Mechanisms of H2 and CO Reaction on the Fe2O3(0001) Surface in Hydrogen-Based Shaft Furnace Based on DFT

doi:10.12068/j.issn.1005-3026.2025.20240199

Abstract

Abstract:

Hydrogen-based shaft furnace process can significantly reduce CO₂ emission， which is an effective way for low-carbon and green development of iron and steel industry. In this study， the reaction mechanism of H₂ and CO with Fe₂O₃ in the hydrogen-based shaft furnace reduction process was investigated in depth based on density functional theory（DFT）. The results show that the most stable adsorption configuration of H₂ molecule has an adsorption energy of -1.65 eV and the CO molecule has an adsorption energy of -2.10 eV， which is favorable for the adsorption of CO molecule. The energy barrier of H₂ molecule for the reaction is 0.64 eV， and CO molecule has an energy barrier of 1.40 eV， which is favorable for the reaction of H₂ molecule with Fe₂O₃ in the kinetic. Increasing temperature is unfavorable for the adsorption of gas molecules， but favoring the kinetics of reduction reaction. And increasing temperature can compensate for the thermodynamic disadvantage of the adsorption and reaction of H₂ molecules. The operating pressure should be increased， while the reduction temperature can be increased appropriately to accelerate the reaction rate， but the adsorption efficiency should be ensured for hydrogen-rich or pure hydrogen shaft furnace.

Key words: hydrogen-based shaft furnace, density functional theory （DFT）, Fe₂O₃, reaction mechanism, adsorption energy, energy barrier

CLC Number:

TF 51

Jue TANG, Man-sheng CHU, Xi-cai LIU, Jie LIU. Mechanisms of H₂ and CO Reaction on the Fe₂O₃(0001) Surface in Hydrogen-Based Shaft Furnace Based on DFT[J]. Journal of Northeastern University(Natural Science), 2025, 46(7): 139-147.

Figures/Tables 7

Fig.1 Convergence test and properties of Fe2O3 and gas molecules

Fig.2 Adsorption energies，bond lengths and bond angles of stable adsorption of H2 molecules on the α-Fe2O3(0001) surfaces after optimization

Fig.3 Partial density of states of H2 molecules adsorbed on the α-Fe2O3(0001) surface

Fig.4 Adsorption energies, bond lengths and bond angles of stable adsorption of CO molecules on the α-Fe2O3(0001) surface after optimization

Fig.5 Partial density of states of CO molecules adsorbed on the α-Fe2O3(0001) surface

Fig.6 Pathways and energy changes during the reaction of the α-Fe2O3(0001) surface with H2 molecules and CO molecules

Fig.7 Adsorption phase diagrams and reduction phase diagrams of H2 and CO molecules on the α-Fe2O3(0001) surface

References 30

[1]	上官方钦，段志伟，崔志峰，等. 新形势下中国钢铁行业碳达峰碳中和若干问题探讨［J］. 钢铁， 2024， 59（9）： 22-31.
	Shangguan Fang-qin， Duan Zhi-wei， Cui Zhi-feng， et al. Discussion on several issues of carbon peak and carbon neutrality in China’s steel industry under new situation［J］. Iron & Steel， 2024， 59（9）： 22-31.
[2]	朱彤，李建. 铁矿石氢还原行为研究［J］. 钢铁， 2024， 59（9）： 84-90.
	Zhu Tong， Li Jian. Study on hydrogen reduction behavior of iron ore［J］. Iron & Steel， 2024， 59（9）： 84-90.
[3]	Prusti P， Rath S S， Dash N， et al. Pelletization of hematite and synthesized magnetite concentrate from a banded hematite quartzite ore： a comparison study［J］. Advanced Powder Technology， 2021， 32（10）： 3735-3745.
[4]	刘西财，石恩泽，赵子川，等. 氢基竖炉条件下制备不同金属化率球团研究［J］. 烧结球团， 2022， 47（1）： 58-64， 126.
	Liu Xi-cai， Shi En-ze， Zhao Zi-chuan， et al. Research on preparation of pellets with different metallization rates under hydrogen-based shaft furnace condition［J］. Sintering and Pelletizing， 2022， 47（1）： 58-64， 126.
[5]	Zhao Z C， Tang J， Chu M S， et al. Direct reduction swelling behavior of pellets in hydrogen-based shaft furnaces under typical atmospheres［J］. International Journal of Minerals， Metallurgy and Materials， 2022， 29（10）： 1891-1900.
[6]	Feng J G， Tang J， Chu M S， et al. Sticking behavior of pellets during direct reduction based on hydrogen metallurgy： an optimization approach using response surface methodology［J］. Journal of Sustainable Metallurgy， 2023， 9（3）： 1139-1154.
[7]	Liu Z J， Lu S F， Wang Y Z， et al. Study on optimization of reduction temperature of hydrogen-based shaft furnace： numerical simulation and multi-criteria evaluation［J］. International Journal of Hydrogen Energy， 2023， 48（42）： 16132-16142.
[8]	Petrushenko I K， Petrushenko K B. Physical adsorption of hydrogen molecules on single-walled carbon nanotubes and carbon-boron-nitrogen heteronanotubes： a comparative DFT study［J］. Vacuum， 2019， 167： 280-286.
[9]	Yu C Y， Li D H， Wang D Y， et al. Three-dimensional triptycene-functionalized covalent organic frameworks with hea net for hydrogen adsorption［J］. Angewandte Chemie （International Edition）， 2022， 61（13）： e202117101.
[10]	Meng Y， Liu X Y， Bai M M， et al. Adsorption or deoxidation of H₂ interacted with Fe₃O₄ surface under different H coverage： a DFT study［J］. Applied Surface Science， 2020， 502： 144097.
[11]	Huang L， Tang M C， Fan M H， et al. Density functional theory study on the reaction between hematite and methane during chemical looping process［J］. Applied Energy， 2015， 159： 132-144.
[12]	Liu A M， Yang Y N， Kong D Z， et al. DFT study of the defective carbon materials with vacancy and heteroatom as catalyst for NRR［J］. Applied Surface Science， 2021， 536： 147851.
[13]	Chen B X， Wang D， Duan X Z， et al. Charge-tuned CO activation over a χ-Fe₅C₂ Fischer-Tropsch catalyst［J］. ACS Catalysis， 2018， 8（4）： 2709-2714.
[14]	Daga Y， Kizilkaya A C. Mechanistic insights into the effect of sulfur on the selectivity of cobalt-catalyzed Fischer-Tropsch synthesis： a DFT study［J］. Catalysts， 2022， 12（4）： 425.
[15]	Kresse G， Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set［J］. Physical Review B， 1996， 54（16）： 11169-11186.
[16]	Kresse G， Furthmüller J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set［J］. Computational Materials Science， 1996， 6（1）： 15-50.
[17]	Blöchl P E. Projector augmented-wave method［J］. Physical Review B， 1994， 50（24）： 17953-17979.
[18]	Perdew J P， Burke K， Ernzerhof M. Generalized gradient approximation made simple［J］. Physical Review Letters， 1996， 77（18）： 3865-3868.
[19]	Dudarev S L， Botton G A， Savrasov S Y， et al. Electron-energy-loss spectra and the structural stability of nickel oxide： an LSDA+U study［J］. Physical Review B， 1998， 57（3）： 1505-1509.
[20]	Ueda D K， Ohyama D J， Sawabe D K， et al. Structure-activity relationship of iron oxides for NO reduction in the presence of C₃H₆， CO， and O₂ ［J］. Chemistry-A European Journal， 2019， 25（61）： 13964-13971.
[21]	Grimme S， Antony J， Ehrlich S， et al. A consistent and accurate ab initio parametrization of density functional dispersion correction （DFT-D） for the 94 elements H-Pu［J］. The Journal of Chemical Physics， 2010， 132（15）： 154104.
[22]	Methfessel M， Paxton A T. High-precision sampling for Brillouin-zone integration in metals［J］. Physical Review B， 1989， 40（6）： 3616-3621.
[23]	Henkelman G， Jónsson H. A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives［J］. The Journal of Chemical Physics， 1999， 111（15）： 7010-7022.
[24]	Lin C F， Qin W， Dong C Q. H₂S adsorption and decomposition on the gradually reduced α-Fe₂O₃（001） surface： a DFT study［J］. Applied Surface Science， 2016， 387： 720-731.
[25]	Finger L W， Hazen R M. Crystal structure and isothermal compression of Fe₂O₃， Cr₂O₃， and V₂O₃ to 50 kbars［J］. Journal of Applied Physics， 1980， 51（10）： 5362-5367.
[26]	王子明. 焦炭和铁氧化物在高炉内气固反应机理［D］. 北京：北京科技大学， 2021.
	Wang Zi-ming. Gas-solid reaction mechanism of coke and iron oxide in blast furnace［D］. Beijing： University of Science and Technology Beijing， 2021.
[27]	Souvi S M O， Badawi M， Paul J F， et al. A DFT study of the hematite surface state in the presence of H₂， H₂O and O₂ ［J］. Surface Science， 2013， 610： 7-15.
[28]	Huber K P， Herzberg G. Molecular spectra and molecular structure. IV. constants of diatomic molecules［M］. ［S. l.］：Van Nostrand Reinhold Co.， 1979.
[29]	Xue P Y， Fu Z M， Chu X L， et al. Density functional theory study on the interaction of CO with the Fe₃O₄（001） surface［J］. Applied Surface Science， 2014， 317： 752-759.
[30]	鲁峰. 流态化直接还原炼铁过程中颗粒黏结与调控的跨尺度关系的研究［D］. 重庆：重庆大学，2019.
	Lu Feng. Multiscale study on the particle agglomeration and control of fluidized bed in the direct reduction process［D］. Chongqing： Chongqing University， 2019.

Mechanisms of H₂ and CO Reaction on the Fe₂O₃(0001) Surface in Hydrogen-Based Shaft Furnace Based on DFT

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