Synthesis Of Oxidized-Thermoregulated Phase Separation Of Ionic Liquid And Studys On Application In Oxidative Desulfurization Of Gasoline

According to the designability of ionic liquids in the structures, new oxidize-thermoregulated ionic liquids are synthesized, and used for catalyzing H2O2oxidative desulfurization of gasoline, in order to realize the integration of reaction and separation, and recycling of the catalysts.13kinds of imidazolium oxidize-thermoregulated ionic liquids were synthesized by using imidazole, epoxy ethane, chlorobutane, phosphotungstic acid as raw materials, and characterized by FT-IR,1H NMR and TG. The polarities of these ionic liquids and their thermoregulated property in DMF/n-octane and DMF/n-heptane biphase system were investigated; Moreover, the effects of the degree of polymerization, the ionic liquids concentration, electrolyte, and organic additives (such as toluene, n-octane, DMF, and so on) on the cloud points of these ionic liquids in water were also studied.22kinds of eighteen amino oxidize-thermoregulated ionic liquids were synthesized by using eighteen amines, ethylene oxide, chlorinated paraffin, and phosphotungstic acid as raw materials, and characterized by FT-IR,1H NMR and TG.. The polarities of these ionic liquids and the effects of the degree of polymerization on the cloud point were investigated. The study showed that these ionic liquids had good thermoregulation in toluene/n-octane. After the further study, we discovered that the thermoregulated performances were effected by the degree of polymerization, V(toluene)/V(n-octane) and m(IL):m(toluene).The imidazolium oxidize-thermoregulated ionic liquids were used for catalyzing H2O2oxidative desulfurization of gasoline. By optimizing the process conditions, the optimum conditions were obtained:The optimum conditions were obtained as follows: the ionic liquid n=17, reaction temperature60℃, n(H2O2):n(S)=10:1, n(S):n(ionic liquids)=4:1, reaction time4h. After reaction, if the gasoline was extracted by DMF (the ratio of catalyst to oil1:1, stirring5min at40℃, standstill10min) one time, the desulfurization rate could reach83.04%, and if extracted3times, the desulfurization rate could reach98.96%. After10recycles of the ionic liquid, the desulfurization rate could still reach76.13%(the gasoline was extracted by DMF for one time). After recycles, the ionic liquid was characterized by FT-IR and the result showed that the structure of the ionic liquid was not changed.The eighteen amino oxidize-thermoregulated ionic liquids were used for catalyzing H2O2oxidative desulfurization of gasoline. The effect of the degree of the polymerization on the reaction was studied, and the result showed that the ionic liquid of n=96(C4) was the best catalyst. After the orthogonal test, we got the optimum conditions as follows:V(toluene):V(octane)=1:1.5, m(ionic liquids):m(toluene)=1.891, n(H2O2):n(S)=10:1, reaction temperature50℃, reaction time90min. After reaction, if the liquid was extracted by DMF (the ratio of catalyst to oil2.5:1, stirring5min at40℃, standstill10min) one time, the desulfurization rate could reach93.47%, and if extracted3times, the desulfurization rate could reach99.58%. After10recycles of the ionic liquid, the desulfurization rate could still reach76.14%(the gasoline was extracted by DMF for one time). After recycles, the ionic liquid was characterized by FT-IR and1H NMR, the result showed that the structure of the ionic liquid was not changed.The synthetic oxidize-thermoregulated ionic liquids used for catalyzing H2O2oxidation desulfurization of gasoline, the ionic liquids achieve the reaction system of "homogeneous reaction at high temperature, and two-phase separation at low temperature ", which provides a new way for catalytic oxidation. And the ionic liquids can effectively reuse.