT-IR,SEM,EDS,XPS,and BET.The experimental results show that the silicon-aluminum ratio has a significant effect on the synthesis of MEKP.The optimal silicon-aluminum ratio is200.Under the reactions of time for 80 minutes,the reaction temperature at 36?,the molar ratio of hydrogen peroxide to methyl ethyl ketone of 1.5,the mass ratio of HZSM-5 zeolites to methyl ethyl ketone of 0.068,the yield of MEKP is 60.07%and the active oxygen content is 9.14%.HZSM-5 still keep good catalytic activity after recycling for 8times.The main products are methyl ethyl ketone peroxide and its synthetic intermediates which were confirmed by using mass spectrometry for.2.Zirconium and titanium modified HZSM-5 zeolites?Zr/HZSM-5,Ti/HZSM-5?were prepared with zirconium and titanium,respectively.They were characterized by XRD,FT-IR,SEM,XPS and BET.The effect of modified zeolite on the synthesis of MEKP was investigated using the ketone dropping method.The results showed that at the reaction time for 80 minutes,the reaction temperature at 36?,the molar ratio of hydrogen peroxide to methyl ethyl ketone of 1.5,the mass ratio of HZSM-5 zeolites to methyl ethyl ketone of 0.068,the MEKP yields are 67.33%,69.36%and 68.51%catalyzed by Zr/HZSM-5 zeolite with zirconium to aluminum ratios of 0.5,1.0 and 2.0,respectively.The MEKP yields are 64.68%,65.53%,and 67.57%on Ti/HZSM-5 zeolite with titanium,respectively.Zirconium modified zeolite shows higher catalytic activity than titanium modified zeolites.3.The metal-organic frameworks of UiO-66 was prepared by hydrothermal method.It was characterized by XRD,IR,SEM and TG-DTA.The test showed that the defect site of the synthesized UiO-66 is 1.47,which the exposed zirconium metal has a good acid catalytic function.UiO-66 was used to catalyze the synthesis of methyl ethyl ketone peroxide.Under the conditions of reaction time for 70 minutes,the reaction temperature at 30?,the molar ratio of hydrogen peroxide to Methyl ethyl ketone of 2.0,mass ratio of UiO-66 to methyl ethyl ketone of 0.045,the active oxygen content is 10.81%,and the MEKP yield is 71.01%.Liquid chromatography-mass spectrometry analysis showed that the synthesis products are methyl ethyl ketone peroxide and its polymers.