The novel process of hydrogen-based shaft furnaces(HSFs)has attracted considerable attention because of their significant reduction of CO_(2)emissions.In this study,the interaction of H_(2)and CO with Fe_(tet1)-and Fe...The novel process of hydrogen-based shaft furnaces(HSFs)has attracted considerable attention because of their significant reduction of CO_(2)emissions.In this study,the interaction of H_(2)and CO with Fe_(tet1)-and Fe_(oct2)-terminated Fe_(3)O_(4)(111)surfaces under HSF conditions,including their adsorption and reduction behaviors,was investigated using the density functional theory method.The results indicated that the H_(2)molecule adsorbed onto the Fe_(tet1)-terminated surface with an adsorption energy(AE)of-1.36 eV,whereas the CO molecule preferentially adsorbed on the Fe_(oct2)-terminated surface with an AE of-1.56 eV.Both H_(2)and CO can readily undergo reduction on the Fe_(tet1)-terminated surface(corresponding to energy barriers of 0.83 eV and 2.23 eV,respectively),but kinetically the reaction of H2is more favorable than that of CO.With regard to the thermodynamics at 400-1400 K,the H_(2)was easy to be adsorbed,while the CO would like to react on the Fe_(tet1)-terminated surface.These thermodynamically tendencies were reversed on the Fe_(oct2)-terminated surface.The thermodynamic disadvantage of the reaction of H_(2)on the Fe_(tet1)-terminated surface was offset by an increase in the temperature.Furthermore,the adsorption of H2 and CO on the Fe_(tet1)-terminated surface was competitive,whereas the adsorption of them on the Fe_(oct2)-terminated surface was synergistic.Therefore,iron ores with a higher proportion of Fe_(tet1)-terminated surface can be applied for the HSF process.In conjunction with the increases in the reduction temperature and the ratio of H_(2)in the reducing gas would promote efficient HSF smelting.These observations provide effective guidance for optimizing the practical operation parameters and advancing the development of the HSF process.展开更多
基金financially supported by the Key Program of National Natural Science Foundation of China(No.U23A20608)the Liaoning Province Science and Technology Plan Joint Program(Key Research and Development Program Project),China(No.2023JH2/101800058)+3 种基金the Science&Technology Plan Project of Hebei Province,China(No.23314601L)the Project of Hydrogen-Based Shaft Furnace Reduction-Electric Furnace Melting And Separation Technology Research and Application for High-Titanium Magnetite Iron Ore(No.HG2023239)the General Program of National Natural Science Foundation of China(No.52274253)the Special Project for Major Scientific and Technological Achievements Transformation in Hebei Province,China(No.23284101Z)。
文摘The novel process of hydrogen-based shaft furnaces(HSFs)has attracted considerable attention because of their significant reduction of CO_(2)emissions.In this study,the interaction of H_(2)and CO with Fe_(tet1)-and Fe_(oct2)-terminated Fe_(3)O_(4)(111)surfaces under HSF conditions,including their adsorption and reduction behaviors,was investigated using the density functional theory method.The results indicated that the H_(2)molecule adsorbed onto the Fe_(tet1)-terminated surface with an adsorption energy(AE)of-1.36 eV,whereas the CO molecule preferentially adsorbed on the Fe_(oct2)-terminated surface with an AE of-1.56 eV.Both H_(2)and CO can readily undergo reduction on the Fe_(tet1)-terminated surface(corresponding to energy barriers of 0.83 eV and 2.23 eV,respectively),but kinetically the reaction of H2is more favorable than that of CO.With regard to the thermodynamics at 400-1400 K,the H_(2)was easy to be adsorbed,while the CO would like to react on the Fe_(tet1)-terminated surface.These thermodynamically tendencies were reversed on the Fe_(oct2)-terminated surface.The thermodynamic disadvantage of the reaction of H_(2)on the Fe_(tet1)-terminated surface was offset by an increase in the temperature.Furthermore,the adsorption of H2 and CO on the Fe_(tet1)-terminated surface was competitive,whereas the adsorption of them on the Fe_(oct2)-terminated surface was synergistic.Therefore,iron ores with a higher proportion of Fe_(tet1)-terminated surface can be applied for the HSF process.In conjunction with the increases in the reduction temperature and the ratio of H_(2)in the reducing gas would promote efficient HSF smelting.These observations provide effective guidance for optimizing the practical operation parameters and advancing the development of the HSF process.
