Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. He...Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal（Fe, Co, Ni, Mo and W） phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.展开更多
An alumina support was modified by fluorine via impregnation to investigate the effect of fluoride content on the reactivity of Ni–Mo/Al2O3 catalyst.The catalyst was characterized by X-ray diffraction,N2 adsorption–...An alumina support was modified by fluorine via impregnation to investigate the effect of fluoride content on the reactivity of Ni–Mo/Al2O3 catalyst.The catalyst was characterized by X-ray diffraction,N2 adsorption–desorption(Brunauer–Emmett–Teller)isotherms,temperature-programmed desorption of ammonia,X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy.Sulfur etherification performance of the catalyst was studied using a fixed-bed reactor.The results show that increasing fluoride content increases the pore volume and pore size but reduces the specific surface area.In addition,the degree of sulfidation of Ni first increases and then decreases.The amounts of strong acid and total acid also increase with increasing fluoride content.Performance evaluation of the catalyst reveals that the fluoride content has a minor effect on the thioetherification performance of the catalyst;however,an optimum fluoride content,which was determined to be 0.2%,can ensure lower olefin saturation and an efficient diene selective hydrogenation.展开更多
The Mo modified Ni/Al_2O_3 catalysts were prepared and sulfided at different temperatures, and their catalytic activity for thioetherification of mercaptans and olefins(or dienes), hydrogenation of dienes and olefins ...The Mo modified Ni/Al_2O_3 catalysts were prepared and sulfided at different temperatures, and their catalytic activity for thioetherification of mercaptans and olefins(or dienes), hydrogenation of dienes and olefins in the thioetherification process using fluidized catalytic cracking(FCC) naphtha as the feedstock was investigated. In order to disclose the correlation between the physicochemical characteristics of catalysts and their catalytic activity, the surface structures and properties of the catalysts sulfided at different temperatures were characterized by the high resolution transmission electronic microscopy(HRTEM), X-ray photoelectron spectroscopy(XPS) and H2-temperature programmed reduction(H_2-TPR) technique. The results showed that an increase of sulfurization temperature not only could promote the sulfurization degree of active metals on the catalysts, but also could adjust the micro-morphology of active species. These changes could improve the catalytic performance of thioetherification, and hydrogenation of dienes and olefins. However, an excess sulfurization temperature was more easily to upgrade the ability of the catalyst for hydrogenation of olefins, which could lead to a decrease of the octane number of the product. It was also showed that a moderate sulfurization temperature not only could improve the catalytic performance of thioetherification and hydrogenation of dienes but also could control hydrogenation of olefins.展开更多
An efficient electrochemical approach has been developed for the construction of 3-sulfanylquinoline derivatives by treating phenylethynylbenzoxazinanones with disulfides in an undivided cell.The protocol provided a c...An efficient electrochemical approach has been developed for the construction of 3-sulfanylquinoline derivatives by treating phenylethynylbenzoxazinanones with disulfides in an undivided cell.The protocol provided a convenient route to functionalized quinolines with good functional group tolerance.Moreover,it does not require any metal catalysts or additives,furnishing a series of biologicalquinolines inmoderatetogoodyields.展开更多
基金supported by the State Key Laboratory of Catalytic Materials and Reaction Engineering(RIPP,SINOPEC)
文摘Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal（Fe, Co, Ni, Mo and W） phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.
基金This work has been supported by the National Natural Science Foundation of China(Grant No.21776303).
文摘An alumina support was modified by fluorine via impregnation to investigate the effect of fluoride content on the reactivity of Ni–Mo/Al2O3 catalyst.The catalyst was characterized by X-ray diffraction,N2 adsorption–desorption(Brunauer–Emmett–Teller)isotherms,temperature-programmed desorption of ammonia,X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy.Sulfur etherification performance of the catalyst was studied using a fixed-bed reactor.The results show that increasing fluoride content increases the pore volume and pore size but reduces the specific surface area.In addition,the degree of sulfidation of Ni first increases and then decreases.The amounts of strong acid and total acid also increase with increasing fluoride content.Performance evaluation of the catalyst reveals that the fluoride content has a minor effect on the thioetherification performance of the catalyst;however,an optimum fluoride content,which was determined to be 0.2%,can ensure lower olefin saturation and an efficient diene selective hydrogenation.
基金support provided by the National Natural Science Foundation of China(Granted No.21276276)
文摘The Mo modified Ni/Al_2O_3 catalysts were prepared and sulfided at different temperatures, and their catalytic activity for thioetherification of mercaptans and olefins(or dienes), hydrogenation of dienes and olefins in the thioetherification process using fluidized catalytic cracking(FCC) naphtha as the feedstock was investigated. In order to disclose the correlation between the physicochemical characteristics of catalysts and their catalytic activity, the surface structures and properties of the catalysts sulfided at different temperatures were characterized by the high resolution transmission electronic microscopy(HRTEM), X-ray photoelectron spectroscopy(XPS) and H2-temperature programmed reduction(H_2-TPR) technique. The results showed that an increase of sulfurization temperature not only could promote the sulfurization degree of active metals on the catalysts, but also could adjust the micro-morphology of active species. These changes could improve the catalytic performance of thioetherification, and hydrogenation of dienes and olefins. However, an excess sulfurization temperature was more easily to upgrade the ability of the catalyst for hydrogenation of olefins, which could lead to a decrease of the octane number of the product. It was also showed that a moderate sulfurization temperature not only could improve the catalytic performance of thioetherification and hydrogenation of dienes but also could control hydrogenation of olefins.
基金supported by the National Natural Science Foundation of China(21801152 and 21572110)the Youth Innovation Science and Technology Plan of Colleges and Universities in Shandong Province(2021KJ076).
文摘An efficient electrochemical approach has been developed for the construction of 3-sulfanylquinoline derivatives by treating phenylethynylbenzoxazinanones with disulfides in an undivided cell.The protocol provided a convenient route to functionalized quinolines with good functional group tolerance.Moreover,it does not require any metal catalysts or additives,furnishing a series of biologicalquinolines inmoderatetogoodyields.
