The Co_3O_4 and Zr-,Ce-,and La-Co_3O_4 catalysts were prepared,characterized,and applied to produce CH_4 from CO_2 catalytic hydrogenation in low temperature as 140–220°C.The results indicated that the addition ...The Co_3O_4 and Zr-,Ce-,and La-Co_3O_4 catalysts were prepared,characterized,and applied to produce CH_4 from CO_2 catalytic hydrogenation in low temperature as 140–220°C.The results indicated that the addition of Zr,Ce,or La to the Co_3O_4 decreased the crystallite sizes of Co and the outer-shell electron density of Co^(3+),and increased the specific surface area,which would provide more active sites for the CO_2 methanation.Especially,the addition of Zr also changed the reducing state of Co_3O_4 via an obvious change in the interaction between Co_3O_4 and ZrO_2.Furthermore,Zr doped into the Co_3O_4 increased the basic intensity of the weak and medium basic sites,as well as the amount of Lewis acid sites,and Br?nsted acid sites were also found on the Zr-Co_3O_4 surface.The introduction of Zr,Ce,or La favored the production of CH_4,and the Zr-Co_3O_4catalyst exhibited the highest CO_2 conversion(58.2%)and CH_4 selectivity(100%)at 200°C,and 0.5 MPa with a gaseous hourly space velocity of 18,000 ml·g^(-1)_(cat)·h^(-1),and the catalytic activity of CO_2methanation for the Zr-,Ce-,and La-Co_3O_4 exhibited more stable than Co_3O_4 in a 20-h reaction.展开更多
基金Supported by the National Natural Science Foundation of China(21366004)Guangxi Natural Science Foundation(2016GXNSFFA380015)the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2016Z003)
文摘The Co_3O_4 and Zr-,Ce-,and La-Co_3O_4 catalysts were prepared,characterized,and applied to produce CH_4 from CO_2 catalytic hydrogenation in low temperature as 140–220°C.The results indicated that the addition of Zr,Ce,or La to the Co_3O_4 decreased the crystallite sizes of Co and the outer-shell electron density of Co^(3+),and increased the specific surface area,which would provide more active sites for the CO_2 methanation.Especially,the addition of Zr also changed the reducing state of Co_3O_4 via an obvious change in the interaction between Co_3O_4 and ZrO_2.Furthermore,Zr doped into the Co_3O_4 increased the basic intensity of the weak and medium basic sites,as well as the amount of Lewis acid sites,and Br?nsted acid sites were also found on the Zr-Co_3O_4 surface.The introduction of Zr,Ce,or La favored the production of CH_4,and the Zr-Co_3O_4catalyst exhibited the highest CO_2 conversion(58.2%)and CH_4 selectivity(100%)at 200°C,and 0.5 MPa with a gaseous hourly space velocity of 18,000 ml·g^(-1)_(cat)·h^(-1),and the catalytic activity of CO_2methanation for the Zr-,Ce-,and La-Co_3O_4 exhibited more stable than Co_3O_4 in a 20-h reaction.
