The aim of this work was to evaluate the catalytic properties of a Ru promoted Co/SBA-15 catalyst for Fischer-Tropsch synthesis （FTS）. The Ru promoted Co/SBA-15 catalyst was prepared by wet impregnation method and w...The aim of this work was to evaluate the catalytic properties of a Ru promoted Co/SBA-15 catalyst for Fischer-Tropsch synthesis （FTS）. The Ru promoted Co/SBA-15 catalyst was prepared by wet impregnation method and was characterized by X-ray diffraction, X-ray energy dispersion spectrophotometer, N2 adsorption-desorption, temperature-programmed reduction and transmission electron microscopy. The Fischer-Tropsch synthesis using the catalyst was carried out to evaluate the catalyst activity and its effect on FTS product distribution. The synthesis was carried out in a slurry reactor operating at 513 K, 20 atm, CO ： H2 molar ratio of 1 ： 1. X-ray diffraction showed that the calcined cobalt catalyst did not modify the structure of SBA-15, proving that Co was present in the form of Co3O4 in the catalyst. The addition of cobalt in SBA-15 decreased the specific superficial area of the molecular sieve. Fischer-Tropsch synthesis activity and C5＋ hydrocarbon selectivity increased with the addition of Ru. The increases in activity and selectivity were attributed to the increased number of active sites resulting from higher reducibility and the synergetic effect of Ru and Co. Ru/Co/SBA-15 catalysts showed moderate conversion （40%） and high selectivity towards the production of C5＋ （80 wt%）.展开更多
The Ni/SBA-15 catalysts were synthesized using the in situ method and the influence of crystallization temperature on nickel utilization efficiency-a critical factor in mesoporous material design-was systematically in...The Ni/SBA-15 catalysts were synthesized using the in situ method and the influence of crystallization temperature on nickel utilization efficiency-a critical factor in mesoporous material design-was systematically investigated.The structural characteristics and nickel anchoring capacity were analyzed using XRD,BET,FT-IR,H2-TPR,and ICP-OES.The results demonstrated that the crystallization temperature significantly affected the framework order of SBA-15 and the surface anchoring efficiency of Ni ions.The nickel utilization efficiency increased from 8.4%at 80℃ to 60.49%at 140℃,but then decreased to 47.25%at 160℃,indicating an optimal crystallization temperature window.This provides crucial guidance for tailoring high-performance metal-doped molecular sieves.The optimal catalyst exhibited excellent performance in the hydrogenation of 1,4-butynediol(BYD):the BYD conversion reached 97.25%with 88.99%selectivity of 1,4-butenediol(BED)within 5 h,and reached 99.73%with 87.34%selectivity of 1,4-butanediol(BDO)after 20 h reaction.These results revealed the critical role of crystallization temperature in metal utilization and provided theoretical support for designing highly active molecular sieve catalysts.展开更多
Dielectric barrier discharge(DBD)plasma excited by a high-frequency alternating-current(AC)power supply is widely employed for the degradation of volatile organic compounds(VOCs).However,the thermal effect generated d...Dielectric barrier discharge(DBD)plasma excited by a high-frequency alternating-current(AC)power supply is widely employed for the degradation of volatile organic compounds(VOCs).However,the thermal effect generated during the discharge process leads to energy waste and low energy utilization efficiency.In this work,an innovative DBD thermally-conducted catalysis(DBD-TCC)system,integrating high-frequency AC-DBD plasma and its generated thermal effects to activate the Co/SBA-15 catalyst,was employed for toluene removal.Specifically,Co/SBA-15 catalysts are closely positioned to the ground electrode of the plasma zone and can be heated and activated by the thermal effect when the voltage exceeds 10 k V.At12.4 k V,the temperature in the catalyst zone reached 261℃ in the DBD-TCC system,resulting in an increase in toluene degradation efficiency of 17%,CO_(2)selectivity of 21.2%,and energy efficiency of 27%,respectively,compared to the DBD system alone.In contrast,the DBD thermally-unconducted catalysis(DBD-TUC)system fails to enhance toluene degradation due to insufficient heat absorption and catalytic activation,highlighting the crucial role of AC-DBD generated heat in the activation of the catalyst.Furthermore,the degradation pathway and mechanism of toluene in the DBD-TCC system were hypothesized.This work is expected to provide an energy-efficient approach for high-frequency AC-DBD plasma removal of VOCs.展开更多
A series of Ni/SBA-15 catalysts with Ni contents ranging from 5wt% to 20wt% as well as 10wt%Ni/10wt%CexZr1-xO2/SBA-15 （x=0, 0.5, 1） were prepared. The structures of the catalysts were characterized using XRD, TPR, T...A series of Ni/SBA-15 catalysts with Ni contents ranging from 5wt% to 20wt% as well as 10wt%Ni/10wt%CexZr1-xO2/SBA-15 （x=0, 0.5, 1） were prepared. The structures of the catalysts were characterized using XRD, TPR, TEM and BET techniques. The catalytic activities of the catalysts for steam reforming of methane were evaluated in a continuous flow microreactor. The results indicated that both the Ni/SBA-15 and the Ni/CexZr1-xO2/SBA-15 catalysts had good catalytic activities at at- mospheric pressure. The 10wt%Ni/SBA-15 catalyst exhibited excellent stability at 800 ℃ for time on stream of 740 h. After the reaction, carbon deposits were not formed on the surface of the catalyst. There existed a regular hexagonal mesoporous structure in the Ni/SBA-15 and the Ni/CexZr1-xO2/SBA-15 catalysts. The nickel species and the CexZr1-xO2 component were all confined in the SBA-15 mesopores. The CexZr1-xO2 could promote dispersion of the nickel species in the Ni/CexZr1-xO2/SBA-15 catalysts.展开更多
A series of the Pt-Sn/SBA-15 catalysts were prepared and their properties characterized by using X-ray powder diffraction （XRD）, N2 adsorption-desorption, high resolution transmission electron microscope, X-ray phot...A series of the Pt-Sn/SBA-15 catalysts were prepared and their properties characterized by using X-ray powder diffraction （XRD）, N2 adsorption-desorption, high resolution transmission electron microscope, X-ray photoelectron spectroscopy （XPS） and H2-temperature programmed reduction. Their performances in long chain alkane dehydrogenation were evaluated in a fixed-bed microreactor with dodecane as a model alkane. The results indicated that SBA-15 maintained the well-order mesoporous structure during the reaction. The performance of the catalyst was found not dominated by its textural properties, but by the molar ratio of Sn to Pt which governed the degree of Sn reduction. Owing to the highest degree of Sn reduction, 1% （by mass） Pt-1.8% （by mass） Sn/SBA-15 showed the best catalytic activity. At 0.1 MPa and 470℃, the molar ratio of hydrogen to alkane at 4, and liquid hourly space velocity （LHSV） 20 h^-1, the dodecane conversion is 10%, and the dodecene selectivity is about 70%.展开更多
A new method for the preparation of SBA-15-supported palladium catalyst for Heck reaction in supercritical carbon dioxide was presented.The newly formed SBA-15-supported palladium catalyst（Ph-SBA-15-PPh_3-Pd） exhibi...A new method for the preparation of SBA-15-supported palladium catalyst for Heck reaction in supercritical carbon dioxide was presented.The newly formed SBA-15-supported palladium catalyst（Ph-SBA-15-PPh_3-Pd） exhibited high catalytic activity for the Heck reaction of 4-nitrobromobenzene with methyl acrylate.The catalyst can be reused several times without a loss of activity.展开更多
A series of Ni/SBA-15 catalysts with 5wt% to 15wt% Ni content as well as a series of 12.5%Ni/Cu/SBA-15 catalysts with 1% to 10% copper content were prepared by the impregnation method. The catalytic performance for pa...A series of Ni/SBA-15 catalysts with 5wt% to 15wt% Ni content as well as a series of 12.5%Ni/Cu/SBA-15 catalysts with 1% to 10% copper content were prepared by the impregnation method. The catalytic performance for partial oxidation of methane was investigated in a continuous flow microreactor under atmospheric pressure. The textural and chemical properties of the catalysts were characterized by XRD, TEM, BET and Hz-TPR techniques. The results indicated that the catalysts modified with Cu promoter showed better performance than those without modification. For the 12.5%Ni/2.5%/Cu/SBA-15 catalyst, at 850 ℃ the conversion of CH4 reached 97.9% and the selectivity of CO and H2 reached 98.0% and 96.0%, respectively. In XRD patterns of the Ni/Cu/SBA-15 catalyst with 7.5 to 10% Cu contents there were CuO characteristic peaks beside NiO characteristic peaks. The mesoporous structure of SBA-15 was retained in all of the catalysts. TPR analysis of the catalysts revealed that a strong interaction between Ni, Cu promoter and SBA-15 support may be existed. This interaction enhanced significantly the redox properties of the catalysts resulting in the higher catalytic activity.展开更多
A series of Ni/SBA-15 catalysts with Ni contents ranging from 5 wt% to 15 wt%, as well as another series of 10%Ni/MgO/SBA-15 catalysts, in which the range of the MgO content was from 1 wt% to 7 wt%, were prepared, and...A series of Ni/SBA-15 catalysts with Ni contents ranging from 5 wt% to 15 wt%, as well as another series of 10%Ni/MgO/SBA-15 catalysts, in which the range of the MgO content was from 1 wt% to 7 wt%, were prepared, and their catalytic performances for the reaction of combined steam and carbon dioxide reforming of methane were investigated in a continuous flow microreactor. The structures of the catalysts were characterized using the XRD, H2-TPR and CO2-TPD techniques. The results indicated that the CO selectivity for this reaction was very close to 100%, and the H2/CO ratio of the product gas could be controlled by changing the H2O/CO2 molar ratio of the feed gas. The simultaneous and plentiful existing of steam and CO2 had a significant influence on the catalytic performance of the 10%Ni/SBA-15 catalyst without modification. After reacting at 850 °C for 120 h over this catalyst, the CH4 conversion dropped from 98% to 85%, and the CO2 conversion decreased from 86% to 53%. However, the 10%Ni/3%MgO/SBA-15 catalyst exhibited a much better catalytic performance, and after reacting for 620 h, the CO2 conversion over this catalyst dropped from 92% to around 77%, while the CH4 conversion was not decreased. Oxidation of the Ni0 species as well as carbon deposition during the reaction were the main reasons for the deactivation of the catalyst without modification. On the other hand, modification by the MgO promoter improved the dispersion of the Ni0 species, and enhanced the CO2 adsorption affinity which in turn depressed the occurring of carbon deposition, and thus retarded the deactivation process.展开更多
A series of Ni/SBA-15 catalysts with Ni contents from 7.5 wt% to 15 wt% were prepared by impregnation method.The effect of O2 and H2O on the combined reforming of the simulated biogas to syngas was investigated in a c...A series of Ni/SBA-15 catalysts with Ni contents from 7.5 wt% to 15 wt% were prepared by impregnation method.The effect of O2 and H2O on the combined reforming of the simulated biogas to syngas was investigated in a continuous flow fixed-bed micro-reactor.The stability of the catalyst was tested at 800 ？C.The results indicated that 10wt%Ni/SBA-15 catalyst exhibited the highest catalytic activities for the combined reforming of the simulated biogas to syngas.Under the reaction conditions of the feed gas molar ratios CH4/CO2/O2/H2O = 2/1/0.6/0.6,GHSV = 24000 ml·gcat^-1·h^-1 and the reaction temperature T = 800 ℃,the conversions of CH4 and CO2 were 92.8% and 76.3%,respectively,and the yields of CO and H2 were 99.0% and 82.0%,respectively.The catalytic activities of the catalyst did not decrease obviously after 100 h reaction time on stream.展开更多
Rod-like, hexagonal and fiber-like SBA-15 mesoporous silicas were synthesized to support MnO_x for toluene oxidation. This study showed that the morphology of the supports greatly influenced the catalytic activity in ...Rod-like, hexagonal and fiber-like SBA-15 mesoporous silicas were synthesized to support MnO_x for toluene oxidation. This study showed that the morphology of the supports greatly influenced the catalytic activity in toluene oxidation. MnO_x supported on rod-like SBA-15(R-SBA-15) displayed the best catalytic activity and the conversion at 230°C reached more than 90%, which was higher than the other two catalysts. MnO_x species consisted of coexisting MnO_2 and Mn_2O_3 on the three kinds of SBA-15 samples. Large amounts of Mn_2O_3 species were formed on the surface and high oxygen mobility was obtained on MnO_x supported on R-SBA-15, according to the H_2 temperature programmed reduction(H_2-TPR)and X-ray photoelectron spectroscopy(XPS) results. The Mn/R-SBA-15 catalyst with greater amounts of Mn_2O_3 species possessed a large amount of surface lattice oxygen, which accelerated the catalytic reaction rate. Therefore, the surface lattice oxygen and high oxygen mobility were critical factors on the catalytic activity of the Mn/R-SBA-15 catalyst.展开更多
The catalytic properties of PtSn-based catalysts supported on siliceous SBA-15 and Al-modified SBA-15, such as Al-incorporated SBA-15 （AlSBA-15） and alumina-modified SBA-15 （Al2O3/SBA-15）, for propane dehydrogenat...The catalytic properties of PtSn-based catalysts supported on siliceous SBA-15 and Al-modified SBA-15, such as Al-incorporated SBA-15 （AlSBA-15） and alumina-modified SBA-15 （Al2O3/SBA-15）, for propane dehydrogenation were investigated. Al2O3/SBA-15 was prepared either by an impregnation method using aluminum nitrate aqueous solution, or by the treatment of SBA-15 with a Al（OC3H7）3 solution in anhydrous toluene. N2-physisorption, FT-IR spectroscopy, solid-state 27Al MAS NMR spectroscopy, hydrogen chemisorption, XRF, NH3 temperature-programmed desorption, X-ray photoelectron spectroscopy and TPO were used to characterize these samples. Among these catalysts, the PtSn-based catalyst supported on Al2O3/SBA-15, which was grafted with Al（OC3H7）3, exhibited the best catalytic performance in terms of activity and stability The possible reason was due to the high Pt metal dispersion and/or the strong interactions among Pt, Sn, and the support.展开更多
The Ni/Mo/SBA-15 catalyst was modified by La2O3 in order to improve its thermal stability and carbon deposition resistance during the CO2 reforming of methane to syngas. The catalytic performance, thermal stability, s...The Ni/Mo/SBA-15 catalyst was modified by La2O3 in order to improve its thermal stability and carbon deposition resistance during the CO2 reforming of methane to syngas. The catalytic performance, thermal stability, structure, dispersion of nickel and carbon deposition of the modified and unmodified catalysts were comparatively investigated by many characterization techniques such as N2 adsorption, H2-TPR, CO2-TPD, XRD, FT-IR and SEM. It was found that the major role of La2O3 additive was to improve the pore structure and inhibit carbon deposition on the catalyst surface. The La2O3 modified Ni/Mo/SBA-15 catalyst possessed a mesoporous structure and high surface area. The high surface area of the La2O3 modified catalysts resulted in strong interaction between Ni and Mo-La, which improved the dispersion of Ni, and retarded the sintering of Ni during the CO2 reforming process. The reaction evaluation results also showed that the La2O3 modified Ni/Mo/SBA-15 catalysts exhibited high stability.展开更多
ZnO-CeO2/SBA-15 catalysts were prepared by two kinds of solid-state grinding method and used for the production of 1,3-butadiene(1,3-BD) from ethanol.A mixture of SBA-15(with or without organic template) and metal pre...ZnO-CeO2/SBA-15 catalysts were prepared by two kinds of solid-state grinding method and used for the production of 1,3-butadiene(1,3-BD) from ethanol.A mixture of SBA-15(with or without organic template) and metal precursors were ground in solid-state.The obtained catalysts were characterized by TG,N2 adsorption-desorption,TEM,XRD,Py-FTIR and NH_3-TPD techniques.Superior dispersion of metal oxides and more exposed acid sites were achieved on the catalyst lOZn_1Ce_5-AS with the presence of organic template in SBA-15 during the solid-state grinding process.The catalytic performance was evaluated in a fixed-bed reactor and a 1,3-butadiene selectivity of as high as 45% is achieved.This is attributed to the coupling effect of Zn and Ce species in the mesopores of SBA-15,in which Zn promotes ethanol dehydrogenation and Ce enhances aldol-condensation,respectively.Additionally,solvent-free method inspires new catalyst synthesis strategy for the production of 1,3-butadiene from ethanol.展开更多
基金supported by the Coordenao de Aperfeioamento de Pessoal de Nível Superior(CAPES)and Petrobras
文摘The aim of this work was to evaluate the catalytic properties of a Ru promoted Co/SBA-15 catalyst for Fischer-Tropsch synthesis （FTS）. The Ru promoted Co/SBA-15 catalyst was prepared by wet impregnation method and was characterized by X-ray diffraction, X-ray energy dispersion spectrophotometer, N2 adsorption-desorption, temperature-programmed reduction and transmission electron microscopy. The Fischer-Tropsch synthesis using the catalyst was carried out to evaluate the catalyst activity and its effect on FTS product distribution. The synthesis was carried out in a slurry reactor operating at 513 K, 20 atm, CO ： H2 molar ratio of 1 ： 1. X-ray diffraction showed that the calcined cobalt catalyst did not modify the structure of SBA-15, proving that Co was present in the form of Co3O4 in the catalyst. The addition of cobalt in SBA-15 decreased the specific superficial area of the molecular sieve. Fischer-Tropsch synthesis activity and C5＋ hydrocarbon selectivity increased with the addition of Ru. The increases in activity and selectivity were attributed to the increased number of active sites resulting from higher reducibility and the synergetic effect of Ru and Co. Ru/Co/SBA-15 catalysts showed moderate conversion （40%） and high selectivity towards the production of C5＋ （80 wt%）.
文摘The Ni/SBA-15 catalysts were synthesized using the in situ method and the influence of crystallization temperature on nickel utilization efficiency-a critical factor in mesoporous material design-was systematically investigated.The structural characteristics and nickel anchoring capacity were analyzed using XRD,BET,FT-IR,H2-TPR,and ICP-OES.The results demonstrated that the crystallization temperature significantly affected the framework order of SBA-15 and the surface anchoring efficiency of Ni ions.The nickel utilization efficiency increased from 8.4%at 80℃ to 60.49%at 140℃,but then decreased to 47.25%at 160℃,indicating an optimal crystallization temperature window.This provides crucial guidance for tailoring high-performance metal-doped molecular sieves.The optimal catalyst exhibited excellent performance in the hydrogenation of 1,4-butynediol(BYD):the BYD conversion reached 97.25%with 88.99%selectivity of 1,4-butenediol(BED)within 5 h,and reached 99.73%with 87.34%selectivity of 1,4-butanediol(BDO)after 20 h reaction.These results revealed the critical role of crystallization temperature in metal utilization and provided theoretical support for designing highly active molecular sieve catalysts.
基金supported by National Natural Science Foundation of China(No.52177130)the Key Projects for Industrial Prospects and Core Technology Research in Suzhou City(No.SYC2022029)。
文摘Dielectric barrier discharge(DBD)plasma excited by a high-frequency alternating-current(AC)power supply is widely employed for the degradation of volatile organic compounds(VOCs).However,the thermal effect generated during the discharge process leads to energy waste and low energy utilization efficiency.In this work,an innovative DBD thermally-conducted catalysis(DBD-TCC)system,integrating high-frequency AC-DBD plasma and its generated thermal effects to activate the Co/SBA-15 catalyst,was employed for toluene removal.Specifically,Co/SBA-15 catalysts are closely positioned to the ground electrode of the plasma zone and can be heated and activated by the thermal effect when the voltage exceeds 10 k V.At12.4 k V,the temperature in the catalyst zone reached 261℃ in the DBD-TCC system,resulting in an increase in toluene degradation efficiency of 17%,CO_(2)selectivity of 21.2%,and energy efficiency of 27%,respectively,compared to the DBD system alone.In contrast,the DBD thermally-unconducted catalysis(DBD-TUC)system fails to enhance toluene degradation due to insufficient heat absorption and catalytic activation,highlighting the crucial role of AC-DBD generated heat in the activation of the catalyst.Furthermore,the degradation pathway and mechanism of toluene in the DBD-TCC system were hypothesized.This work is expected to provide an energy-efficient approach for high-frequency AC-DBD plasma removal of VOCs.
基金Financial funds from the Chinese Natural Science Foundation(Project No.20473009)the Beijing Natural Science Foundation(Project No.8062023)+1 种基金the National Basic Research Program of China(Project No.2005CB221405)the National"863"Project of China(No.2006 AA10Z425)are gratefully acknowledged.
文摘A series of Ni/SBA-15 catalysts with Ni contents ranging from 5wt% to 20wt% as well as 10wt%Ni/10wt%CexZr1-xO2/SBA-15 （x=0, 0.5, 1） were prepared. The structures of the catalysts were characterized using XRD, TPR, TEM and BET techniques. The catalytic activities of the catalysts for steam reforming of methane were evaluated in a continuous flow microreactor. The results indicated that both the Ni/SBA-15 and the Ni/CexZr1-xO2/SBA-15 catalysts had good catalytic activities at at- mospheric pressure. The 10wt%Ni/SBA-15 catalyst exhibited excellent stability at 800 ℃ for time on stream of 740 h. After the reaction, carbon deposits were not formed on the surface of the catalyst. There existed a regular hexagonal mesoporous structure in the Ni/SBA-15 and the Ni/CexZr1-xO2/SBA-15 catalysts. The nickel species and the CexZr1-xO2 component were all confined in the SBA-15 mesopores. The CexZr1-xO2 could promote dispersion of the nickel species in the Ni/CexZr1-xO2/SBA-15 catalysts.
基金Supported by the National Natural Science Foundation of China （20376005）.
文摘A series of the Pt-Sn/SBA-15 catalysts were prepared and their properties characterized by using X-ray powder diffraction （XRD）, N2 adsorption-desorption, high resolution transmission electron microscope, X-ray photoelectron spectroscopy （XPS） and H2-temperature programmed reduction. Their performances in long chain alkane dehydrogenation were evaluated in a fixed-bed microreactor with dodecane as a model alkane. The results indicated that SBA-15 maintained the well-order mesoporous structure during the reaction. The performance of the catalyst was found not dominated by its textural properties, but by the molar ratio of Sn to Pt which governed the degree of Sn reduction. Owing to the highest degree of Sn reduction, 1% （by mass） Pt-1.8% （by mass） Sn/SBA-15 showed the best catalytic activity. At 0.1 MPa and 470℃, the molar ratio of hydrogen to alkane at 4, and liquid hourly space velocity （LHSV） 20 h^-1, the dodecane conversion is 10%, and the dodecene selectivity is about 70%.
基金National Natural Science Foundation of China(No.20603005)the Specialized Research Fund for the Doctoral Program of Higher Education(No.20090041110012) for their financial support
文摘A new method for the preparation of SBA-15-supported palladium catalyst for Heck reaction in supercritical carbon dioxide was presented.The newly formed SBA-15-supported palladium catalyst（Ph-SBA-15-PPh_3-Pd） exhibited high catalytic activity for the Heck reaction of 4-nitrobromobenzene with methyl acrylate.The catalyst can be reused several times without a loss of activity.
基金supported by the National Basic Research Program of China (Project No. 2005CB221405)the National "863" Project of China (No.2006AA10Z425)
文摘A series of Ni/SBA-15 catalysts with 5wt% to 15wt% Ni content as well as a series of 12.5%Ni/Cu/SBA-15 catalysts with 1% to 10% copper content were prepared by the impregnation method. The catalytic performance for partial oxidation of methane was investigated in a continuous flow microreactor under atmospheric pressure. The textural and chemical properties of the catalysts were characterized by XRD, TEM, BET and Hz-TPR techniques. The results indicated that the catalysts modified with Cu promoter showed better performance than those without modification. For the 12.5%Ni/2.5%/Cu/SBA-15 catalyst, at 850 ℃ the conversion of CH4 reached 97.9% and the selectivity of CO and H2 reached 98.0% and 96.0%, respectively. In XRD patterns of the Ni/Cu/SBA-15 catalyst with 7.5 to 10% Cu contents there were CuO characteristic peaks beside NiO characteristic peaks. The mesoporous structure of SBA-15 was retained in all of the catalysts. TPR analysis of the catalysts revealed that a strong interaction between Ni, Cu promoter and SBA-15 support may be existed. This interaction enhanced significantly the redox properties of the catalysts resulting in the higher catalytic activity.
基金the National Basic Research Program ofChina (Project No. 2005CB221405)the National "863" Project ofChina (No. 2006AA10Z425)the Beijing Natural Science Foun-dation (Project No: 8062023)
文摘A series of Ni/SBA-15 catalysts with Ni contents ranging from 5 wt% to 15 wt%, as well as another series of 10%Ni/MgO/SBA-15 catalysts, in which the range of the MgO content was from 1 wt% to 7 wt%, were prepared, and their catalytic performances for the reaction of combined steam and carbon dioxide reforming of methane were investigated in a continuous flow microreactor. The structures of the catalysts were characterized using the XRD, H2-TPR and CO2-TPD techniques. The results indicated that the CO selectivity for this reaction was very close to 100%, and the H2/CO ratio of the product gas could be controlled by changing the H2O/CO2 molar ratio of the feed gas. The simultaneous and plentiful existing of steam and CO2 had a significant influence on the catalytic performance of the 10%Ni/SBA-15 catalyst without modification. After reacting at 850 °C for 120 h over this catalyst, the CH4 conversion dropped from 98% to 85%, and the CO2 conversion decreased from 86% to 53%. However, the 10%Ni/3%MgO/SBA-15 catalyst exhibited a much better catalytic performance, and after reacting for 620 h, the CO2 conversion over this catalyst dropped from 92% to around 77%, while the CH4 conversion was not decreased. Oxidation of the Ni0 species as well as carbon deposition during the reaction were the main reasons for the deactivation of the catalyst without modification. On the other hand, modification by the MgO promoter improved the dispersion of the Ni0 species, and enhanced the CO2 adsorption affinity which in turn depressed the occurring of carbon deposition, and thus retarded the deactivation process.
基金supported by the National Basic Research Program of China(Project No.2005CB221405)the National "863" Project of China (No.2006AA10Z425)the Beijing Natural Science Foundation (Project No: 8062023)
文摘A series of Ni/SBA-15 catalysts with Ni contents from 7.5 wt% to 15 wt% were prepared by impregnation method.The effect of O2 and H2O on the combined reforming of the simulated biogas to syngas was investigated in a continuous flow fixed-bed micro-reactor.The stability of the catalyst was tested at 800 ？C.The results indicated that 10wt%Ni/SBA-15 catalyst exhibited the highest catalytic activities for the combined reforming of the simulated biogas to syngas.Under the reaction conditions of the feed gas molar ratios CH4/CO2/O2/H2O = 2/1/0.6/0.6,GHSV = 24000 ml·gcat^-1·h^-1 and the reaction temperature T = 800 ℃,the conversions of CH4 and CO2 were 92.8% and 76.3%,respectively,and the yields of CO and H2 were 99.0% and 82.0%,respectively.The catalytic activities of the catalyst did not decrease obviously after 100 h reaction time on stream.
基金supported by the National Nature Science Foundation of China (Nos.21377016 and 21577014)Programme of Introducing Talents of Discipline to Universities (No.B13012)Program for Changjiang Scholars and Innovative Research Team in University (No.IRT_13R05)
文摘Rod-like, hexagonal and fiber-like SBA-15 mesoporous silicas were synthesized to support MnO_x for toluene oxidation. This study showed that the morphology of the supports greatly influenced the catalytic activity in toluene oxidation. MnO_x supported on rod-like SBA-15(R-SBA-15) displayed the best catalytic activity and the conversion at 230°C reached more than 90%, which was higher than the other two catalysts. MnO_x species consisted of coexisting MnO_2 and Mn_2O_3 on the three kinds of SBA-15 samples. Large amounts of Mn_2O_3 species were formed on the surface and high oxygen mobility was obtained on MnO_x supported on R-SBA-15, according to the H_2 temperature programmed reduction(H_2-TPR)and X-ray photoelectron spectroscopy(XPS) results. The Mn/R-SBA-15 catalyst with greater amounts of Mn_2O_3 species possessed a large amount of surface lattice oxygen, which accelerated the catalytic reaction rate. Therefore, the surface lattice oxygen and high oxygen mobility were critical factors on the catalytic activity of the Mn/R-SBA-15 catalyst.
基金supported by the National Nature Science Foundation of China (50873026, 21106017)the Production and Research Prospective Joint Research Project (BY2009153)+1 种基金the Science and Technology Support Program (BE2008129) of Jiangsu Province of ChinaSpecialized Research Fund for the Doctoral Program of Higher Education of China (20100092120047)
文摘The catalytic properties of PtSn-based catalysts supported on siliceous SBA-15 and Al-modified SBA-15, such as Al-incorporated SBA-15 （AlSBA-15） and alumina-modified SBA-15 （Al2O3/SBA-15）, for propane dehydrogenation were investigated. Al2O3/SBA-15 was prepared either by an impregnation method using aluminum nitrate aqueous solution, or by the treatment of SBA-15 with a Al（OC3H7）3 solution in anhydrous toluene. N2-physisorption, FT-IR spectroscopy, solid-state 27Al MAS NMR spectroscopy, hydrogen chemisorption, XRF, NH3 temperature-programmed desorption, X-ray photoelectron spectroscopy and TPO were used to characterize these samples. Among these catalysts, the PtSn-based catalyst supported on Al2O3/SBA-15, which was grafted with Al（OC3H7）3, exhibited the best catalytic performance in terms of activity and stability The possible reason was due to the high Pt metal dispersion and/or the strong interactions among Pt, Sn, and the support.
基金supported by the Key Project of Chinese National Programs for Fundamental Research and Development(973 Program 2005CB221204)the Natural Science Fund of China(20676087)
文摘The Ni/Mo/SBA-15 catalyst was modified by La2O3 in order to improve its thermal stability and carbon deposition resistance during the CO2 reforming of methane to syngas. The catalytic performance, thermal stability, structure, dispersion of nickel and carbon deposition of the modified and unmodified catalysts were comparatively investigated by many characterization techniques such as N2 adsorption, H2-TPR, CO2-TPD, XRD, FT-IR and SEM. It was found that the major role of La2O3 additive was to improve the pore structure and inhibit carbon deposition on the catalyst surface. The La2O3 modified Ni/Mo/SBA-15 catalyst possessed a mesoporous structure and high surface area. The high surface area of the La2O3 modified catalysts resulted in strong interaction between Ni and Mo-La, which improved the dispersion of Ni, and retarded the sintering of Ni during the CO2 reforming process. The reaction evaluation results also showed that the La2O3 modified Ni/Mo/SBA-15 catalysts exhibited high stability.
基金financial support from the National Natural Science Foundation of China(No.21878227)。
文摘ZnO-CeO2/SBA-15 catalysts were prepared by two kinds of solid-state grinding method and used for the production of 1,3-butadiene(1,3-BD) from ethanol.A mixture of SBA-15(with or without organic template) and metal precursors were ground in solid-state.The obtained catalysts were characterized by TG,N2 adsorption-desorption,TEM,XRD,Py-FTIR and NH_3-TPD techniques.Superior dispersion of metal oxides and more exposed acid sites were achieved on the catalyst lOZn_1Ce_5-AS with the presence of organic template in SBA-15 during the solid-state grinding process.The catalytic performance was evaluated in a fixed-bed reactor and a 1,3-butadiene selectivity of as high as 45% is achieved.This is attributed to the coupling effect of Zn and Ce species in the mesopores of SBA-15,in which Zn promotes ethanol dehydrogenation and Ce enhances aldol-condensation,respectively.Additionally,solvent-free method inspires new catalyst synthesis strategy for the production of 1,3-butadiene from ethanol.
