The 7 wt%rare earth metal oxide promoted Ni-SiO_(2) catalysts of Ni-7Pr_(6)O_(11)-SiO_(2),Ni-7Nd_(2)O_(3)-SiO_(2),and Ni-7Sm_(2)O_(3)-SiO_(2) were prepared by the complex-decomposition method,and were comparatively ev...The 7 wt%rare earth metal oxide promoted Ni-SiO_(2) catalysts of Ni-7Pr_(6)O_(11)-SiO_(2),Ni-7Nd_(2)O_(3)-SiO_(2),and Ni-7Sm_(2)O_(3)-SiO_(2) were prepared by the complex-decomposition method,and were comparatively evaluated for pressurized carbon dioxide reforming of methane(CRM)under severe conditions of 750℃,1.0 MPa,CH_(4)/CO_(2)=1,and gas hourly space velocity of 53200 mL/(g·h).The addition of rare earth metal oxide does not affect the Ni dispersion,and all of the catalysts show similarly high Ni dispersion of16.0%±0.2%.As a result,all of the catalysts are highly active for pressurized CRM,the initial CH_(4) conversions of which approach the thermodynamic equilibrium(47.0%±0.2%).In contrast,a clearly favorable effect of the added rare earth metal oxide on the stability of Ni-SiO_(2)was revealed from the CRM results for a time-on-stream of 50 h,and the highest stability without an observable decrease in the conversions of CH_(4)and CO_(2)was obtained over Ni-7Sm_(2)O_(3)-SiO_(2).Based on the characterization results of thermogravimetric differential scanning calorimetry(TG-DSC)and transmission electron microscopy(TEM),the improved stability of Ni-7Pr_(6)O_(11)-SiO_(2),Ni-7Nd_(2)O_(3)-SiO_(2),and Ni-7Sm_(2)O_(3)-SiO_(2)for pressurized CRM was manifested mainly as the suppressed formation of carbon nanotubes over the catalyst surface,the extent of which is dependent on the specific rare earth metal oxide.Moreover,the consecutive temperature programmed surface reaction of CH_(4),CO_(2),and O_(2)over Ni-7Sm_(2)O_(3)-SiO_(2)vigorously reveals that the addition of Sm_(2)O_(3)into Ni-SiO_(2)inhibits the CH_(4)decomposition but enhances the oxidization of the carbon species by CO_(2),leading to the well-balanced rates for forming and removing the coke over Ni-7Sm_(2)O_(3)-SiO_(2).These findings are not only beneficial to deeply understanding the promotional effect of rare earth metal oxides on Ni-based catalysts for CRM,but also important for extending the application of the less studied rare earth metal oxides as promoters for the metalsupported catalysts.展开更多
基金Project supported by the National Natural Science Foundation of China(U1862116)the Fundamental Research Funds for the Central Universities(GK201901001).
文摘The 7 wt%rare earth metal oxide promoted Ni-SiO_(2) catalysts of Ni-7Pr_(6)O_(11)-SiO_(2),Ni-7Nd_(2)O_(3)-SiO_(2),and Ni-7Sm_(2)O_(3)-SiO_(2) were prepared by the complex-decomposition method,and were comparatively evaluated for pressurized carbon dioxide reforming of methane(CRM)under severe conditions of 750℃,1.0 MPa,CH_(4)/CO_(2)=1,and gas hourly space velocity of 53200 mL/(g·h).The addition of rare earth metal oxide does not affect the Ni dispersion,and all of the catalysts show similarly high Ni dispersion of16.0%±0.2%.As a result,all of the catalysts are highly active for pressurized CRM,the initial CH_(4) conversions of which approach the thermodynamic equilibrium(47.0%±0.2%).In contrast,a clearly favorable effect of the added rare earth metal oxide on the stability of Ni-SiO_(2)was revealed from the CRM results for a time-on-stream of 50 h,and the highest stability without an observable decrease in the conversions of CH_(4)and CO_(2)was obtained over Ni-7Sm_(2)O_(3)-SiO_(2).Based on the characterization results of thermogravimetric differential scanning calorimetry(TG-DSC)and transmission electron microscopy(TEM),the improved stability of Ni-7Pr_(6)O_(11)-SiO_(2),Ni-7Nd_(2)O_(3)-SiO_(2),and Ni-7Sm_(2)O_(3)-SiO_(2)for pressurized CRM was manifested mainly as the suppressed formation of carbon nanotubes over the catalyst surface,the extent of which is dependent on the specific rare earth metal oxide.Moreover,the consecutive temperature programmed surface reaction of CH_(4),CO_(2),and O_(2)over Ni-7Sm_(2)O_(3)-SiO_(2)vigorously reveals that the addition of Sm_(2)O_(3)into Ni-SiO_(2)inhibits the CH_(4)decomposition but enhances the oxidization of the carbon species by CO_(2),leading to the well-balanced rates for forming and removing the coke over Ni-7Sm_(2)O_(3)-SiO_(2).These findings are not only beneficial to deeply understanding the promotional effect of rare earth metal oxides on Ni-based catalysts for CRM,but also important for extending the application of the less studied rare earth metal oxides as promoters for the metalsupported catalysts.
