Allyl Chloride Epoxidation Over TS-1 Catalysts In Fixed-bed Reactor

Micro TS-1 samples were synthesized and modified with TPAOH aqueous,and then extruded to shaped catalysts for allyl chloride epoxidation.The allyl chloride epoxidation reactions were carried out in a fixed-bed reactor with hydrogen peroxide as an oxidant.The effect of reaction conditions such as temperature,allyl chloride velocity,molar ratio of allyl chloride to hydrogen peroxide was investigated.The reaction conditions were optimized with orthogonal design.At the same time,the effect of reactor material on the reaction results was also studied.Finally,the deactivation of the catalysts and the regeneration method were investigated.The results show that:1.The optimized reaction conditions of allyl chloride epoxidation with hydrogen peroxide as an oxidant over TS-1 in a fixed-bed reactor(made of stainless steel) are as follows:40℃, molar ratio of allyl chloride to hydrogen peroxide 3.01,velocity of allyl chloride 0.6 h^-1,ratio of length to diameter of catalyst bed 5,volume ratio of methanol to allyl chloride 8.5,size of the shaped catalyst 1 mm×1 mm.Under the optimized reaction conditions,the conversion of allyl chloride,selectivity to epichlorohydrin,conversion and efficiency of hydrogen peroxide can be 27.6%,86.6%,96.8%and 85.7%,respectively.2.The optimized reaction conditions of allyl chloride epoxidation with hydrogen peroxide as an oxidant over TS-1 in a fixed-bed reactor(made of glass) are as follows:47.5℃,molar tatio of allyl chloride to hydrogen peroxide 3.01,velocity of allyl chloride 0.4 h^-1.The others are the same as above.Under these conditions,the conversion of allyl chloride, selectivity to epichlorohydrin,conversion and efficiency of hydrogen peroxide can be 20,7%, 82.0%,96.7%and 64.4%,respectively.3.Dilute hydrogen peroxide aqueous can regenerate the deactivated TS-1 catalysts.The optimized regeneration conditions are as follows,80℃,methanol wash time 6 h,velocity of methanol 1 h^-1,1.5%hydrogen peroxide aqueous wash 12 h,velocity 5 h^-1,feed without allyl chloride wash 1 h.The catalysts can be regenerated successfully and the stability is good.