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
Alumina-supported bimetallic cobalt-nickel catalyst has been prepared and employed in a fixed-bed reactor for the direct production of synthesis gas from glycerol steam reforming. Physicochemical properties of the 5Co...Alumina-supported bimetallic cobalt-nickel catalyst has been prepared and employed in a fixed-bed reactor for the direct production of synthesis gas from glycerol steam reforming. Physicochemical properties of the 5Co-10Ni/85Al2O3 catalyst were determined from N2-physisorption, H2-chemisorption, CO2 and NH3-temperature-programmed desorption measurements as well as X-ray diffraction analysis. Both weak and strong acid sites are present on the catalyst surface. The acidic:basic ratio is about 7. Carbon deposition was evident at 923 K;addition of H2 however has managed to reduce the carbon deposition. Significantly, this has resulted in the increment of CH4 formation rate, consistent with the increased carbon gasification and methanation. Carbon deposition was almost non-existent, particularly at 1023 K. In addition, the inclusion of hydrogen also has contributed to the decrease of CO2 and increase of CO formation rates. This was attributed to the reverse water-gas-shift reaction. Overall, both the CO2:CO and CO2:CH4 ratios decrease with the hydrogen partial pressure.展开更多
Ni/CeO_(2) catalysts(nCeO_(2):n_(Ni)=0,1,4,7,10)supported on SiC porous ce ramics for ethanol steam reforming(ESR)were investigated with respect to hydrogen production performance and growth of carbon deposition.The o...Ni/CeO_(2) catalysts(nCeO_(2):n_(Ni)=0,1,4,7,10)supported on SiC porous ce ramics for ethanol steam reforming(ESR)were investigated with respect to hydrogen production performance and growth of carbon deposition.The oxygen released from CeO_(2) enables the oxidation of CH_(x) species to serve as carbon precursors,thus providing Ni/CeO_(2) catalysts with stronger resistance to carbon deposition compared with Ni catalysts.The Ni/CeO_(2) catalysts prepared by inverse microemulsion and impregnation methods exhibit regular semicircular spherical shape on SiC porous ceramics.Under 500℃for 25 h of ESR reaction,the ethanol conversion rate over Ni/CeO_(2) catalysts(n_(CeO_(2)):n_(Ni)=7)is sustained up to 100%and H_(2) selectivity is essentially kept at 74%.The by-product selectivity declines stepwise with increasing content of CeO_(2),which is attributed to the adsorption and oxidation of CO and of CH_(x) species as CH_4 precursor from CeO_(2).The scanning electron microscopy(SEM)and transform electron microscopy(TEM)results reveal that further loading of CeO_(2) on the surface of Ni catalysts can alleviate both migration and sintering of Ni particles.Furthermore,carbon deposition on Ni/CeO_(2) catalysts preferentially outgrow filamentous rather than amorphous carbon,with a tendency for the latter to be more deactivated.展开更多
We have dispersed individual Pd atoms onto ZnO nanowires(NWs)as single‐atom catalysts(SACs)and evaluated their catalytic performance for several selected catalytic reactions.The Pd1/ZnO SAC is highly active,stable,an...We have dispersed individual Pd atoms onto ZnO nanowires(NWs)as single‐atom catalysts(SACs)and evaluated their catalytic performance for several selected catalytic reactions.The Pd1/ZnO SAC is highly active,stable,and selective towards CO2for steam reforming of methanol to produce hydrogen.This catalyst system is active for oxidation of CO and H2but performs poorly for preferential oxidation of CO in hydrogen‐rich stream primarily due to the strong competitive oxidation of H2on ZnO supported Pd1atoms.At ambient pressure,reverse water‐gas‐shift reaction occurs on the Pd1/ZnO SAC.This series of tests of catalytic reactions clearly demonstrate the importance of selecting the appropriate metal and support to develop SACs for catalytic transformation of molecules.展开更多
Catalytic steam reforming is a promising route for tar conversion to high energy syngas in the process of biomass gasification. However, the catalyst deactivation caused by the deposition of residual carbon is still a...Catalytic steam reforming is a promising route for tar conversion to high energy syngas in the process of biomass gasification. However, the catalyst deactivation caused by the deposition of residual carbon is still a major challenge. In this paper, a modified Ni-based Ni-Co/Al2O3-CaO (Ni-Co/AC) catalyst and a conventional Ni/Al2O3 (Ni/A) catalyst were prepared and tested for tar catalytic removal in which toluene was selected as the model component. Experiments were conducted to reveal the influences of the reaction temperature and the ratio between steam to carbon on the toluene conversion and the hydrogen yield. The physicochemical properties of the modified Ni-based catalyst were determined by a series of characterization methods. The results indicated that the Ni-Co alloy was determined over the Ni-Co/AC catalyst. The doping of CaO and the presence of Ni-Co alloy promoted the performance of toluene catalytic dissociation over Ni-Co/AC catalyst compared with that over Ni/A catalyst. After testing in steam for 40 h, the carbon conversion over Ni-Co/AC maintained above 86% and its resistance to carbon deposition was superior to Ni/A catalyst.展开更多
Hydrogen was prepared via catalytic steam reforming of bio-oil which was obtained from fast pyrolysis of biomass in a fluidized bed reactor.Influential factors including temperature,weight hourly space velocity(WHSV) ...Hydrogen was prepared via catalytic steam reforming of bio-oil which was obtained from fast pyrolysis of biomass in a fluidized bed reactor.Influential factors including temperature,weight hourly space velocity(WHSV) of bio-oil,mass ratio of steam to bio-oil(S/B) as well as catalyst type on hydrogen selectivity and other desirable gas products were investigated.Based on hydrogen in stoichiometric potential and carbon balance in gaseous phase and feed,hydrogen yield and carbon selectivity were examined.The experimental results show that higher temperature favors the hydrogen selectivity by H2 mole fraction in gaseous products stream and it plays an important role in hydrogen yield and carbon selectivity.Higher hydrogen selectivity and yield,and carbon selectivity were obtained at lower bio-oil WHSV.In catalytic steam reforming system a maximum steam concentration value exists,at which hydrogen selectivity and yield,and carbon selectivity keep constant.Through experiments,preferential operation conditions were obtained as follows:temperature 800～850℃,bio-oil WHSV below 3.0 h-1,and mass ratio of steam to bio-oil 10～12.The performance tests indicate that Ni-based catalysts are optional,especially Ni/α-Al2O3 effective in the steam reforming process.展开更多
Internal reformation of low steam methane fuel is highly beneficial for improving the energy efficiency and reducing the system complexity and cost of solid oxide fuel cells(SOFCs).However,anode coking for the Ni-base...Internal reformation of low steam methane fuel is highly beneficial for improving the energy efficiency and reducing the system complexity and cost of solid oxide fuel cells(SOFCs).However,anode coking for the Ni-based anode should be prevented before the technology becomes a reality.A multi-physics fully coupled model is employed to simulate the operations of SOFCs fueled by low steam methane.The multi-physics model produces I-V relations that are in excellent agreement with the experimental results.The multi-physics model and the experimental non-coking current density deduced kinetic carbon activity criterion are used to examine the effect of operating parameters and the anode diffusion barrier layer on the propensity of carbon deposition.The interplays among the fuel utilization ratio,current generation,thickness of the barrier layer and the cell operating voltage are revealed.It is demonstrated that a barrier layer of 400μm thickness is an optimal and safe anode design to achieve high power density and non-coking operations.The anode structure design can be very useful for the development of high efficiency and low cost SOFC technology.展开更多
A number of nanostructured carbon materials were proposed as new effective promoters for preparing modified Cu/ZnO/Al 2O 3 catalyst system for efficient hydrogen production from methanol steam reforming. Compared to t...A number of nanostructured carbon materials were proposed as new effective promoters for preparing modified Cu/ZnO/Al 2O 3 catalyst system for efficient hydrogen production from methanol steam reforming. Compared to the catalysts modified by other type of carbon materials, the ACF-promoted catalyst prepared via carbonate-coprecipitation method exhibit the highest performance in the low-temperature steam reforming of methanol. It was suggested that the intrinsic high surface area nature of ACF material may favor the generation of modified catalysts with a high surface area and improved component dispersion, thus leading to improved performance for methanol steam reforming.展开更多
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.
文摘Alumina-supported bimetallic cobalt-nickel catalyst has been prepared and employed in a fixed-bed reactor for the direct production of synthesis gas from glycerol steam reforming. Physicochemical properties of the 5Co-10Ni/85Al2O3 catalyst were determined from N2-physisorption, H2-chemisorption, CO2 and NH3-temperature-programmed desorption measurements as well as X-ray diffraction analysis. Both weak and strong acid sites are present on the catalyst surface. The acidic:basic ratio is about 7. Carbon deposition was evident at 923 K;addition of H2 however has managed to reduce the carbon deposition. Significantly, this has resulted in the increment of CH4 formation rate, consistent with the increased carbon gasification and methanation. Carbon deposition was almost non-existent, particularly at 1023 K. In addition, the inclusion of hydrogen also has contributed to the decrease of CO2 and increase of CO formation rates. This was attributed to the reverse water-gas-shift reaction. Overall, both the CO2:CO and CO2:CH4 ratios decrease with the hydrogen partial pressure.
基金Project supported by the Natural Science Foundation of Hunan Province,China (2022JJ30133)。
文摘Ni/CeO_(2) catalysts(nCeO_(2):n_(Ni)=0,1,4,7,10)supported on SiC porous ce ramics for ethanol steam reforming(ESR)were investigated with respect to hydrogen production performance and growth of carbon deposition.The oxygen released from CeO_(2) enables the oxidation of CH_(x) species to serve as carbon precursors,thus providing Ni/CeO_(2) catalysts with stronger resistance to carbon deposition compared with Ni catalysts.The Ni/CeO_(2) catalysts prepared by inverse microemulsion and impregnation methods exhibit regular semicircular spherical shape on SiC porous ceramics.Under 500℃for 25 h of ESR reaction,the ethanol conversion rate over Ni/CeO_(2) catalysts(n_(CeO_(2)):n_(Ni)=7)is sustained up to 100%and H_(2) selectivity is essentially kept at 74%.The by-product selectivity declines stepwise with increasing content of CeO_(2),which is attributed to the adsorption and oxidation of CO and of CH_(x) species as CH_4 precursor from CeO_(2).The scanning electron microscopy(SEM)and transform electron microscopy(TEM)results reveal that further loading of CeO_(2) on the surface of Ni catalysts can alleviate both migration and sintering of Ni particles.Furthermore,carbon deposition on Ni/CeO_(2) catalysts preferentially outgrow filamentous rather than amorphous carbon,with a tendency for the latter to be more deactivated.
基金funded by the National Science Foundation (CHE-1465057)
文摘We have dispersed individual Pd atoms onto ZnO nanowires(NWs)as single‐atom catalysts(SACs)and evaluated their catalytic performance for several selected catalytic reactions.The Pd1/ZnO SAC is highly active,stable,and selective towards CO2for steam reforming of methanol to produce hydrogen.This catalyst system is active for oxidation of CO and H2but performs poorly for preferential oxidation of CO in hydrogen‐rich stream primarily due to the strong competitive oxidation of H2on ZnO supported Pd1atoms.At ambient pressure,reverse water‐gas‐shift reaction occurs on the Pd1/ZnO SAC.This series of tests of catalytic reactions clearly demonstrate the importance of selecting the appropriate metal and support to develop SACs for catalytic transformation of molecules.
基金This work was financially supported by the National Nature Science Foundation of China(Grant Nos.51922040 and 51821004)the Fok Ying Tung Education Foundation(Grant No.161051)the Fundamental Research Funds for the Central Universities(Nos.2018ZD08 and 2020DF01).
文摘Catalytic steam reforming is a promising route for tar conversion to high energy syngas in the process of biomass gasification. However, the catalyst deactivation caused by the deposition of residual carbon is still a major challenge. In this paper, a modified Ni-based Ni-Co/Al2O3-CaO (Ni-Co/AC) catalyst and a conventional Ni/Al2O3 (Ni/A) catalyst were prepared and tested for tar catalytic removal in which toluene was selected as the model component. Experiments were conducted to reveal the influences of the reaction temperature and the ratio between steam to carbon on the toluene conversion and the hydrogen yield. The physicochemical properties of the modified Ni-based catalyst were determined by a series of characterization methods. The results indicated that the Ni-Co alloy was determined over the Ni-Co/AC catalyst. The doping of CaO and the presence of Ni-Co alloy promoted the performance of toluene catalytic dissociation over Ni-Co/AC catalyst compared with that over Ni/A catalyst. After testing in steam for 40 h, the carbon conversion over Ni-Co/AC maintained above 86% and its resistance to carbon deposition was superior to Ni/A catalyst.
基金Supported by Research Program Foundation of Science and Technology Commission of Shanghai Municipality (No041612002)
文摘Hydrogen was prepared via catalytic steam reforming of bio-oil which was obtained from fast pyrolysis of biomass in a fluidized bed reactor.Influential factors including temperature,weight hourly space velocity(WHSV) of bio-oil,mass ratio of steam to bio-oil(S/B) as well as catalyst type on hydrogen selectivity and other desirable gas products were investigated.Based on hydrogen in stoichiometric potential and carbon balance in gaseous phase and feed,hydrogen yield and carbon selectivity were examined.The experimental results show that higher temperature favors the hydrogen selectivity by H2 mole fraction in gaseous products stream and it plays an important role in hydrogen yield and carbon selectivity.Higher hydrogen selectivity and yield,and carbon selectivity were obtained at lower bio-oil WHSV.In catalytic steam reforming system a maximum steam concentration value exists,at which hydrogen selectivity and yield,and carbon selectivity keep constant.Through experiments,preferential operation conditions were obtained as follows:temperature 800～850℃,bio-oil WHSV below 3.0 h-1,and mass ratio of steam to bio-oil 10～12.The performance tests indicate that Ni-based catalysts are optional,especially Ni/α-Al2O3 effective in the steam reforming process.
基金supported by the National Natural Science Foundation of China (No.11574284 abd No.11774324)the National Basic Research Program of China (No.2012CB215405)Collaborative Innovation Center of Suzhou Nano Science and Technology
文摘Internal reformation of low steam methane fuel is highly beneficial for improving the energy efficiency and reducing the system complexity and cost of solid oxide fuel cells(SOFCs).However,anode coking for the Ni-based anode should be prevented before the technology becomes a reality.A multi-physics fully coupled model is employed to simulate the operations of SOFCs fueled by low steam methane.The multi-physics model produces I-V relations that are in excellent agreement with the experimental results.The multi-physics model and the experimental non-coking current density deduced kinetic carbon activity criterion are used to examine the effect of operating parameters and the anode diffusion barrier layer on the propensity of carbon deposition.The interplays among the fuel utilization ratio,current generation,thickness of the barrier layer and the cell operating voltage are revealed.It is demonstrated that a barrier layer of 400μm thickness is an optimal and safe anode design to achieve high power density and non-coking operations.The anode structure design can be very useful for the development of high efficiency and low cost SOFC technology.
文摘A number of nanostructured carbon materials were proposed as new effective promoters for preparing modified Cu/ZnO/Al 2O 3 catalyst system for efficient hydrogen production from methanol steam reforming. Compared to the catalysts modified by other type of carbon materials, the ACF-promoted catalyst prepared via carbonate-coprecipitation method exhibit the highest performance in the low-temperature steam reforming of methanol. It was suggested that the intrinsic high surface area nature of ACF material may favor the generation of modified catalysts with a high surface area and improved component dispersion, thus leading to improved performance for methanol steam reforming.
