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基于CH4-H2体系的氢还原技术发展现状

张润,  谭钞文,  党杰

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文章导航 > 钢铁钒钛  > 2024 >  45(6): 7-18
张润, 谭钞文, 党杰. 基于CH4-H2体系的氢还原技术发展现状[J]. 钢铁钒钛, 2024, 45(6): 7-18. doi: 10.7513/j.issn.1004-7638.2024.06.002
引用本文: 张润, 谭钞文, 党杰. 基于CH4-H2体系的氢还原技术发展现状[J]. 钢铁钒钛, 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
Citation: 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
shu

基于CH4-H2体系的氢还原技术发展现状

doi: 10.7513/j.issn.1004-7638.2024.06.002

  • 重庆大学材料科学与工程学院, 重庆 400040

基金项目: 国家自然科学基金（52074057、52222408）；重庆市自然科学基金创新发展联合基金项目（CSTB2024NSCQ-LZX0045）。
详细信息
    作者简介:

    张润，1995年出生，男，四川南充人，博士研究生，长期从事钛资源高值利用、氢冶金研究工作，E-mail：zhangrun@cqu.edu.cn

    通讯作者:

    党杰，1988年出生，男，甘肃白银人，教授，长期从事钒钛资源高值利用、氢冶金、电解水制氢研究工作，E-mail：jiedang@cqu.edu.cn

  • 中图分类号: TF803.12

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

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

    摘要
  • 摘要: 在“双碳”目标与“双高”限制的双重挑战下，火法冶金领域正面临能耗与碳排放的双重压力，对清洁能源的需求愈发迫切。氢能，作为一种可再生清洁能源，为火法冶金带来了节能低碳、绿色转型的新曙光。基于CH4-H2体系的氢还原技术，凭借其优良的还原能力和低碳无污染的特性，已成为冶金领域研究的热点。阐述了CH4-H2体系的还原热力学与动力学原理，以及国内外相关技术及研究进展，总结了该技术在还原金属矿物（铁、钛、镍、锌、钴、铬、锰）方面的研究成果与发展方向，并针对尚未解决的问题进行了系统分析。基于CH4-H2体系的氢还原技术有巨大的应用潜力，这些探讨将有助于推动该技术的进一步发展。
    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.
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  • 图  1  CH4-H2混合气体的热力学计算

    (a) 热力学平衡物相计算[10]；(b) 碳的热力学活度计算[11]

    Figure  1.  Thermodynamic calculation of CH4-H2 gas mixture

    下载: 全尺寸图片 幻灯片

    图  2  金属氧化物与CH4的多界面反应模型[12]

    (a) 球形颗粒模型；(b) 圆柱形模型；(c) 层状模型；(d) 660 ℃下NiO的还原度与反应时间的关系

    Figure  2.  Multi-interface reaction model of metal oxides and CH4[12]

    下载: 全尺寸图片 幻灯片

    图  3  不同温度下铁精矿在CH4-H2体系中的还原产物XRD谱 [18]

    Figure  3.  XRD pattern of reduction products of iron concentrate in CH4-H2 system at different temperatures[18]

    (a) 1 h；(2) 3 h

    下载: 全尺寸图片 幻灯片

    图  4  双界面收缩核模型和裂核模型的示意[23]

    (a) 双界面收缩核模型；(b) 裂核模型

    Figure  4.  Schematic diagram of the two-interface shrinking-core model and the crackling-core model[23]

    下载: 全尺寸图片 幻灯片

    图  5  CH4-H2-N2 体系下含钛物相的还原过程示意[26-27]

    (a) TiO2； (b) 钛精矿

    Figure  5.  Schematic diagram of the reduction process of titanium-bearing phases in CH4-H2-N2 system[26-27]

    下载: 全尺寸图片 幻灯片

    图  6  CH4N2O添加量对8% CH4-8% N2-84% H2体系中含钛高炉渣还原的影响[28]

    （a）不添加Fe2O3和（b）添加5% Fe2O3的样品在1150 ℃还原8 h的XRD谱；（c）不添加Fe2O3和 (d)添加5% Fe2O3样品的半定量计算；(e) Ti（C, N, O）半定量含量的比较

    Figure  6.  Effect of CH4N2O addition on the reduction of titanium-bearing blast slag in the 8% CH4-8% N2-84% H2 system[28]

    下载: 全尺寸图片 幻灯片

    图  7  CaTiO3、MgTiO3和Mg2TiO4在CH4-H2开放体系中的热力学平衡物相分析[31]

    Figure  7.  Thermodynamic equilibrium phase analysis of CaTiO3, MgTiO3 and Mg2TiO4 in the CH4-H2 open system[31]

    (a) 1300 ℃；(b) 1350 ℃；(c) 1400 ℃；(d) 1200 ℃； (e) 1300 ℃；(f) 1400 ℃； (g) 1200 ℃；(h) 1300 ℃； (i) 1400 ℃

    下载: 全尺寸图片 幻灯片

    图  8  CH4还原NiO/Ni丝上多晶NiO的成核—生长过程[35]

    Figure  8.  Nucleation-growth process of the polycrystalline NiO on NiO/Ni filament reduced by CH4[35]

    下载: 全尺寸图片 幻灯片

    图  9  CH4与红土镍矿反应机理[38]

    Figure  9.  Mechanism diagram of the reaction between CH4 and the laterite nickel ore[38]

    下载: 全尺寸图片 幻灯片

    图  10  铬铁矿球团在CH4和H2气氛中的还原行为和抗压强度[47]

    （a）50%,（b）20%,（c）10%,（d）5% CH4比例下的综合金属化率；（e）每克球团的CH4输入量与综合金属化率之间的关系；（f）综合金属化率与球团的平均抗压强度之间的关系；（g）每克球团的CH4输入量与球团的平均抗压强度之间的关系

    Figure  10.  Reduction behavior and compressive strength of the chromite pellets in CH4 and H2 atmospheres[47]

    下载: 全尺寸图片 幻灯片
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