Current development status of hydrogen reduction technology with the CH<sub>4</sub>-H<sub>2</sub> system

Zhang Run; Tan Chaowen; Dang Jie

doi:10.7513/j.issn.1004-7638.2024.06.002

Volume 45 Issue 6

Dec. 2024

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Article Navigation > IRON STEEL VANADIUM TITANIUM > 2024 > 45(6): 7-18

Zhang Run, Tan Chaowen, Dang Jie. Current development status of hydrogen reduction technology with the CH4-H2 system[J]. IRON STEEL VANADIUM TITANIUM, 2024, 45(6): 7-18. doi: 10.7513/j.issn.1004-7638.2024.06.002

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Zhang Run, Tan Chaowen, Dang Jie. Current development status of hydrogen reduction technology with the CH₄-H₂ system[J]. IRON STEEL VANADIUM TITANIUM, 2024, 45(6): 7-18. doi: 10.7513/j.issn.1004-7638.2024.06.002

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Current development status of hydrogen reduction technology with the CH₄-H₂ system

doi: 10.7513/j.issn.1004-7638.2024.06.002

College of Materials Science and Engineering, Chongqing University, Chongqing 400040, China

Received Date: 2024-08-19
Available Online: 2024-12-30
Publish Date: 2024-12-30

Abstract

Abstract

Under the dual challenges posed by the “dual carbon” goals and “double high” restrictions, the field of pyrometallurgy is experiencing significant pressures related to energy consumption and carbon emissions, thereby heightening the urgent need for clean energy. Hydrogen energy, as a renewable clean energy source, offers a new dawn for pyrometallurgy in terms of energy-saving, low-carbon, and green transformation. Hydrogen reduction technology based on the CH₄-H₂ system, with its excellent reduction capability and low-carbon, pollution-free characteristics, has emerged as a research hotspot in the metallurgical field. This paper elucidates the reduction thermodynamics and kinetics principles of the CH₄-H₂ system, systematically reviews the relevant domestic and international technologies and research progress, summarizes the research achievements and development directions of this technology in the reduction of metallic minerals (iron, titanium, nickel, zinc, cobalt, chromium, and manganese), and conducts a systematic analysis of the unresolved issues. The hydrogen reduction technology based on the CH₄-H₂ system holds immense application potential, and these discussions will contribute to advancing the further development of this technology.
- metallic mineral,
- pyrometallurgy,
- hydrogen reduction technology,
- CH₄-H₂ system

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[1]	Zhang Jianliang, Zong Yanbing, Li Kejiang, et al. Progress and outlook of new low-carbon ironmaking technologies in the world[J]. Iron and Steel, 2024, 59(9): 45-55, 155. (张建良, 宗燕兵, 李克江, 等. 全球低碳炼铁新工艺技术进展及展望[J]. 钢铁, 2024, 59(9): 45-55, 155. Zhang Jianliang, Zong Yanbing, Li Kejiang, et al. Progress and outlook of new low-carbon ironmaking technologies in the world[J]. Iron and Steel, 2024, 59(9): 45-55, 155.
[2]	Tang Jue, Chu Mansheng, Li Feng, et al. Development and progress on hydrogen metallurgy[J]. International Journal of Minerals Metallurgy and Materials, 2020,27(6):713-723. doi: 10.1007/s12613-020-2021-4
[3]	Jiang Zhouhua, Yang Ce, Zhu Hongchun, et al. Research status and prospect of hydrogen metallurgy steelmaking technology[J]. Iron & Steel, 2024,59(9):140-155. (姜周华, 杨策, 朱红春, 等. 氢冶金炼钢技术的研究现状与展望[J]. 钢铁, 2024,59(9):140-155. Jiang Zhouhua, Yang Ce, Zhu Hongchun, et al. Research status and prospect of hydrogen metallurgy steelmaking technology[J]. Iron & Steel, 2024, 59（9）: 140-155.
[4]	Luo Dayong. Natural gas production in China from 2018-2023[J]. International Petroleum Economics, 2024,32(4):105. (罗大勇. 2018-2023年中国天然气产量[J]. 国际石油经济, 2024,32(4):105. doi: 10.3969/j.issn.1004-7298.2024.04.016 Luo Dayong. Natural gas production in China from 2018-2023[J]. International Petroleum Economics, 2024, 32（4）: 105. doi: 10.3969/j.issn.1004-7298.2024.04.016
[5]	Bost N, Ammar M R, Bouchetou M L, et al. The catalytic effect of iron oxides on the formation of nano-carbon by the Boudouard reaction in refractories[J]. Journal of the European Ceramic Society, 2016,36(8):2133-2142. doi: 10.1016/j.jeurceramsoc.2016.02.052
[6]	Shen Fengman, Ding Zhimin, Wang Shuo, et al. Development and application of carbon deposition state diagram for H-C-O system[J]. Iron and Steel, 2024,59(9):122-129. (沈峰满, 丁智敏, 王硕, 等. 关于H-C-O体系析碳状态分布图的开发与应用[J]. 钢铁, 2024,59(9):122-129. Shen Fengman, Ding Zhimin, Wang Shuo, et al. Development and application of carbon deposition state diagram for H-C-O system[J]. Iron and Steel, 2024, 59（9）: 122-129.
[7]	Shen Fengman. Development of H-C-O system mass balance and chemical equilibrium diagram[J]. Iron and Steel, 2023,58(6):12-17. (沈峰满. H-C-O体系质量及化学平衡衡算图的开发[J]. 钢铁, 2023,58(6):12-17. Shen Fengman. Development of H-C-O system mass balance and chemical equilibrium diagram[J]. Iron and Steel, 2023, 58（6）: 12-17.
[8]	Shen Fengman, Zhang Weiling, Zheng Aijun, et al. Regulation of carbon deposition during preparation process of hydrogen-rich reducing gas by natural gas reforming-An application example of H-C-O system mass balance and chemical equilibrium diagram[J]. Iron and Steel, 2023,58(7):9-16. (沈峰满, 章苇玲, 郑艾军, 等. 关于天然气重整制备富氢还原气体过程中析碳问题的调控——H-C-O体系质量及化学平衡衡算图的应用例[J]. 钢铁, 2023,58(7):9-16. Shen Fengman, Zhang Weiling, Zheng Aijun, et al. Regulation of carbon deposition during preparation process of hydrogen-rich reducing gas by natural gas reforming-An application example of H-C-O system mass balance and chemical equilibrium diagram[J]. Iron and Steel, 2023, 58（7）: 9-16.
[9]	Shen Fengman, Zheng Aijun, Zheng Haiyan, et al. Thoughts on preparation of hydrogen-based reduction gas and process of direct reduction iron[J]. Iron and Steel, 2022,57(3):10-15. (沈峰满, 郑艾军, 郑海燕, 等. 关于直接还原铁工艺及还原气制备的若干思考[J]. 钢铁, 2022,57(3):10-15. Shen Fengman, Zheng Aijun, Zheng Haiyan, et al. Thoughts on preparation of hydrogen-based reduction gas and process of direct reduction iron[J]. Iron and Steel, 2022, 57（3）: 10-15.
[10]	Zhang Run, Liu Dong, Fan Gangqiang, et al. Thermodynamic and experimental study on the reduction and carbonization of TiO₂ through gas-solid reaction[J]. International Journal of Energy Research, 2019,43(9):4253-4263. doi: 10.1002/er.4551
[11]	Halli P, Taskinen P, Eriҫ R H. Mechanisms and kinetics of solid state reduction of titano magnetite ore with methane[J]. Journal of Sustainable Metallurgy, 2017,3(2):191-206. doi: 10.1007/s40831-016-0063-7
[12]	Lü Zepeng, Dang Jie. Mathematical modeling of the reaction of metal oxides with methane[J]. RSC Advances, 2020,10(19):11233-11243. doi: 10.1039/C9RA09418K
[13]	Rashidi H, Ebrahim H A, Dabir B. Reduction kinetics of nickel oxide by methane as reducing agent based on thermogravimetry[J]. Thermochimica Acta, 2013,561:41-48. doi: 10.1016/j.tca.2013.03.014
[14]	Ni Hongwei, Cang Daqiang, Jiang Junpu, et al. Suitable gas-phase compositions for the preparation of iron carbide from H₂-CH₄ gas[J]. Journal of East China Institute of Metallurgy, 1997,3:203-208. (倪红卫, 苍大强, 姜钧普, 等. 用H₂-CH₄气制备碳化铁的合适气相成分[J]. 华东冶金学院学报, 1997,3:203-208. Ni Hongwei, Cang Daqiang, Jiang Junpu, et al. Suitable gas-phase compositions for the preparation of iron carbide from H₂-CH₄ gas[J]. Journal of East China Institute of Metallurgy, 1997, 3: 203-208.
[15]	Ma Jianghua, Li Guangqiang. Influence of iron ore porosity on its reduction and iron carbide generation[J]. Journal of Process Engineering, 2007,6:1132-1137. (马江华, 李光强. 铁矿石孔隙度对其还原和碳化铁生成的影响[J]. 过程工程学报, 2007,6:1132-1137. doi: 10.3321/j.issn:1009-606x.2007.06.014 Ma Jianghua, Li Guangqiang. Influence of iron ore porosity on its reduction and iron carbide generation[J]. Journal of Process Engineering, 2007, 6: 1132-1137. doi: 10.3321/j.issn:1009-606x.2007.06.014
[16]	Li Guangqiang, Wang Henghui, Yang Jian, et al. Preparation of iron carbide from high phosphorus oolitic hematite[J]. Advanced Materials Research, 2014,88-883:98-101.
[17]	Wang Henghui, Li Guangqiang, Yang Jian, et al. The behavior of phosphorus during reduction and carburization of high-phosphorus oolitic hematite with H₂ and CH₄[J]. Metall Mater Trans B, 2016,47:2571-2581. doi: 10.1007/s11663-016-0709-7
[18]	Zhang Run, Wang Chao, You Yang, et al. Reduction and carbonization of iron concentrate with hydrogen-rich gas[J]. The Minerals, Metals & Materials Series, 2024: 29-38.
[19]	Ghosh D, Roy A K, Ghosh A. Reduction of ferric oxide pellets with methane[J]. Transactions of the Iron and Steel Institute of Japan, 1986,26(3):186-193. doi: 10.2355/isijinternational1966.26.186
[20]	Monazam E R, Breault R W, Siriwardane R, et al. Kinetics of the reduction of hematite (Fe₂O₃) by methane (CH₄) during chemical looping combustion: A global mechanism[J]. Chemical Engineering Journal, 2013,232:478-487. doi: 10.1016/j.cej.2013.07.091
[21]	Zhang G Q, Ostrovski O. Reduction of ilmenite concentrates by methane-containing gas: Part I. Effects of ilmenite composition, temperature and gas composition[J]. Canadian Metallurgical Quarterly, 2001,40(3):317-326. doi: 10.1179/cmq.2001.40.3.317
[22]	Zhang Guangqing, Ostrovski O. Reduction of ilmenite concentrates by methane containing gas, Part II: Effects of preoxidation and sintering[J]. Canadian Metallurgical Quarterly, 2001,40(4):489-497. doi: 10.1179/cmq.2001.40.4.489
[23]	Zhang Guangqing, Ostrovski O. Kinetic modeling of titania reduction by a methane-hydrogen-argon gas mixture[J]. Metallurgical and Materials Transactions B, 2001,32(3):465-473. doi: 10.1007/s11663-001-0032-8
[24]	Dang Jie, Fatollahi F F, Pistorius P C, et al. Synthesis of titanium oxycarbide from titanium slag by methane-containing gas[J]. Metallurgical and Materials Transactions B, 2018,49(1):123-131. doi: 10.1007/s11663-017-1123-5
[25]	Dang Jie, Fatollahi F F, Pistorius P C, et al. Synthesis of titanium oxycarbide from concentrates of natural ilmenite (weathered and unweathered) and natural rutile, using a methane-hydrogen gas mixture[J]. Metallurgical and Materials Transactions B, 2017,48(5):2440-2446. doi: 10.1007/s11663-017-1048-z
[26]	Fan Gangqiang, Hou Youling, Huang Dejun, et al. Synthesis of Ti(C, N, O) ceramic from rutile at low temperature by CH₄-H₂-N₂ gas mixture[J]. International Journal of Refractory Metals and Hard Materials, 2021,101:105659. doi: 10.1016/j.ijrmhm.2021.105659
[27]	Fan Gangqiang, Dang Jie, Zhang Run, et al. Synthesis of Ti(C, O, N) from ilmenite at low temperature by a novel reducing and carbonitriding approach[J]. International Journal of Energy Research, 2020,44(6):4861-4874. doi: 10.1002/er.5283
[28]	Fan Gangqiang, Wang Meng, Dang Jie, et al. A novel recycling approach for efficient extraction of titanium from high-titanium-bearing blast furnace slag[J]. Waste Management, 2021,120:626-634. doi: 10.1016/j.wasman.2020.10.024
[29]	Zhang Run, Dang Jie, Liu Dong, et al. Reduction of perovskite-geikielite by methane-hydrogen gas mixture: Thermodynamic analysis and experimental results [J]. Science of The Total Environment, 2020,699: 134355.
[30]	Zhang Run, Fan Gangqiang, Song Mingbo, et al. Thermodynamic analysis and reduction of anosovite with methane at low temperature[C]//Energy Technology 2020: Recycling, Carbon Dioxide Management, and Other Technologies. Springer International Publishing, 2020:285-294.
[31]	Zhang Run, Hou Youling, Fan Gangqiang, et al. Gas-based reduction and carbonization of titanium minerals in titanium-bearing blast furnace slag: A combined thermodynamic, experimental and DFT study[J]. International Journal of Hydrogen Energy, 2022,47(12):7586-7599. doi: 10.1016/j.ijhydene.2021.12.119
[32]	Alizadeh R, Jamshidi E, Ale Ebrahim H. Kinetic study of nickel oxide reduction by methane[J]. Chemical Engineering & Technology, 2007,30(8):1123-1128.
[33]	Rashidi H, Ale E H, Dabir B. Application of random pore model for synthesis gas production by nickel oxide reduction with methane[J]. Energy Conversion and Management, 2013,74:249-260. doi: 10.1016/j.enconman.2013.04.044
[34]	Altay M C, Eroglu S. Isothermal reaction of NiO powder with undiluted CH₄ at 1000 K to 1300 K (727 °C to 1027 °C)[J]. Metallurgical and Materials Transactions B, 2017,48(4):2067-2076. doi: 10.1007/s11663-017-0991-z
[35]	Kharatyan S L, Chatilyan H A, Manukyan K V. Kinetics and mechanism of nickel oxide reduction by methane[J]. The Journal of Physical Chemistry C, 2019,123(35):21513-21521. doi: 10.1021/acs.jpcc.9b04506
[36]	Pickles C A, Anthony W. Thermodynamic modelling of the reduction of a saprolitic laterite ore by methane[J]. Minerals Engineering, 2018,120:47-59. doi: 10.1016/j.mineng.2018.02.006
[37]	Li Bo, Ding Zhiguang, Wei Yonggang, et al. Reduction of nickel and iron from low-grade nickel laterite ore via a solid-state deoxidization method using methane[J]. Materials Transactions, 2018,59(7):1180-1185. doi: 10.2320/matertrans.M2017351
[38]	Liu Fei, Li Bo, Wei Yonggang, et al. Effect of elemental sulfur on the reduction process of laterite nickel ore under the action of methane[J]. Materials Transactions, 2023,64(12):2754-2763. doi: 10.2320/matertrans.MT-M2022189
[39]	Ale E H, Jamshidi E. Kinetic study of zinc oxide reduction by methane[J]. Chemical Engineering Research & Design, 2001,79(A1):62-70.
[40]	Ale E H, Jamshidi E. Effect of mass transfer and bulk flow on the zinc oxide reduction by methane[J]. Industrial & Engineering Chemistry Research, 2002,41(11):2630-2636.
[41]	Ao Xianquan. Basic research on the synthesis of syngas and zinc metal by methane reduction of zinc oxide in molten salt system[D]. Kunming: Kunming University of Science and Technology, 2008. (敖先权. 熔盐体系中甲烷还原氧化锌制取合成气和金属锌的基础研究[D]. 昆明: 昆明理工大学, 2008. Ao Xianquan. Basic research on the synthesis of syngas and zinc metal by methane reduction of zinc oxide in molten salt system[D]. Kunming: Kunming University of Science and Technology, 2008.
[42]	Khoshandam B, Jamshidi E, Kumar R V. Reduction of cobalt oxide with methane[J]. Metallurgical and Materials Transactions B, 2004,35(5):825-828. doi: 10.1007/s11663-004-0076-7
[43]	Shirchi S, Khoshandam B, Hormozi F. Reduction kinetics of cobalt oxide powder by methane in a fluidized bed reactor[J]. Journal of the Taiwan Institute of Chemical Engineers, 2015,51:171-176. doi: 10.1016/j.jtice.2015.01.030
[44]	Qayyum M A, Reeve D A. Reduction of chromites to sponge ferrochromium in methane-hydrogen mixtures[J]. Canadian Metallurgical Quarterly, 1976,15(3):193-200. doi: 10.1179/cmq.1976.15.3.193
[45]	Leikola M, Taskinen P, Eric R H. Reduction of Kemi chromite with methane[J]. Journal of the Southern African Institute of Mining and Metallurgy, 2018,118(6):575-580.
[46]	Anacleto N, Ostrovski O. Solid-state reduction of chromium oxide by methane-containing gas[J]. Metallurgical and Materials Transactions B, 2004,35(4):609-615. doi: 10.1007/s11663-004-0001-0
[47]	Wu Shaowen, Feng Xiaoming, Zhang Yanling, et al. Methane-hydrogen-based pre-reduction chromite: reduction behavior and pellet compressive strength[J]. Journal of Metals, 2024,76(9):4858-4872.
[48]	Anacleto N, Ostrovski O, Ganguly S. Reduction of manganese oxides by methane-containing gas[J]. ISIJ International, 2004,44(9):1480-1487. doi: 10.2355/isijinternational.44.1480
[49]	Ostrovski O, Zhang G. Reduction and carburization of metal oxides by methane-containing gas[J]. AIChE Journal, 2005,52(1):300-310.
[50]	Liu Bingbing, Zhang Yuanbo, Su Zijian, et al. Thermodynamic analysis and reduction of MnO₂ by methane-hydrogen gas mixture[J]. Journal of Metals, 2017,69(9):1669-1675.