A series of NiMo/FDU-12 catalysts with tunable pore diameters and mesostructures have been controllably synthesized by adjusting the synthetic hydrothermal temperature and applied for the hydrodesulfurization of diben...A series of NiMo/FDU-12 catalysts with tunable pore diameters and mesostructures have been controllably synthesized by adjusting the synthetic hydrothermal temperature and applied for the hydrodesulfurization of dibenzothiophene and its derivative.The state-of-the-art electron tomography revealed that the pore sizes of FDU-12 supports were enlarged with the increase in the hydrothermal temperature and the mesostructures were transformed from ordered cage-type pores to locally disordered channels.Meanwhile,the MoS2 morphology altered from small straight bar to semibending arc to spherical shape and finally to larger straight bar with the change of support structures.Among them,FDU-12 hydrothermally treated at 150℃possessed appropriate pore diameter and connected pore structure and was favorable for the formation of highly active MoS2 with curved morphology;thus,its corresponding catalyst exhibited the best HDS activity.Furthermore,it was indicated that the isomerization pathway could be significantly improved for HDS of 4,6-dimethyldibenzothiophene after the addition of aluminum,which was expected to be applied to the removal of the macromolecular sulfur compounds.Our study sheds lights on the relationship between support effect,active sites morphology and HDS performance,and also provides a guidance for the development of highly active HDS catalysts.展开更多
Mesoporous silica supported Cs2.5H0.5PW12O40 catalysts were prepared by impregnation method, and several silica supports with different pore size were utilized. N2 adsorption, XRD and ICP-AES techniques were utilized ...Mesoporous silica supported Cs2.5H0.5PW12O40 catalysts were prepared by impregnation method, and several silica supports with different pore size were utilized. N2 adsorption, XRD and ICP-AES techniques were utilized to characterize the silica supports and catalysts. XRD results showed that the dispersion of Cs2.5H0.5PW12 was better for the silica support with larger pore size. The catalytic activity results showed that the pore size played important role on the catalyst activity and the molecular weight of PTHF. When Cs2.5H0.5PW12O40 was dispersed on larger pore size silica support, the catalysts showed good performances for the synthesis of PTHE The molecular weight of PTHF product on the sample in which Cs2.5H0.5PW12O40 was dispersed on larger pore support was higher than that on the catalyst with smaller pore support. The leaching amounts of the active components for the supported Cs2.5H0.5PW12O40 catalysts were much lower. After five reaction cycles, there were still good activities and stabilities for the supported Cs2.5H0.5PW12O40 catalysts with larger pore silica supports. These results were much better than those of the supported heteropolyacid H3PW12O40 catalyst.展开更多
A series of heteropoly acid (HPA) based Al2O3 catalysts with three-dimensional ordered (3DOM) structure were synthesized by colloidal crystal template method.Interconnected macropores (250 nm) could be clearly observe...A series of heteropoly acid (HPA) based Al2O3 catalysts with three-dimensional ordered (3DOM) structure were synthesized by colloidal crystal template method.Interconnected macropores (250 nm) could be clearly observed by scanning electron microscope (SEM) and transmission electron microscope (TEM).Mesopores could be detected by N2 adsorption-desorption isotherms which further confirmed the 3DOM structural characteristics of catalyst.Moreover,Keggin-type HPW was highly dispersed in the Al2O3 framework,which suggested by powder X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR) results.The oxidation desulfurization (ODS) performance of 3DOM H3PW12O40/Al2O3 of refractory sulphur compounds was evaluated in the presence of hydrogen peroxide.It oxidized 98.5% of dibenzothiophene (DBT) into corresponding sulfone within 3 h,which exhibited superior ODS performance than corresponding mesoporous and microporous H3PW12O40/Al2O3 catalyst.The enhancement of ODS efficiency is related to the improvement of mass transfer of DBT in the pore channel resulting from the interconnected 3DOM structure.Furthermore,the as-prepared catalyst still demonstrates outstanding cycle performance after 6 runs,which could be easily recovered from the model fuel.展开更多
Solid acid MoO_(3)/ZrO_(2)-TiO_(2)catalysts were prepared by impregnation method,and catalytic hydrolysis of difluorodichloromethane(CFC-12)over the catalyst was studied.The presence of MoO_(3)/ZrO_(2)-TiO_(2)catalyst...Solid acid MoO_(3)/ZrO_(2)-TiO_(2)catalysts were prepared by impregnation method,and catalytic hydrolysis of difluorodichloromethane(CFC-12)over the catalyst was studied.The presence of MoO_(3)/ZrO_(2)-TiO_(2)catalyst in polycrystalline state could be clearly observed by transmission electron microscopy(TEM).Mesopores were detected by N2 adsorption-desorption isotherms which further confirmed the MoO_(3)/ZrO_(2)-TiO_(2)structural characteristics of catalyst.The results of NH_(3)-TPD showed that the calcination temperatures had a great influence on the acidity of the catalyst,and the weak acidic site had a strong catalytic activity for the catalytic hydrolysis of CFC-12.Moreover,ZrO_(2)-TiO_(2)was highly dispersed in the MoO_(3)framework,suggested by powder X-ray diffraction(XRD)and N_(2)adsorption-desorption results.The effects of the catalyst calcination temperatures on the conversion rate of CFC-12 were studied.The effects of catalytic hydrolysis temperatures and water vapor concentration on the catalytic hydrolysis rate of CFC-12 were also studied.The solid acid MoO_(3)/ZrO_(2)-TiO_(2)was calcined at 500℃for 3 h at a catalytic hydrolysis temperature of 400℃and water vapor concentration of 83.18%,and catalytic hydrolysis rate of CFC-12 reached 98.65%.The hydrolysis rate of CFC-12 remained above 65.34%after 30 hours continuous reaction.展开更多
Synthetic method of solid superacid TiSiW 12 O 40 /TiO 2 was described.The synthesis of iso amyl propionate catalyzed by TiSiW 12 O 40 /TiO 2 has been studied and the factors influencing on the yield is discussed.It s...Synthetic method of solid superacid TiSiW 12 O 40 /TiO 2 was described.The synthesis of iso amyl propionate catalyzed by TiSiW 12 O 40 /TiO 2 has been studied and the factors influencing on the yield is discussed.It shows that it’s an excellent catalyst,the yield of the iso amyl propionate can be over 77% when the molar ratio of iso amyl alcohol and propionic acid is 1.2,the quality of TiSiW 12 O 40 /TiO 2 is equal to 1.5% feed stock,the reaction time is 80min and the reaction temperature is about 103～107℃.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant Nos.21776048,21576290,21106182)the Natural Science Foundation of Fujian Province(2018J06002)。
文摘A series of NiMo/FDU-12 catalysts with tunable pore diameters and mesostructures have been controllably synthesized by adjusting the synthetic hydrothermal temperature and applied for the hydrodesulfurization of dibenzothiophene and its derivative.The state-of-the-art electron tomography revealed that the pore sizes of FDU-12 supports were enlarged with the increase in the hydrothermal temperature and the mesostructures were transformed from ordered cage-type pores to locally disordered channels.Meanwhile,the MoS2 morphology altered from small straight bar to semibending arc to spherical shape and finally to larger straight bar with the change of support structures.Among them,FDU-12 hydrothermally treated at 150℃possessed appropriate pore diameter and connected pore structure and was favorable for the formation of highly active MoS2 with curved morphology;thus,its corresponding catalyst exhibited the best HDS activity.Furthermore,it was indicated that the isomerization pathway could be significantly improved for HDS of 4,6-dimethyldibenzothiophene after the addition of aluminum,which was expected to be applied to the removal of the macromolecular sulfur compounds.Our study sheds lights on the relationship between support effect,active sites morphology and HDS performance,and also provides a guidance for the development of highly active HDS catalysts.
基金supported by the National Natural Science Foundation of China(No.20776089)
文摘Mesoporous silica supported Cs2.5H0.5PW12O40 catalysts were prepared by impregnation method, and several silica supports with different pore size were utilized. N2 adsorption, XRD and ICP-AES techniques were utilized to characterize the silica supports and catalysts. XRD results showed that the dispersion of Cs2.5H0.5PW12 was better for the silica support with larger pore size. The catalytic activity results showed that the pore size played important role on the catalyst activity and the molecular weight of PTHF. When Cs2.5H0.5PW12O40 was dispersed on larger pore size silica support, the catalysts showed good performances for the synthesis of PTHE The molecular weight of PTHF product on the sample in which Cs2.5H0.5PW12O40 was dispersed on larger pore support was higher than that on the catalyst with smaller pore support. The leaching amounts of the active components for the supported Cs2.5H0.5PW12O40 catalysts were much lower. After five reaction cycles, there were still good activities and stabilities for the supported Cs2.5H0.5PW12O40 catalysts with larger pore silica supports. These results were much better than those of the supported heteropolyacid H3PW12O40 catalyst.
基金Funded by the National Natural Science Foundation of China(No.21476177)。
文摘A series of heteropoly acid (HPA) based Al2O3 catalysts with three-dimensional ordered (3DOM) structure were synthesized by colloidal crystal template method.Interconnected macropores (250 nm) could be clearly observed by scanning electron microscope (SEM) and transmission electron microscope (TEM).Mesopores could be detected by N2 adsorption-desorption isotherms which further confirmed the 3DOM structural characteristics of catalyst.Moreover,Keggin-type HPW was highly dispersed in the Al2O3 framework,which suggested by powder X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR) results.The oxidation desulfurization (ODS) performance of 3DOM H3PW12O40/Al2O3 of refractory sulphur compounds was evaluated in the presence of hydrogen peroxide.It oxidized 98.5% of dibenzothiophene (DBT) into corresponding sulfone within 3 h,which exhibited superior ODS performance than corresponding mesoporous and microporous H3PW12O40/Al2O3 catalyst.The enhancement of ODS efficiency is related to the improvement of mass transfer of DBT in the pore channel resulting from the interconnected 3DOM structure.Furthermore,the as-prepared catalyst still demonstrates outstanding cycle performance after 6 runs,which could be easily recovered from the model fuel.
基金Funded by the National Natural Science Foundation of China(No.51568068)the Young and Middle-aged Academic and Technical Leaders Reserve Talent Program(No.202105AC160054)。
文摘Solid acid MoO_(3)/ZrO_(2)-TiO_(2)catalysts were prepared by impregnation method,and catalytic hydrolysis of difluorodichloromethane(CFC-12)over the catalyst was studied.The presence of MoO_(3)/ZrO_(2)-TiO_(2)catalyst in polycrystalline state could be clearly observed by transmission electron microscopy(TEM).Mesopores were detected by N2 adsorption-desorption isotherms which further confirmed the MoO_(3)/ZrO_(2)-TiO_(2)structural characteristics of catalyst.The results of NH_(3)-TPD showed that the calcination temperatures had a great influence on the acidity of the catalyst,and the weak acidic site had a strong catalytic activity for the catalytic hydrolysis of CFC-12.Moreover,ZrO_(2)-TiO_(2)was highly dispersed in the MoO_(3)framework,suggested by powder X-ray diffraction(XRD)and N_(2)adsorption-desorption results.The effects of the catalyst calcination temperatures on the conversion rate of CFC-12 were studied.The effects of catalytic hydrolysis temperatures and water vapor concentration on the catalytic hydrolysis rate of CFC-12 were also studied.The solid acid MoO_(3)/ZrO_(2)-TiO_(2)was calcined at 500℃for 3 h at a catalytic hydrolysis temperature of 400℃and water vapor concentration of 83.18%,and catalytic hydrolysis rate of CFC-12 reached 98.65%.The hydrolysis rate of CFC-12 remained above 65.34%after 30 hours continuous reaction.
文摘Synthetic method of solid superacid TiSiW 12 O 40 /TiO 2 was described.The synthesis of iso amyl propionate catalyzed by TiSiW 12 O 40 /TiO 2 has been studied and the factors influencing on the yield is discussed.It shows that it’s an excellent catalyst,the yield of the iso amyl propionate can be over 77% when the molar ratio of iso amyl alcohol and propionic acid is 1.2,the quality of TiSiW 12 O 40 /TiO 2 is equal to 1.5% feed stock,the reaction time is 80min and the reaction temperature is about 103～107℃.
