A titania pillared interlayered clay（Ti-PILC） supported vanadia catalyst（V2O5/TiO2-PILC） was prepared by wet impregnation for the selective catalytic reduction（SCR） of NO with ammonia. Compared to the traditiona...A titania pillared interlayered clay（Ti-PILC） supported vanadia catalyst（V2O5/TiO2-PILC） was prepared by wet impregnation for the selective catalytic reduction（SCR） of NO with ammonia. Compared to the traditional V2O5/TiO2 and V2O5-MoO3/TiO2 catalysts, the V2O5/TiO2-PILC catalyst exhibited a higher activity and better SO2 and H2O resistance in the NH3-SCR reaction. Characterization using TPD, in situ DRIFT and XPS showed that surface sulfate and/or sulfite species and ionic SO4^（2-）species were formed on the catalyst in the presence of SO2. The ionic SO4^（2-） species on the catalyst surface was one reason for deactivation of the catalyst in SCR. The formation of the ionic SO4^（2-） species was correlated with the amount of surface adsorbed oxygen species. Less adsorbed oxygen species gave less ionic SO4^（2-） species on the catalyst.展开更多
The selective oxidation of n-butane to maleic anhydride (MA) on a vanadium-phosphorus oxide (VPO) catalyst was studied using on-line gas-chromatography combined with mass spectrometry(GC-MS) and transient response tec...The selective oxidation of n-butane to maleic anhydride (MA) on a vanadium-phosphorus oxide (VPO) catalyst was studied using on-line gas-chromatography combined with mass spectrometry(GC-MS) and transient response technique. The reaction intermediates, buterie and furan, were found in the reaction effluent under near industrial feed condition (3% butane+15%O2), while dihydrofuran was detected at high butane concentration (12% butane, 5%O2). Some intermediates of MA decomposition were also identified. Detection of these intermediates shows that the vanadium phosphorus oxides are able to dehydrogenate butane to butene, and butene further to form MA. Based on these observations, a modified scheme of reaction network is proposed. The transient experiments show that butane in the gas phase may directly react with oxygen both on the surface and from the metal oxide lattice, without a proceeding adsorption step. Gas phase oxygen can be adsorbed and transformed to surface lattice oxygen but it can not participate in selective oxidation. Adsorbed oxygen leads to deep oxidation, while lattice oxygen leads to selective oxidation.展开更多
The oxidative dehydrogenation（ODH） of propane on monomeric VO3 supported by CeO2（111）（VO3/CeO 2（111）） is studied by periodic density functional theory calculations. Detailed energetic, structural, and electron...The oxidative dehydrogenation（ODH） of propane on monomeric VO3 supported by CeO2（111）（VO3/CeO 2（111）） is studied by periodic density functional theory calculations. Detailed energetic, structural, and electronic properties of these reactions are determined. The calculated activation energies of the breaking of the first and second C–H bonds of propane on the VO3/CeO2（111） catalyst are compared, and it is found that both the unique structural and electronic effects of the VO3/CeO2（111） catalyst contribute to the relatively easy rupture of the first C–H bond of the propane molecule during the ODH reaction. In particular, the so-called new empty localized states that are mainly constituted of O2 porbitals of the ceria-supported VO3 species are determined to be crucial for assisting the cleavage of the first C–H bond of the propane molecule. Following this they become occupied and the remaining C–H bonds become increasingly difficult to break owing to the increasing repulsion between the localized 4 felectrons at the Cecations, resulting in the adsorption of more H and other moieties. This work illustrates that CeO2-supported monomeric vanadium oxides can exhibit unique activity and selectivity for the catalytic ODH of alkanes to alkenes.展开更多
In order to evaluate the role of vanadium in the hydrogenation (HYD) reaction, a series of alumina supported vanadium catalysts were prepared and characterized by SEM, XRD, Raman spectrometry, 51V NMR, XPS, as well as...In order to evaluate the role of vanadium in the hydrogenation (HYD) reaction, a series of alumina supported vanadium catalysts were prepared and characterized by SEM, XRD, Raman spectrometry, 51V NMR, XPS, as well as TPR analyses. The catalytic performance of vanadium in HYD of model molecules (naphthalene) and real feedstock (Kuwait atmospheric residue) was studied after sulfidation of the catalysts. It can be concluded that the HYD capabilities of V/Al2O3 catalysts are lower than that of conventional NiMo/Al2O3 catalyst (RefNiMo). The V/Al2O3 catalysts can only facilitate hydrogenation of the first ring of naphthalene, but have little effect on the further hydrogenation of tetralin. Owing to the different forms of metals and sulfur compounds in residue, the weak HYD activity of V/Al2O3 catalysts is able to facilitate the HDM reaction of the residue, albeit with a slight effect on HDS activity.展开更多
The catalytic activity of carbon nanotubes-supported vanadium oxide(V_2O_5/CNTs) catalysts in the selective catalytic reduction(SCR) of NO with NH_3 at low temperatures(<250℃) was investigated.The effects of V_2O_...The catalytic activity of carbon nanotubes-supported vanadium oxide(V_2O_5/CNTs) catalysts in the selective catalytic reduction(SCR) of NO with NH_3 at low temperatures(<250℃) was investigated.The effects of V_2O_5loading,reaction temperature,and presence of SO_2 on the SCR activity were evaluated.The results show that V_2O_5/CNTs catalysts exhibit high activity for NO reduction with NH_3 at low-temperatures.The catalysts also show very high stability in the presence of SO_2.More interestingly,their activities are significantly promoted instead of being poisoned by SO_2.The promoting effect of SO_2 is distinctly associated with V_2O_5 loading,particularly maximized at low V_2O_5 loading,which indicated the role of CNTs support in this effect.The promoting effect of SO_2 at low temperatures suggests that V_2O_5/CNTs catalysts are promising catalytic materials for low-temperature SCR reactions.展开更多
TiO2 photocatalysts loaded with V2O5 were prepared via a modified hydrolysis process,and characterized by X-ray diffraction,transmission electron microscopy,Raman spectra and diffuse reflectance UV-Vis spectra measure...TiO2 photocatalysts loaded with V2O5 were prepared via a modified hydrolysis process,and characterized by X-ray diffraction,transmission electron microscopy,Raman spectra and diffuse reflectance UV-Vis spectra measurements. The photocatalytic activity of V2O5/TiO2 was investigated by employing splitting of water for O2 evolution. The results indicate that V2O5 loading can pronouncedly improve the photocatalytic activity of TiO2 with Fe3+ as an electron acceptor under UV or visible light irradiation. The optimum mass fraction of the loaded V2O5 is 8%,and the largest speed of O2 evolution for 8%V2O5 (mass fraction) loaded TiO2 catalyst is 118.2 μmol/(L.h) under UV irradiation,and 83.7 μmol/(L.h) under visible light irradiation.展开更多
Effects of vanadium on light olefins selectivity of FCC catalysts were investigated with vanadium having different oxidation numbers （hereinafter abbreviated as Oxnum）. Molecular modeling studies showed that vanadiu...Effects of vanadium on light olefins selectivity of FCC catalysts were investigated with vanadium having different oxidation numbers （hereinafter abbreviated as Oxnum）. Molecular modeling studies showed that vanadium with low Oxnum could affect the chemical conversion of large-size hydrocarbon molecules. However, the vanadium deposited on equilibrium catalyst bad high Oxnum because of the oxidation reaction taking place in the regenerator, so an activation method to reduce vanadium Oxnum named ＂selective activation＂ was introduced. It was proved by means of Electron Paramagnetic Resonance （EPR） and Temperature-Programmed Reduction （TPR） methods that the vanadium Oxnum was decreased, when the catalyst was activated. The molecular modeling studies are consistent well with the lab evaluation results. The light olefins selectivity of activated equilibrium catalysts was better than that achieved by the inactivated catalysts. Similar results were observed with the lab vanadium-contaminated catalyst. The light olefins selectivity of the catalyst was optimized when the vanadium Oxnum was close to 2 （VO）.展开更多
基金supported by the National Natural Science Foundation of China(21277009,21577005)~~
文摘A titania pillared interlayered clay（Ti-PILC） supported vanadia catalyst（V2O5/TiO2-PILC） was prepared by wet impregnation for the selective catalytic reduction（SCR） of NO with ammonia. Compared to the traditional V2O5/TiO2 and V2O5-MoO3/TiO2 catalysts, the V2O5/TiO2-PILC catalyst exhibited a higher activity and better SO2 and H2O resistance in the NH3-SCR reaction. Characterization using TPD, in situ DRIFT and XPS showed that surface sulfate and/or sulfite species and ionic SO4^（2-）species were formed on the catalyst in the presence of SO2. The ionic SO4^（2-） species on the catalyst surface was one reason for deactivation of the catalyst in SCR. The formation of the ionic SO4^（2-） species was correlated with the amount of surface adsorbed oxygen species. Less adsorbed oxygen species gave less ionic SO4^（2-） species on the catalyst.
基金Supported by the National Natural Science Foundation of China (No. 29792073-3).
文摘The selective oxidation of n-butane to maleic anhydride (MA) on a vanadium-phosphorus oxide (VPO) catalyst was studied using on-line gas-chromatography combined with mass spectrometry(GC-MS) and transient response technique. The reaction intermediates, buterie and furan, were found in the reaction effluent under near industrial feed condition (3% butane+15%O2), while dihydrofuran was detected at high butane concentration (12% butane, 5%O2). Some intermediates of MA decomposition were also identified. Detection of these intermediates shows that the vanadium phosphorus oxides are able to dehydrogenate butane to butene, and butene further to form MA. Based on these observations, a modified scheme of reaction network is proposed. The transient experiments show that butane in the gas phase may directly react with oxygen both on the surface and from the metal oxide lattice, without a proceeding adsorption step. Gas phase oxygen can be adsorbed and transformed to surface lattice oxygen but it can not participate in selective oxidation. Adsorbed oxygen leads to deep oxidation, while lattice oxygen leads to selective oxidation.
基金supported by the National Natural Science Foundation of China(21421004,21573067,91545103)Program of Shanghai Academic Research Leader(17XD1401400)~~
文摘The oxidative dehydrogenation（ODH） of propane on monomeric VO3 supported by CeO2（111）（VO3/CeO 2（111）） is studied by periodic density functional theory calculations. Detailed energetic, structural, and electronic properties of these reactions are determined. The calculated activation energies of the breaking of the first and second C–H bonds of propane on the VO3/CeO2（111） catalyst are compared, and it is found that both the unique structural and electronic effects of the VO3/CeO2（111） catalyst contribute to the relatively easy rupture of the first C–H bond of the propane molecule during the ODH reaction. In particular, the so-called new empty localized states that are mainly constituted of O2 porbitals of the ceria-supported VO3 species are determined to be crucial for assisting the cleavage of the first C–H bond of the propane molecule. Following this they become occupied and the remaining C–H bonds become increasingly difficult to break owing to the increasing repulsion between the localized 4 felectrons at the Cecations, resulting in the adsorption of more H and other moieties. This work illustrates that CeO2-supported monomeric vanadium oxides can exhibit unique activity and selectivity for the catalytic ODH of alkanes to alkenes.
基金supported by the National Basic Research Program of China(973 Program No.2012CB224802)
文摘In order to evaluate the role of vanadium in the hydrogenation (HYD) reaction, a series of alumina supported vanadium catalysts were prepared and characterized by SEM, XRD, Raman spectrometry, 51V NMR, XPS, as well as TPR analyses. The catalytic performance of vanadium in HYD of model molecules (naphthalene) and real feedstock (Kuwait atmospheric residue) was studied after sulfidation of the catalysts. It can be concluded that the HYD capabilities of V/Al2O3 catalysts are lower than that of conventional NiMo/Al2O3 catalyst (RefNiMo). The V/Al2O3 catalysts can only facilitate hydrogenation of the first ring of naphthalene, but have little effect on the further hydrogenation of tetralin. Owing to the different forms of metals and sulfur compounds in residue, the weak HYD activity of V/Al2O3 catalysts is able to facilitate the HDM reaction of the residue, albeit with a slight effect on HDS activity.
基金Supported by the National Natural Science Foundation of China(21006065)the Zhejiang Provincial Natural Science Foundation of China(Y5100009)
文摘The catalytic activity of carbon nanotubes-supported vanadium oxide(V_2O_5/CNTs) catalysts in the selective catalytic reduction(SCR) of NO with NH_3 at low temperatures(<250℃) was investigated.The effects of V_2O_5loading,reaction temperature,and presence of SO_2 on the SCR activity were evaluated.The results show that V_2O_5/CNTs catalysts exhibit high activity for NO reduction with NH_3 at low-temperatures.The catalysts also show very high stability in the presence of SO_2.More interestingly,their activities are significantly promoted instead of being poisoned by SO_2.The promoting effect of SO_2 is distinctly associated with V_2O_5 loading,particularly maximized at low V_2O_5 loading,which indicated the role of CNTs support in this effect.The promoting effect of SO_2 at low temperatures suggests that V_2O_5/CNTs catalysts are promising catalytic materials for low-temperature SCR reactions.
基金Project(08JJ3022) supported by the Natural Science Foundation of Hunan Province, China
文摘TiO2 photocatalysts loaded with V2O5 were prepared via a modified hydrolysis process,and characterized by X-ray diffraction,transmission electron microscopy,Raman spectra and diffuse reflectance UV-Vis spectra measurements. The photocatalytic activity of V2O5/TiO2 was investigated by employing splitting of water for O2 evolution. The results indicate that V2O5 loading can pronouncedly improve the photocatalytic activity of TiO2 with Fe3+ as an electron acceptor under UV or visible light irradiation. The optimum mass fraction of the loaded V2O5 is 8%,and the largest speed of O2 evolution for 8%V2O5 (mass fraction) loaded TiO2 catalyst is 118.2 μmol/(L.h) under UV irradiation,and 83.7 μmol/(L.h) under visible light irradiation.
文摘Effects of vanadium on light olefins selectivity of FCC catalysts were investigated with vanadium having different oxidation numbers （hereinafter abbreviated as Oxnum）. Molecular modeling studies showed that vanadium with low Oxnum could affect the chemical conversion of large-size hydrocarbon molecules. However, the vanadium deposited on equilibrium catalyst bad high Oxnum because of the oxidation reaction taking place in the regenerator, so an activation method to reduce vanadium Oxnum named ＂selective activation＂ was introduced. It was proved by means of Electron Paramagnetic Resonance （EPR） and Temperature-Programmed Reduction （TPR） methods that the vanadium Oxnum was decreased, when the catalyst was activated. The molecular modeling studies are consistent well with the lab evaluation results. The light olefins selectivity of activated equilibrium catalysts was better than that achieved by the inactivated catalysts. Similar results were observed with the lab vanadium-contaminated catalyst. The light olefins selectivity of the catalyst was optimized when the vanadium Oxnum was close to 2 （VO）.
