A new type of Ni/MgO catalyst was prepared using atmospheric high-frequency discharge cold plasma. The influences of conventional method, plasma method, and plasma plus calcination method on the catalytic activity wer...A new type of Ni/MgO catalyst was prepared using atmospheric high-frequency discharge cold plasma. The influences of conventional method, plasma method, and plasma plus calcination method on the catalytic activity were studied and the CO2 reforming of methane was chosen as the probe reaction. The catalysts were characterized by X-ray diffraction （XRD）, transmission electron microscope （TEM）, X-ray photoelectron spectroscopy, and CO2 temperature-programmed surface reaction techniques. The results suggested that the nickel-based catalyst prepared by plasma plus calcination method possessed a smaller particle size and a higher dispersion of active component, better low-temperature activity and enhanced anti-coking ability. The conversion of CO2 and CH4 was 90.70% and 89.37%, respectively, and the reaction lasted for 36 h without obvious deactivation under 101.325 kPa and 750°C with CO2/CH4 = 1/1.展开更多
Nano ZrO2 and MgO-ZrO2 were prepared by a self-assembly route and were employed as the support for Ni catalysts used in hydrogen production from glycerol reforming in supercritical water （SCW）. The reforming experim...Nano ZrO2 and MgO-ZrO2 were prepared by a self-assembly route and were employed as the support for Ni catalysts used in hydrogen production from glycerol reforming in supercritical water （SCW）. The reforming experiments were conducted in a tubular fixed-bed flow reactor over a temperature range of 600-800 ℃. The influences of process variables such as temperature, contact time, and water to glycerol ratio on hydrogen yield were investigated and the catalysts were charactered by ICP, BET, XRD and SEM. The results showed that high hydrogen yield was obtained from glycerol by reforming in supercritical water over the Ni/MgO-ZrO2 catalysts in a short contact time. The MgO in the catalyst showed significant promotion effect for hydrogen production likely due to the formation of the alkaline active site. Even when the glycerol feed concentration was up to 45 wt%, glycerol was completely gasified and transfered to the gas products containing hydrogen, carbon dioxide, and methane along with small amounts of carbon monoxide. At a diluted feed concentration of 5 wt%, near theoretical yield of 7 mole of H2/mol of glycerol could be obtained.展开更多
The CO2reforming of CH4is studied over MgO‐promoted Ni catalysts,which were supported on alumina prepared from hydrotalcite.This presents an improved stability compared with non‐promoted catalysts.The introduction o...The CO2reforming of CH4is studied over MgO‐promoted Ni catalysts,which were supported on alumina prepared from hydrotalcite.This presents an improved stability compared with non‐promoted catalysts.The introduction of the MgO promoter was achieved through the‘‘memory effect’’of the Ni‐Al hydrotalcite structure,and ICP‐MS confirmed that only0.42wt.%of Mg2+ions were added into the Ni‐Mg/Al catalyst.Although no differences in the Ni particle size and basicity strength were observed,the Ni‐Mg/Al catalyst showed a higher catalytic stability than the Ni/Al catalyst.A series of surface reaction experiments were used and showed that the addition of a MgO promoter with low concentration can promote CO2dissociation to form active surface oxygen arising from the formation of the Ni‐MgO interface sites.Therefore,the carbon‐resistance promotion by nature was suggested to contribute to an oxidative environment around Ni particles,which would increase the conversion of carbon residues from CH4cracking to yield CO on the Ni metal surface.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.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
Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH_4/CO_2 reforming.To explore the reason of this phenomenon,Ni4,Ni8,and Ni12 which re flect the different cluster thicknesses su...Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH_4/CO_2 reforming.To explore the reason of this phenomenon,Ni4,Ni8,and Ni12 which re flect the different cluster thicknesses supported on the MgO(100) slabs,have been employed to simulate Ni/MgO catalysts,and the reaction pathways of CH_4/CO_2 reforming on Nix/MgO(100) models are investigated by density functional theory.The reforming mechanisms of CH_4/CO_2 on different Nix/MgO(100) indicate the energy barriers of CH_4 dissociated adsorption,CH dissociation,and C oxidation three factors are all declining with the decrease of the Ni cluster sizes.The Hirshfeld charges analyses of three steps as described above show only Ni atoms in bottom two layers can obtain electrons from the MgO supporters,and the main electron transfer occurs between adsorbed species and their directly contacted Ni atoms.Due to more electron-rich Ni atoms in contact with the MgO supporters,the Ni/MgO catalysts with small Ni particles have a strong metal particle size effect and lead to its better catalytic activity.展开更多
Carbon nanotubes (CNTs) have been synthesized over Ni-MgO and Ni-Sm-MgO catalysts by decomposition of CH4 at 650 ℃. The addition of Sm into Ni-MgO catalyst not only promotes the catalytic activity and lifetime of the...Carbon nanotubes (CNTs) have been synthesized over Ni-MgO and Ni-Sm-MgO catalysts by decomposition of CH4 at 650 ℃. The addition of Sm into Ni-MgO catalyst not only promotes the catalytic activity and lifetime of the catalyst, but also improves the graphitization and heat stability of carbon nanotubes. The yield of CNTs obtained over the Ni-10Sm-MgO catalyst reaches 33 g C·(g Ni)-1, being more than 5 times higher than that of the Ni-MgO catalyst. XRD and TPR results of the catalysts indicate that there is a remarkable interaction of Ni with Sm species, which facilitates the reduction of nickel and restrains the Ni particles from agglomerating.展开更多
基金supported by the National Natural Science Foundation of China(No.11075113)the Doctoral R&D Foundation of Yibin University(2010B12)
文摘A new type of Ni/MgO catalyst was prepared using atmospheric high-frequency discharge cold plasma. The influences of conventional method, plasma method, and plasma plus calcination method on the catalytic activity were studied and the CO2 reforming of methane was chosen as the probe reaction. The catalysts were characterized by X-ray diffraction （XRD）, transmission electron microscope （TEM）, X-ray photoelectron spectroscopy, and CO2 temperature-programmed surface reaction techniques. The results suggested that the nickel-based catalyst prepared by plasma plus calcination method possessed a smaller particle size and a higher dispersion of active component, better low-temperature activity and enhanced anti-coking ability. The conversion of CO2 and CH4 was 90.70% and 89.37%, respectively, and the reaction lasted for 36 h without obvious deactivation under 101.325 kPa and 750°C with CO2/CH4 = 1/1.
基金supported by the National Natural Science Foundation (21076047 and 21276054)the Natural Science Foundation of Zhongkai University of Agriculture and Engineering (G3100026)
文摘Nano ZrO2 and MgO-ZrO2 were prepared by a self-assembly route and were employed as the support for Ni catalysts used in hydrogen production from glycerol reforming in supercritical water （SCW）. The reforming experiments were conducted in a tubular fixed-bed flow reactor over a temperature range of 600-800 ℃. The influences of process variables such as temperature, contact time, and water to glycerol ratio on hydrogen yield were investigated and the catalysts were charactered by ICP, BET, XRD and SEM. The results showed that high hydrogen yield was obtained from glycerol by reforming in supercritical water over the Ni/MgO-ZrO2 catalysts in a short contact time. The MgO in the catalyst showed significant promotion effect for hydrogen production likely due to the formation of the alkaline active site. Even when the glycerol feed concentration was up to 45 wt%, glycerol was completely gasified and transfered to the gas products containing hydrogen, carbon dioxide, and methane along with small amounts of carbon monoxide. At a diluted feed concentration of 5 wt%, near theoretical yield of 7 mole of H2/mol of glycerol could be obtained.
基金supported by the National Natural Science Fundation of China(U1361202,51276120)~~
文摘The CO2reforming of CH4is studied over MgO‐promoted Ni catalysts,which were supported on alumina prepared from hydrotalcite.This presents an improved stability compared with non‐promoted catalysts.The introduction of the MgO promoter was achieved through the‘‘memory effect’’of the Ni‐Al hydrotalcite structure,and ICP‐MS confirmed that only0.42wt.%of Mg2+ions were added into the Ni‐Mg/Al catalyst.Although no differences in the Ni particle size and basicity strength were observed,the Ni‐Mg/Al catalyst showed a higher catalytic stability than the Ni/Al catalyst.A series of surface reaction experiments were used and showed that the addition of a MgO promoter with low concentration can promote CO2dissociation to form active surface oxygen arising from the formation of the Ni‐MgO interface sites.Therefore,the carbon‐resistance promotion by nature was suggested to contribute to an oxidative environment around Ni particles,which would increase the conversion of carbon residues from CH4cracking to yield CO on the Ni metal surface.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
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 Natural Science Foundation of China(U1361202,51276120)
文摘Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH_4/CO_2 reforming.To explore the reason of this phenomenon,Ni4,Ni8,and Ni12 which re flect the different cluster thicknesses supported on the MgO(100) slabs,have been employed to simulate Ni/MgO catalysts,and the reaction pathways of CH_4/CO_2 reforming on Nix/MgO(100) models are investigated by density functional theory.The reforming mechanisms of CH_4/CO_2 on different Nix/MgO(100) indicate the energy barriers of CH_4 dissociated adsorption,CH dissociation,and C oxidation three factors are all declining with the decrease of the Ni cluster sizes.The Hirshfeld charges analyses of three steps as described above show only Ni atoms in bottom two layers can obtain electrons from the MgO supporters,and the main electron transfer occurs between adsorbed species and their directly contacted Ni atoms.Due to more electron-rich Ni atoms in contact with the MgO supporters,the Ni/MgO catalysts with small Ni particles have a strong metal particle size effect and lead to its better catalytic activity.
文摘Carbon nanotubes (CNTs) have been synthesized over Ni-MgO and Ni-Sm-MgO catalysts by decomposition of CH4 at 650 ℃. The addition of Sm into Ni-MgO catalyst not only promotes the catalytic activity and lifetime of the catalyst, but also improves the graphitization and heat stability of carbon nanotubes. The yield of CNTs obtained over the Ni-10Sm-MgO catalyst reaches 33 g C·(g Ni)-1, being more than 5 times higher than that of the Ni-MgO catalyst. XRD and TPR results of the catalysts indicate that there is a remarkable interaction of Ni with Sm species, which facilitates the reduction of nickel and restrains the Ni particles from agglomerating.
