CO2 methanation with Hydrogen to form CH4 offers a solution for off-peak renewable energy storage. γ-alumina-supported Mo and Ni-Mo catalysts were used in CO2 methanation, either in their reduced or in their carburiz...CO2 methanation with Hydrogen to form CH4 offers a solution for off-peak renewable energy storage. γ-alumina-supported Mo and Ni-Mo catalysts were used in CO2 methanation, either in their reduced or in their carburized form. The presence of Ni improved the carburization extent of Mo-species, resulting in increased catalytic activity and selectivity for the catalytic CO2 methanation reaction. Carburization generally enhances the basicity of the materials and thus CO2 absorption on their surface. At 300°C, the conversions of CO2 for the reduced Ni-Mo/Al2O3 catalyst and Ni-Mo2C/Al2O3 catalysts were 5.3% and 13.8% respectively with a corresponding selectivity in CH4 of 10.0% and 98.1%, respectively.展开更多
The novel nickel-based catalysts with a nickel content of 12 wt% were prepared with the zirconia-alumina composite as the supports. The new carriers, ZrO2 improved alumina, were synthesized by three methods, i.e., imp...The novel nickel-based catalysts with a nickel content of 12 wt% were prepared with the zirconia-alumina composite as the supports. The new carriers, ZrO2 improved alumina, were synthesized by three methods, i.e., impregnation-precipitation, co-precipitation, and impregnation method. The catalytic properties of these catalysts were investigated in the methanation of carbon dioxide, and the samples were characterized by X-ray diffraction （XRD）, X-ray photoelectron spectroscope （XPS）, temperature-programmed reduction （TPR） and temperature-programmed desorption （TPD） techniques. The new catalysts showed higher catalytic activity and better stability than Ni/γ-Al2O3. Furthermore, as a support for new nickel catalyst, the ZrO2-Al2O3 composite prepared by the impregnation-precipitation method was more efficient than the other supports in the methanation of carbon dioxide. The highly dispersed zirconium oxide on the surface of γ-Al2O3 inhibited the formation of nickel aluminate-like phase, which was responsible for the better dispersion of Ni species and easier reduction of NiO species, leading to the enhanced catalytic performance of corresponding catalyst.展开更多
CO2 methanation has been a hot topic because of its important application in the spacecraft and potential utilization of carbon dioxide. Nickel catalyst is active for this reaction. However, its activity still needs t...CO2 methanation has been a hot topic because of its important application in the spacecraft and potential utilization of carbon dioxide. Nickel catalyst is active for this reaction. However, its activity still needs to be improved. Dielectric barrier discharge （DBD） plasma, initiated at ambient condition and operated at -150 ℃, has been employed in this work for decomposition of nickel precursor to prepare Ni/MgAl2O4. The plasma decomposition results in high dispersion, unique structure, enhanced reducibility of Ni particles and promoted catalyst-support interaction. An improved activity of CO2 methanation with a higher yield of methane has been achieved over the plasma decomposed catalyst, compared to the catalyst prepared thermally. For example, the methane yield of the plasma prepared catalyst is 71.8% at 300 ℃ but it is 62.9% over the thermal prepared catalyst. The catalyst characterization confirmed that CO2 methanation over the DBD plasma prepared catalyst follows pathway of CO methanation.展开更多
The increasing anthropogenic emissions of greenhouse gases(GHG)is encouraging extensive research in CO_(2)utilisation.Dry reforming of methane(DRM)depicts a viable strategy to convert both CO_(2)and CH4into syngas,a w...The increasing anthropogenic emissions of greenhouse gases(GHG)is encouraging extensive research in CO_(2)utilisation.Dry reforming of methane(DRM)depicts a viable strategy to convert both CO_(2)and CH4into syngas,a worthwhile chemical intermediate.Among the different active phases for DRM,the use of nickel as catalyst is economically favourable,but typically deactivates due to sintering and carbon deposition.The stabilisation of Ni at different loadings in cerium zirconate inorganic complex structures is investigated in this work as strategy to develop robust Ni-based DRM catalysts.XRD and TPR-H2analyses confirmed the existence of different phases according to the Ni loading in these materials.Besides,superficial Ni is observed as well as the existence of a CeNiO_(3)perovskite structure.The catalytic activity was tested,proving that 10 wt.%Ni loading is the optimum which maximises conversion.This catalyst was also tested in long-term stability experiments at 600and 800℃in order to study the potential deactivation issues at two different temperatures.At 600℃,carbon formation is the main cause of catalytic deactivation,whereas a robust stability is shown at 800℃,observing no sintering of the active phase evidencing the success of this strategy rendering a new family of economically appealing CO_(2)and biogas mixtures upgrading catalysts.展开更多
A series of tungsten promoted alumina supported nickel catalysts has been prepared for the carbon dioxide reforming of methane to synthesis gas. The catalysts have been characterized by means of XRD, TEM, and Laser R...A series of tungsten promoted alumina supported nickel catalysts has been prepared for the carbon dioxide reforming of methane to synthesis gas. The catalysts have been characterized by means of XRD, TEM, and Laser Raman spectroscopy. It is shown that the addition of tungsten to the nickel catalyst can stabilize the catalyst and increase the resistance to carbon deposition. Adding a suitable amount of tungsten can also increase the catalyst activity to be close to that of supported noble metal catalysts. The carburisation of the tungsten modified nickel catalyst decreases the catalyst activity at lower reaction temperatures(<1123K), but has no effect on the catalyst performance at higher reaction temperatures. The alumina supported nickel catalyst modified by 0.67%(mass fraction) WO_3 has the equivalent equilibrium constant of the dry reforming reaction to that of alumina supported 5%(mass fraction) Ru at 873 K, and also has a lower activation energy for dry reforming than the latter.展开更多
文摘CO2 methanation with Hydrogen to form CH4 offers a solution for off-peak renewable energy storage. γ-alumina-supported Mo and Ni-Mo catalysts were used in CO2 methanation, either in their reduced or in their carburized form. The presence of Ni improved the carburization extent of Mo-species, resulting in increased catalytic activity and selectivity for the catalytic CO2 methanation reaction. Carburization generally enhances the basicity of the materials and thus CO2 absorption on their surface. At 300°C, the conversions of CO2 for the reduced Ni-Mo/Al2O3 catalyst and Ni-Mo2C/Al2O3 catalysts were 5.3% and 13.8% respectively with a corresponding selectivity in CH4 of 10.0% and 98.1%, respectively.
基金supported by the Southwest Research & Design Institute of Chemical Industy (SKLIV GR-22010-01)the National Basic Research Program of China (973 Program, 2011CB201202) of Ministry of Science and Technology
文摘The novel nickel-based catalysts with a nickel content of 12 wt% were prepared with the zirconia-alumina composite as the supports. The new carriers, ZrO2 improved alumina, were synthesized by three methods, i.e., impregnation-precipitation, co-precipitation, and impregnation method. The catalytic properties of these catalysts were investigated in the methanation of carbon dioxide, and the samples were characterized by X-ray diffraction （XRD）, X-ray photoelectron spectroscope （XPS）, temperature-programmed reduction （TPR） and temperature-programmed desorption （TPD） techniques. The new catalysts showed higher catalytic activity and better stability than Ni/γ-Al2O3. Furthermore, as a support for new nickel catalyst, the ZrO2-Al2O3 composite prepared by the impregnation-precipitation method was more efficient than the other supports in the methanation of carbon dioxide. The highly dispersed zirconium oxide on the surface of γ-Al2O3 inhibited the formation of nickel aluminate-like phase, which was responsible for the better dispersion of Ni species and easier reduction of NiO species, leading to the enhanced catalytic performance of corresponding catalyst.
基金supported by the National Natural Science Foundation of China(under contracts#21476157 and#21406177)
文摘CO2 methanation has been a hot topic because of its important application in the spacecraft and potential utilization of carbon dioxide. Nickel catalyst is active for this reaction. However, its activity still needs to be improved. Dielectric barrier discharge （DBD） plasma, initiated at ambient condition and operated at -150 ℃, has been employed in this work for decomposition of nickel precursor to prepare Ni/MgAl2O4. The plasma decomposition results in high dispersion, unique structure, enhanced reducibility of Ni particles and promoted catalyst-support interaction. An improved activity of CO2 methanation with a higher yield of methane has been achieved over the plasma decomposed catalyst, compared to the catalyst prepared thermally. For example, the methane yield of the plasma prepared catalyst is 71.8% at 300 ℃ but it is 62.9% over the thermal prepared catalyst. The catalyst characterization confirmed that CO2 methanation over the DBD plasma prepared catalyst follows pathway of CO methanation.
基金The authots would like to thank the National Natural Science Foundation of China(No:20273043)the National Key Basic Reseatch Project of China(G 1999022407)for providing financial support for this project.
基金supported by grant PID2019-108502RJ-I00 and grant IJC2019-040560-I both funded by MCIN/AEI/10.13039/501100011033RYC2018-024387-I funded by MCIN/AEI/10.13039/501100011033 and by ESF Investing in your future。
文摘The increasing anthropogenic emissions of greenhouse gases(GHG)is encouraging extensive research in CO_(2)utilisation.Dry reforming of methane(DRM)depicts a viable strategy to convert both CO_(2)and CH4into syngas,a worthwhile chemical intermediate.Among the different active phases for DRM,the use of nickel as catalyst is economically favourable,but typically deactivates due to sintering and carbon deposition.The stabilisation of Ni at different loadings in cerium zirconate inorganic complex structures is investigated in this work as strategy to develop robust Ni-based DRM catalysts.XRD and TPR-H2analyses confirmed the existence of different phases according to the Ni loading in these materials.Besides,superficial Ni is observed as well as the existence of a CeNiO_(3)perovskite structure.The catalytic activity was tested,proving that 10 wt.%Ni loading is the optimum which maximises conversion.This catalyst was also tested in long-term stability experiments at 600and 800℃in order to study the potential deactivation issues at two different temperatures.At 600℃,carbon formation is the main cause of catalytic deactivation,whereas a robust stability is shown at 800℃,observing no sintering of the active phase evidencing the success of this strategy rendering a new family of economically appealing CO_(2)and biogas mixtures upgrading catalysts.
基金Supported by the National Natural Science Foundation of China
文摘A series of tungsten promoted alumina supported nickel catalysts has been prepared for the carbon dioxide reforming of methane to synthesis gas. The catalysts have been characterized by means of XRD, TEM, and Laser Raman spectroscopy. It is shown that the addition of tungsten to the nickel catalyst can stabilize the catalyst and increase the resistance to carbon deposition. Adding a suitable amount of tungsten can also increase the catalyst activity to be close to that of supported noble metal catalysts. The carburisation of the tungsten modified nickel catalyst decreases the catalyst activity at lower reaction temperatures(<1123K), but has no effect on the catalyst performance at higher reaction temperatures. The alumina supported nickel catalyst modified by 0.67%(mass fraction) WO_3 has the equivalent equilibrium constant of the dry reforming reaction to that of alumina supported 5%(mass fraction) Ru at 873 K, and also has a lower activation energy for dry reforming than the latter.
