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Hydrogen energy has a revolutionary impact on China’s energy structure and consumption system. The hydrogen metallurgy process relying on a hydrogen-based shaft furnace is an effective way to optimize the steel process flow, energy structure, and product structure. It is also a fundamental and disruptive cutting-edge technology for China’s steel industry to achieve carbon neutrality. Based on an overview of the current research and development status of hydrogen metallurgy technologies in China and abroad, this article clarified the prospect of hydrogen metallurgy technologies and analyzed the key issues that constrained the development of the hydrogen-based shaft furnace process in China. On this basis, suggestions for addressing the challenges were proposed.

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氢能对中国能源结构和消费体系产生革命性影响,基于氢基竖炉的氢冶金短流程是优化钢铁工艺流程、能源结构和产品结构的有效途径,是中国钢铁产业实现碳中和的兜底技术和颠覆性前沿技术。文章在概述国内外氢冶金工艺研发现状的基础上,明确氢冶金技术的前景,剖析中国发展氢基竖炉工艺所面临的制约性问题,并提出应对挑战的建议。

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李峰,讲师。主要从事氢冶金关键理论及技术研究。承担国家自然科学基金、国家资助博士后计划、中央高校基本科研业务费等项目8项。发表论文20余篇,授权发明专利10余件。电子信箱:

储满生,教授。东北大学低碳钢铁前沿技术研究院院长,低碳钢铁前沿技术教育部工程研究中心主任,辽宁省低碳钢铁前沿技术工程研究中心主任。国家“万人计划”科技创新领军人才、教育部新世纪人才。主要从事氢冶金、低碳智能化高炉、特色冶金资源高效清洁利用等关键理论及技术研究。主持国家低碳专项、国家高技术研究发展计划、国家自然科学基金、科技部重大国际合作等项目50余项。获省部级科技奖励4项。出版专著6部,发表论文490余篇,授权发明专利60余件。电子信箱:

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李峰,讲师。主要从事氢冶金关键理论及技术研究。承担国家自然科学基金、国家资助博士后计划、中央高校基本科研业务费等项目8项。发表论文20余篇,授权发明专利10余件。电子信箱:

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李峰,讲师。主要从事氢冶金关键理论及技术研究。承担国家自然科学基金、国家资助博士后计划、中央高校基本科研业务费等项目8项。发表论文20余篇,授权发明专利10余件。电子信箱:

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储满生,教授。东北大学低碳钢铁前沿技术研究院院长,低碳钢铁前沿技术教育部工程研究中心主任,辽宁省低碳钢铁前沿技术工程研究中心主任。国家“万人计划”科技创新领军人才、教育部新世纪人才。主要从事氢冶金、低碳智能化高炉、特色冶金资源高效清洁利用等关键理论及技术研究。主持国家低碳专项、国家高技术研究发展计划、国家自然科学基金、科技部重大国际合作等项目50余项。获省部级科技奖励4项。出版专著6部,发表论文490余篇,授权发明专利60余件。电子信箱:

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储满生,教授。东北大学低碳钢铁前沿技术研究院院长,低碳钢铁前沿技术教育部工程研究中心主任,辽宁省低碳钢铁前沿技术工程研究中心主任。国家“万人计划”科技创新领军人才、教育部新世纪人才。主要从事氢冶金、低碳智能化高炉、特色冶金资源高效清洁利用等关键理论及技术研究。主持国家低碳专项、国家高技术研究发展计划、国家自然科学基金、科技部重大国际合作等项目50余项。获省部级科技奖励4项。出版专著6部,发表论文490余篇,授权发明专利60余件。电子信箱:

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2. Institute for Frontier Technologies of Low-Carbon Steelmaking, Northeastern University, Shenyang 110819, China, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null), CN=AuthorExt(id=1242113962758705928, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, authorId=1242113962628682500, language=CN, stringName=刘西财, firstName=null, middleName=null, lastName=null, prefix=null, suffix=null, authorComment=null, nameInitials=null, affiliation=null, department=null, xref=1, 2, address=1.东北大学冶金学院,沈阳 110819
2.东北大学低碳钢铁前沿技术研究院,沈阳 110819, bio=null, bioImg=null, bioContent=null, aboutCorrespAuthor=null)}, companyList=[AuthorCompany(id=1242113961512997599, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, xref=null, ext=[AuthorCompanyExt(id=1242113961521386208, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, companyId=1242113961512997599, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1. School of Metallurgy, Northeastern University, Shenyang 110819, China), AuthorCompanyExt(id=1242113961525580513, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, companyId=1242113961512997599, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.东北大学冶金学院,沈阳 110819)]), AuthorCompany(id=1242113961588495074, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, xref=null, ext=[AuthorCompanyExt(id=1242113961596883683, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, companyId=1242113961588495074, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2. Institute for Frontier Technologies of Low-Carbon Steelmaking, Northeastern University, Shenyang 110819, China), AuthorCompanyExt(id=1242113961605272292, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, companyId=1242113961588495074, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2.东北大学低碳钢铁前沿技术研究院,沈阳 110819)])])], keywords=[Keyword(id=1242113962892923657, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, language=EN, orderNo=1, keyword=hydrogen metallurgy), Keyword(id=1242113962947449610, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, language=EN, orderNo=2, keyword=hydrogen-based shaft furnace), Keyword(id=1242113963001975563, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, language=EN, orderNo=3, keyword=coke oven gas), Keyword(id=1242113963052307212, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, language=EN, orderNo=4, keyword=all-hydrogen shaft furnace), Keyword(id=1242113963106833165, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, language=CN, orderNo=1, keyword=氢冶金), Keyword(id=1242113963165553422, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, language=CN, orderNo=2, keyword=氢基竖炉), Keyword(id=1242113963215885071, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, language=CN, orderNo=3, keyword=焦炉煤气), Keyword(id=1242113963278799632, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, language=CN, orderNo=4, keyword=全氢竖炉)], refs=[Reference(id=1242113966802015022, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2022, volume=null, issue=null, pageStart=null, pageEnd=null, url=https://www.ceads.net.cn/user/search.php?kwtype=0&pagelang=cn&searchtype=titlekeyword&typeid=105&q=2022, language=null, rfNumber=[1], rfOrder=0, authorNames=CEADs Emerging Economy Carbon Dioxide Emissions Report, journalName=null, refType=null, unstructuredReference=CEADs Emerging Economy Carbon Dioxide Emissions Report, 2022. https://www.ceads.net.cn/user/search.php?kwtype=0&pagelang=cn&searchtype=titlekeyword&typeid=105&q=2022., articleTitle=null, refAbstract=null), Reference(id=1242113966869123887, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2024, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[2], rfOrder=1, authorNames=Niu W Q, Li Y, Li Q, journalName=Fuel, refType=null, unstructuredReference=Niu W Q, Li Y, Li Q, et al. Physical and chemical properties of metallurgical coke and its evolution in the blast furnace ironmaking process[J]. Fuel, 2024, 366, doi: 10.1016/j.fuel.2024.131277., articleTitle=Physical and chemical properties of metallurgical coke and its evolution in the blast furnace ironmaking process, refAbstract=null), Reference(id=1242113966919455536, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2022, volume=53, issue=6, pageStart=4075, pageEnd=4086, url=null, language=null, rfNumber=[3], rfOrder=2, authorNames=Zhou Y L, Jiang X, Wang X A, journalName=Metallurgical and Materials Transactions B, refType=null, unstructuredReference=Zhou Y L, Jiang X, Wang X A, et al. Optimizing iron ore proportion aimed for low cost by linear programming method[J]. Metallurgical and Materials Transactions B, 2022, 53(6): 4075-4086., articleTitle=Optimizing iron ore proportion aimed for low cost by linear programming method, refAbstract=null), Reference(id=1242113966973981489, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=10.1007/s40831-020-00276-5, pmid=null, pmcid=null, year=2020, volume=6, issue=2, pageStart=307, pageEnd=332, url=null, language=null, rfNumber=[4], rfOrder=3, authorNames=Harvey L D D, journalName=Journal of Sustainable Metallurgy, refType=null, unstructuredReference=Harvey L D D. Analysis of the theoretical and practical energy requirements to produce iron and steel, with summary equations that can be applied in developing future energy scenarios[J]. Journal of Sustainable Metallurgy, 2020, 6(2): 307-332., articleTitle=Analysis of the theoretical and practical energy requirements to produce iron and steel, with summary equations that can be applied in developing future energy scenarios, refAbstract=This paper derives from first principles simple relationships that can be used to compute energy requirements for the production of hot metal (pig iron) in a blast furnace (BF) or direct reduced iron (DRI) in a direct reduction furnace (DRF), and the transformation of hot metal and DRI into crude steel in a basic oxygen furnace (BOF) or electric arc furnace (EAF) with the addition of scrap iron or scrap steel of varying purity. These relationships account for the impact of changing iron ore grade, in the amount and type of impurities in iron, and the impact of the addition of fluxes and the production of slag. Changing proportions of hot metal and scrap to the BOF, or of DRI and scrap to the EAF, are accounted for. The energy flow analysis presented here, combined with the mass flow analysis presented in a companion paper, provides a foundation for tracking the impact on energy use and iron losses of alternative pathways that might be used in the future as part of a broad-based effort to reduce energy use and associated greenhouse gas emissions.), Reference(id=1242113967036896050, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2019, volume=5, issue=3, pageStart=391, pageEnd=401, url=null, language=null, rfNumber=[5], rfOrder=4, authorNames=Mousa E, Lundgren M, Sundqvist Ökvist L, journalName=Journal of Sustainable Metallurgy, refType=null, unstructuredReference=Mousa E, Lundgren M, Sundqvist Ökvist L, et al. Reduced carbon consumption and CO2 emission at the blast furnace by use of briquettes containing torrefied sawdust[J]. Journal of Sustainable Metallurgy, 2019, 5(3): 391-401., articleTitle=Reduced carbon consumption and CO2 emission at the blast furnace by use of briquettes containing torrefied sawdust, refAbstract=null), Reference(id=1242113967095616307, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2022, volume=12, issue=11, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[6], rfOrder=5, authorNames=Lan C C, Hao Y J, Shao J N, journalName=Metals, refType=null, unstructuredReference=Lan C C, Hao Y J, Shao J N, et al. Effect of H2 on blast furnace ironmaking: A review[J]. Metals, 2022, 12(11), doi: 10.3390/met12111864., articleTitle=Effect of H2 on blast furnace ironmaking: A review, refAbstract=null), Reference(id=1242113967162725172, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2023, volume=15, issue=12, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[7], rfOrder=6, authorNames=Zhang Z D, Tang J, Shi Q, journalName=Sustainability, refType=null, unstructuredReference=Zhang Z D, Tang J, Shi Q, et al. Effects of shaft tuyere parameters on gas movement behavior and burden reduction in oxygen blast furnace[J]. Sustainability, 2023, 15(12), doi: 10.3390/su15129159., articleTitle=Effects of shaft tuyere parameters on gas movement behavior and burden reduction in oxygen blast furnace, refAbstract=null), Reference(id=1242113967225639733, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2023, volume=30, issue=9, pageStart=1714, pageEnd=1731, url=null, language=null, rfNumber=[8], rfOrder=7, authorNames=Bao J W, Chu M S, Liu Z G, journalName=Journal of Iron and Steel Research International, refType=null, unstructuredReference=Bao J W, Chu M S, Liu Z G, et al. Evolution behavior and mechanism of iron carbon agglomerates under simulated blast furnace smelting conditions[J]. Journal of Iron and Steel Research International, 2023, 30(9): 1714-1731., articleTitle=Evolution behavior and mechanism of iron carbon agglomerates under simulated blast furnace smelting conditions, refAbstract=null), Reference(id=1242113967275971382, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2023, volume=30, issue=9, pageStart=1651, pageEnd=1666, url=null, language=null, rfNumber=[9], rfOrder=8, authorNames=Shi Q, Tang J, Chu M S, journalName=International Journal of Minerals, Metallurgy and Materials, refType=null, unstructuredReference=Shi Q, Tang J, Chu M S. Key issues and progress of industrial big data-based intelligent blast furnace ironmaking technology[J]. International Journal of Minerals, Metallurgy and Materials, 2023, 30(9): 1651-1666., articleTitle=Key issues and progress of industrial big data-based intelligent blast furnace ironmaking technology, refAbstract=null), Reference(id=1242113967343080247, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2016, volume=55, issue=null, pageStart=537, pageEnd=549, url=null, language=null, rfNumber=[10], rfOrder=9, authorNames=Quader M A, Ahmed S, Dawal S Z, journalName=Renewable and Sustainable Energy Reviews, refType=null, unstructuredReference=Quader M A, Ahmed S, Dawal S Z, et al. Present needs, recent progress and future trends of energy-efficient ultra-low carbon dioxide (CO2) steelmaking (ULCOS) program[J]. Renewable and Sustainable Energy Reviews, 2016, 55: 537-549., articleTitle=Present needs, recent progress and future trends of energy-efficient ultra-low carbon dioxide (CO2) steelmaking (ULCOS) program, refAbstract=null), Reference(id=1242113967397606200, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2023, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[11], rfOrder=10, authorNames=Shao L, Xu J, Saxén H, journalName=Fuel, refType=null, unstructuredReference=Shao L, Xu J, Saxén H, et al. A numerical study on process intensification of hydrogen reduction of iron oxide pellets in a shaft furnace[J]. Fuel, 2023, 348, doi: 10.1016/j.fuel.2023.128375., articleTitle=A numerical study on process intensification of hydrogen reduction of iron oxide pellets in a shaft furnace, refAbstract=null), Reference(id=1242113967464715065, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=10.1007/s12613-020-2021-4, pmid=null, pmcid=null, year=2020, volume=27, issue=6, pageStart=713, pageEnd=723, url=null, language=null, rfNumber=[12], rfOrder=11, authorNames=Tang J, Chu M S, Li F, journalName=International Journal of Minerals, Metallurgy and Materials, refType=null, unstructuredReference=Tang J, Chu M S, Li F, et al. Development and progress on hydrogen metallurgy[J]. International Journal of Minerals, Metallurgy and Materials, 2020, 27(6): 713-723., articleTitle=Development and progress on hydrogen metallurgy, refAbstract=Hydrogen metallurgy is a technology that applies hydrogen instead of carbon as a reduction agent to reduce CO(2)emission, and the use of hydrogen is beneficial to promoting the sustainable development of the steel industry. Hydrogen metallurgy has numerous applications, such as H(2)reduction ironmaking in Japan, ULCORED and hydrogen-based steelmaking in Europe; hydrogen flash ironmaking technology in the US; HYBRIT in the Nordics; Midrex H-2 (TM) by Midrex Technologies, Inc. (United States); H2FUTURE by Voestalpine (Austria); and SAL-COS by Salzgitter AG (Germany). Hydrogen-rich blast furnaces (BFs) with COG injection are common in China. Running BFs have been industrially tested by AnSteel, XuSteel, and BenSteel. In a currently under construction pilot plant of a coal gasification-gas-based shaft furnace with an annual output of 10000 t direct reduction iron (DRI), a reducing gas composed of 57vol% H(2)and 38vol% CO is prepared via the Ende method. The life cycle of the coal gasification-gas-based shaft furnace-electric furnace short process (30wt% DRI + 70wt% scrap) is assessed with 1 t of molten steel as a functional unit. This plant has a total energy consumption per ton of steel of 263.67 kg standard coal and a CO(2)emission per ton of steel of 829.89 kg, which are superior to those of a traditional BF converter process. Considering domestic materials and fuels, hydrogen production and storage, and hydrogen reduction characteristics, we believe that a hydrogen-rich shaft furnace will be suitable in China. Hydrogen production and storage with an economic and large-scale industrialization will promote the further development of a full hydrogen shaft furnace.), Reference(id=1242113967523435322, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2021, volume=46, issue=17, pageStart=10548, pageEnd=10569, url=null, language=null, rfNumber=[13], rfOrder=12, authorNames=Liu W G, Zuo H B, Wang J S, journalName=International Journal of Hydrogen Energy, refType=null, unstructuredReference=Liu W G, Zuo H B, Wang J S, et al. The production and application of hydrogen in steel industry[J]. International Journal of Hydrogen Energy, 2021, 46(17): 10548-10569., articleTitle=The production and application of hydrogen in steel industry, refAbstract=null), Reference(id=1242113967594738491, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2019, volume=90, issue=10, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[14], rfOrder=13, authorNames=Spreitzer D, Schenk J, journalName=Steel Research International, refType=null, unstructuredReference=Spreitzer D, Schenk J. Reduction of iron oxides with hydrogen: A review[J]. Steel Research International, 2019, 90(10), doi: 10.1002/srin.201900108., articleTitle=Reduction of iron oxides with hydrogen: A review, refAbstract=null), Reference(id=1242113967649264444, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2018, volume=40, issue=3, pageStart=26, pageEnd=30, url=null, language=null, rfNumber=[15], rfOrder=14, authorNames=魏侦凯, 郭瑞, 谢全安, journalName=华北理工大学学报(自然科学版), refType=null, unstructuredReference=魏侦凯, 郭瑞, 谢全安. 日本环保炼铁工艺COURSE50新技术[J]. 华北理工大学学报(自然科学版), 2018, 40(3): 26-30., articleTitle=日本环保炼铁工艺COURSE50新技术, refAbstract=null), Reference(id=1242113967703790397, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, doi=null, pmid=null, pmcid=null, year=2018, volume=40, issue=3, pageStart=26, pageEnd=30, url=null, language=null, rfNumber=[15], rfOrder=15, authorNames=Wei Z K, Guo R, Xie Q A, journalName=Journal of North China University of Science and Technology (Natural Science Edition), refType=null, unstructuredReference=Wei Z K, Guo R, Xie Q A. COURSE50 new technology of Japan’s environmental ironmaking process[J]. Journal of North China University of Science and Technology (Natural Science Edition), 2018, 40(3): 26-30. 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Compressive strength of oxidized pellets under different ore blending schemes

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序号 1号
铁精矿/%
2号
铁精矿/%
3号
铁精矿/%
抗压强度/
(N·个-1
配料-1 85 0 15 3 432
配料-2 80 10 10 3 401
配料-3 60 10 30 3 366
配料-4 40 10 50 3 208
配料-5 85 15 0 3 394
), ArticleFig(id=1242113966307087144, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, language=CN, label=表1, caption=

不同配矿方案下氧化球团抗压强度

, figureFileSmall=null, figureFileBig=null, tableContent=
序号 1号
铁精矿/%
2号
铁精矿/%
3号
铁精矿/%
抗压强度/
(N·个-1
配料-1 85 0 15 3 432
配料-2 80 10 10 3 401
配料-3 60 10 30 3 366
配料-4 40 10 50 3 208
配料-5 85 15 0 3 394
), ArticleFig(id=1242113966370001705, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, language=EN, label=Table 2, caption=

Comparison of oxidized pellet indicators used in hydrogen-based shaft furnace and blast furnace

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球团指标 高炉 氢基竖炉
TFe/% 62 >67
SiO2/% ≈5 ≤2
抗压强度/N 2 000 2 500
还原膨胀/% <20 <15
还原粉化RDI+3.15/% ≥90 ≥95
还原性RI40/(%·min-1 >0.6 0.9~1.4
), ArticleFig(id=1242113966424527658, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, language=CN, label=表2, caption=

氢基竖炉与高炉用氧化球团指标对比

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球团指标 高炉 氢基竖炉
TFe/% 62 >67
SiO2/% ≈5 ≤2
抗压强度/N 2 000 2 500
还原膨胀/% <20 <15
还原粉化RDI+3.15/% ≥90 ≥95
还原性RI40/(%·min-1 >0.6 0.9~1.4
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Cost comparison of hydrogen production processes

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制氢工艺 氢气成本/(元·Nm-3 生产规模/(Nm3·h-1 备注
电解水制氢 2.5~4.0 10~200
天然气蒸汽重整制氢 0.8~1.5 200~200 000 含炼厂气制氢
石油蒸汽重整制氢 0.7~1.6 500~200 000 含液化气制氢
甲醇裂解制氢 1.8~2.5 50~500
液氨裂解制氢 2.0~2.5 10~200
丙烷脱氢制丙烯副产氢 0.4~0.8 10 000~200 000 含乙烷/丙烷脱氢
钢铁厂尾气副产氢 0.5~1.0 10 000~200 000 含焦化
煤气化制氢 0.6~1.2 1 000~200 000
), ArticleFig(id=1242113966550356780, tenantId=1146029695717560320, journalId=1146032081894723586, articleId=1157002946429936412, language=CN, label=表3, caption=

常见制氢工艺成本对比

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制氢工艺 氢气成本/(元·Nm-3 生产规模/(Nm3·h-1 备注
电解水制氢 2.5~4.0 10~200
天然气蒸汽重整制氢 0.8~1.5 200~200 000 含炼厂气制氢
石油蒸汽重整制氢 0.7~1.6 500~200 000 含液化气制氢
甲醇裂解制氢 1.8~2.5 50~500
液氨裂解制氢 2.0~2.5 10~200
丙烷脱氢制丙烯副产氢 0.4~0.8 10 000~200 000 含乙烷/丙烷脱氢
钢铁厂尾气副产氢 0.5~1.0 10 000~200 000 含焦化
煤气化制氢 0.6~1.2 1 000~200 000
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中国氢冶金工艺现状、挑战及发展对策
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李峰 1, 2 , 储满生 1, 2, , 唐珏 1, 2 , 赵子川 1, 2 , 冯金格 1, 2 , 刘西财 1, 2
前瞻科技 | 综述与述评 2024,3(4): 44-57
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前瞻科技 | 综述与述评 2024, 3(4): 44-57
中国氢冶金工艺现状、挑战及发展对策
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李峰1, 2 , 储满生1, 2, , 唐珏1, 2, 赵子川1, 2, 冯金格1, 2, 刘西财1, 2
作者信息
  • 1.东北大学冶金学院,沈阳 110819
  • 2.东北大学低碳钢铁前沿技术研究院,沈阳 110819
  • 李峰,讲师。主要从事氢冶金关键理论及技术研究。承担国家自然科学基金、国家资助博士后计划、中央高校基本科研业务费等项目8项。发表论文20余篇,授权发明专利10余件。电子信箱:

    储满生,教授。东北大学低碳钢铁前沿技术研究院院长,低碳钢铁前沿技术教育部工程研究中心主任,辽宁省低碳钢铁前沿技术工程研究中心主任。国家“万人计划”科技创新领军人才、教育部新世纪人才。主要从事氢冶金、低碳智能化高炉、特色冶金资源高效清洁利用等关键理论及技术研究。主持国家低碳专项、国家高技术研究发展计划、国家自然科学基金、科技部重大国际合作等项目50余项。获省部级科技奖励4项。出版专著6部,发表论文490余篇,授权发明专利60余件。电子信箱:

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Current Status, Challenges, and Development Strategies of Hydrogen Metallurgy Technologies in China
Feng LI1, 2 , Mansheng CHU1, 2, , Jue TANG1, 2, Zichuan ZHAO1, 2, Jin’ge FENG1, 2, Xicai LIU1, 2
Affiliations
  • 1. School of Metallurgy, Northeastern University, Shenyang 110819, China
  • 2. Institute for Frontier Technologies of Low-Carbon Steelmaking, Northeastern University, Shenyang 110819, China
出版时间: 2024-12-20 doi: 10.3981/j.issn.2097-0781.2024.04.004
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氢能对中国能源结构和消费体系产生革命性影响,基于氢基竖炉的氢冶金短流程是优化钢铁工艺流程、能源结构和产品结构的有效途径,是中国钢铁产业实现碳中和的兜底技术和颠覆性前沿技术。文章在概述国内外氢冶金工艺研发现状的基础上,明确氢冶金技术的前景,剖析中国发展氢基竖炉工艺所面临的制约性问题,并提出应对挑战的建议。

氢冶金  /  氢基竖炉  /  焦炉煤气  /  全氢竖炉

Hydrogen energy has a revolutionary impact on China’s energy structure and consumption system. The hydrogen metallurgy process relying on a hydrogen-based shaft furnace is an effective way to optimize the steel process flow, energy structure, and product structure. It is also a fundamental and disruptive cutting-edge technology for China’s steel industry to achieve carbon neutrality. Based on an overview of the current research and development status of hydrogen metallurgy technologies in China and abroad, this article clarified the prospect of hydrogen metallurgy technologies and analyzed the key issues that constrained the development of the hydrogen-based shaft furnace process in China. On this basis, suggestions for addressing the challenges were proposed.

hydrogen metallurgy  /  hydrogen-based shaft furnace  /  coke oven gas  /  all-hydrogen shaft furnace
李峰, 储满生, 唐珏, 赵子川, 冯金格, 刘西财. 中国氢冶金工艺现状、挑战及发展对策. 前瞻科技, 2024 , 3 (4) : 44 -57 . DOI: 10.3981/j.issn.2097-0781.2024.04.004
Feng LI, Mansheng CHU, Jue TANG, Zichuan ZHAO, Jin’ge FENG, Xicai LIU. Current Status, Challenges, and Development Strategies of Hydrogen Metallurgy Technologies in China[J]. Science and Technology Foresight, 2024 , 3 (4) : 44 -57 . DOI: 10.3981/j.issn.2097-0781.2024.04.004
2022年,中国二氧化碳排放量约为102亿t,其中钢铁行业碳排放量约占15%[1]。钢铁工业是国民经济的重要基础产业,化石能源依赖程度高,碳排放量大,是国家实施“碳达峰与碳中和”(简称“双碳”)目标的关键领域。针对高炉的减排技术正在日益革新[2-5],但由于焦炭的不可替代性,低碳高炉技术的最大碳减排量仅为24%[6-10],无法实现碳中和。而氢冶金短流程,特别是氢基竖炉短流程,碳减排效果可以达到50%以上[11-13],是优化钢铁工艺流程、能源结构和产品结构的有效途径,是中国钢铁产业实现碳中和的兜底技术和颠覆性前沿技术,逐渐成为钢铁冶金未来发展的新方向和制高点。
文章概述国内外氢基竖炉直接还原工艺的研发现状,明确氢冶金技术的前景,剖析中国发展氢基竖炉工艺所面临的制约性问题,在此基础上,就中国氢冶金工艺发展所面临的挑战提出对策建议。
目前,世界上正在运行的氢基竖炉直接还原工艺主要有MIDREX、HYL、PERED工艺。近年来,日本、韩国、欧盟、瑞典、德国、美国等均有氢冶金项目规划。例如,日本COURSE50富氢还原炼铁、欧盟ULCOS计划项目、瑞典HYBRIT(Hydrogen Breakthrough Ironmaking Technology)项目、MIDREX H2、H2 FUTURE、德国SALCOS等[14-18]
1966年,Midrex Technologies, Inc.公司在美国俄勒冈钢厂建成直径450 mm、日产1.5 t的竖炉装置,目前已有单台年产能200万t的MIDREX工艺生产设备。据统计,在直接还原总生产能力中,其中56%左右的直接还原铁(Direct Reduction Iron, DRI)是MIDREX竖炉生产的。
近年来,MIDREX H2®被提出,该工艺是指100%采用H2作为入炉还原气,工艺流程如图1所示。为了控制炉温和增碳,在实际还原过程中通入还原气的H2含量约为90%,其他为CO、CO2、H2O和CH4,这些成分是由于采用天然气进行炉温控制和DRI渗碳时引入的。2022年10月11日,Midrex Technologies, Inc.在瑞典北部的博登建设世界上第一座100%氢直接还原铁商业工厂,采用100%绿色氢将每年生产210万t直接还原铁。与传统炼钢相比,该工艺可减少95%的CO2排放。
1955年,HYL公司建成一座有5个反应罐的氢基竖炉直接还原厂,还原气含H2 75%、CO 14%、CO2 8%、CH4 3%、H2O 1%、H2/CO 5.36,后发展为HYL-III竖炉。目前,世界上采用HYL/Energiron工艺生产DRI或热压块铁(Hot Briquetted Iron, HBI)的工业装置2023年总产量达到1 656万t。
随着技术的逐渐成熟,HYL-III氢基竖炉工艺流程(图2)中的重整炉逐渐发生了变化,水蒸气重整天然气的比例逐渐减少,到最后完全取消甲烷水蒸气重整设备,将天然气直接加热进入竖炉使用,推出了甲烷零重整的HYL-ZR法,将煤气加热温度逐步提高到950 ℃,入炉前再补吹氧气将工艺煤气温度提高到1 050 ℃,甲烷在氢基竖炉内发生自重整。目前,共有3座氢基竖炉(印度2座、阿联酋1座)取消了重整器,采用HYL-ZR零重整工艺生产,纽柯与Tenova合作建成了年产250万t DRI的HYL-ZR氢基竖炉,该工艺的开发可为氢基竖炉气源的选择提供多种可行的途径。
2018年6月,在瑞典北部卢勒奥的一家钢铁试验工厂举行了HYBRIT项目的动工仪式,该项目有望将钢厂的碳排放降至接近零。该项目工艺流程与高炉工艺流程的对比如图3所示。项目于2016—2017年进行初步可行性研究;2018—2019年建设试点工厂,在2020—2024年进行试运行,2028年计划将试验工厂扩大,并作为工业化生产设施连续数月进行24 h运转。工厂将在2035年实现正式工业化生产,可使瑞典、芬兰CO2排放分别降低10%、7%。
HYBRIT新工艺主要考虑了造块、制氢、氢气直接还原、电炉工序,其二氧化碳排放、可再生能源消耗、化石能源消耗(煤)、电力消耗分别为25 kg、560 kW·h、42 kW·h、3 488 kW·h,其中能源消耗总计4 090 kW·h(含可再生能源560 kW·h)。与高炉流程相比,HYBRIT新工艺CO2排放降低98.44%;能源消耗减少了36.19%。
ULCOS(Ultra Low CO2 Steel Making)是由15个欧洲国家及48家企业和机构联合发起的超低CO2炼钢项目,旨在根据能源结构,通过碳、氢、电这3种可能途径降低还原剂和燃料用量,将CO2排放量降低至少50%。采用氢气作为还原剂的氢气还原炼铁技术,氢气来源于电解水,尾气产物只有水,可大幅降低CO2排放量。整体工艺流程如图4所示。
该流程氢气直接还原竖炉的碳排放几乎为零,若考虑电力产生的碳排放,全流程CO2排放量仅有300 kg/t钢,与传统高炉工艺1 850 kg/t钢的CO2排放量相比减少84%。氢气直接还原炼钢技术促进钢铁产业的可持续发展,但该工艺的未来发展很大程度上取决于氢气大规模、经济、绿色制取与储运。
2019年4月,德国萨尔茨吉特钢铁公司与Tenova公司提出以氢气为还原剂炼铁,从而减少CO2排放的SALCOS项目。该项目旨在对原有的高炉-转炉炼钢工艺路线进行逐步改造,把以高炉-转炉为基础的碳密集型钢铁生产工艺,逐步转变为竖炉直接还原炼铁-电炉工艺路线,同时实现富余氢气的多用途利用,预计将整个钢铁生产的碳排放减少95%。
SALCOS项目的思路是采用风力发电,电解水制氢和氧,再将氢气输送给冷轧工序作为还原性气体,将氧气输送给高炉使用。2018年1月完成了系统工业化环境运行,2019年1月完成了连续2 000 h的系统测试,产量达40 Nm3 H2/h。在此基础上,开展了GrInHy 2.0项目,其规划如图5所示。GrInHy 2.0项目通过钢企产生的余热资源生产水蒸气,用水蒸气与绿色可再生能源发电,然后采用高温电解水法生产氢气。氢气既可用于直接还原铁生产,也可用于钢铁生产的后道工序,如作为冷轧退火的还原气体。
中晋冶金科技有限公司已建成利用焦炉煤气制氢实现氢冶金的生产线,其中主要包括核心项目30万t/a直接还原铁项目和气源项目100万t/a焦化项目。该项目采用焦炉煤气干重整工艺制备氢基竖炉用还原气,即以焦炉气与竖炉自产的炉顶气为原料,经过净化和干重整转化后得到还原气用于直接还原铁生产,其工艺流程如图6所示。该工艺初步验证了氢基直接还原铁技术在中国的可行性和可靠性,为中国氢基竖炉生产直接还原铁的发展奠定了良好的基础。
河钢集团有限公司(简称河钢集团,HBIS)与特诺恩公司合作开发,建设基于焦炉煤气的氢基竖炉示范工程,其工艺如图7所示。该项目旨在通过改变能源消耗结构,使用富氢气体代替长流程依赖的焦炭和煤,从工艺源头削减排放。通过对副产物CO2进行捕集和精制,制成成品级CO2产品用于下游产业,完成末端治理。2022年12月16日,河钢集团120万t氢冶金示范工程一期全线贯通,2023年5月已实现安全顺利连续生产绿色DRI产品,并于2024年3月29日,系统开展“氢基竖炉-近零碳排电弧炉”炼钢关键技术研发和工程应用研究,最终实现粗钢近零碳排放目标,助力绿色高品质钢铁材料研发应用。
该工艺焦炉煤气消耗量约550 Nm3/t DRI[19],与同等规模的高炉-转炉长流程相比,氢冶金二氧化碳减排70%,每年可减少碳排放80万t,以DRI为原料开发出多种高端绿色新材料,助力突破中国高端金属材料的“卡脖子”难题。
2023年12月23日,由中国宝武钢铁集团有限公司(简称中国宝武)建设的国内首套百万吨级氢基竖炉项目在广东湛江成功点火投产。一期工程规模100万t/a,同时使用天然气、焦炉煤气和氢气,且比例可调,还原煤气的H2含量超过57%,该项目工艺流程见图8,竖炉本体、煤气加热炉、工艺气体压缩机均按高氢气比例的工况要求配置,焦炉煤气采用竖炉自处理与部分氧化法重整相结合的工艺技术。与同等规模铁水产量传统铁前全流程高炉炼铁工艺相比,CO2排放量可降低58%~89%,可减少CO2排放50万t/a以上。未来宝钢湛江钢铁有限公司将在氢基竖炉的基础上,利用南海地区光伏、风能配套上“光-电-氢”“风-电-氢”绿色能源,形成与钢铁冶金工艺相匹配的全循环、封闭的流程,产线碳排放较长流程降低90%以上,并通过“碳捕集”“森林碳汇”等实现绿氢全流程零碳工厂。
2024年1月,中国钢研科技集团有限公司自主研发和建设的纯氢多稳态竖炉示范工程,在山东省临沂市临港区正式运行。该示范线年产能为5万t,顺利运行300 h,氢气加热温度达到1 050 ℃以上,金属化率达到93%。2024年4月完成了第2次生产运行,直接还原铁的金属化率达到96%以上。
该项目使用氢气(含量高于95%)作为还原剂,初步打通了从纯氢还原到高纯铁制备的全流程工艺,开发了纯氢分体式竖炉、松料及排料装置、氢气高温电加热器等核心装备,通过研发氢气高温加热、冷却气余热全效利用、多维度松料、多梯度氢气喷吹等关键技术实现纯氢竖炉高还原效率、高能量利用率,有效推动了“绿电-制氢-用氢”的新能源产业链形成,为中国钢铁行业实现碳中和目标提供支撑。
东北大学围绕氢基竖炉炉料性能协同优化、氢基竖炉直接还原、基于氢冶金的钒钛磁铁矿高效低碳冶炼新工艺等方面进行了深入研究,构建了氢基竖炉直接还原基础理论体系,形成具有自主知识产权的氢基竖炉直接还原关键技术。在前期技术积累的基础上,自主研发设计了氢气加热炉、氢气竖炉等核心装备,建设万吨级氢气竖炉直接还原示范线。
1)氢基竖炉还原用炉料制备
针对高品位铁精矿精选过程矿物高效解离、高品位铁精矿氧化焙烧固结机理、高品位优质氧化球团制备工艺技术及氢基竖炉炉料冶金特性多目标优化开展研究,成功开发磁铁精矿精选高品位铁精矿技术,以全铁(TFe)65%左右、晶粒粗大、可磨的普通磁铁精矿为原料,可生产出TFe>70.0%、SiO2<2.0%的高品位铁精矿。在此基础上,对不同种类高品位铁精矿的基础特性进行研究,通过单矿及配矿实验,实现不同种类高品位铁精矿之间的优势互补,制备出满足氢基竖炉用原料要求的高品位氧化球团,同时构建出高品位铁精矿资源基础特性数据库,为大规模使用氢基竖炉冶炼奠定良好的原料基础。该技术现已应用于国内某钢铁企业的高品位氧化球团生产线。
表1为不同配矿方案下氧化球团抗压强度。在所有的5种铁精矿的配矿方案中,配料-1系列氧化球团的抗压强度最高,达到了3 432 N/个;配料-4系列氧化球团的抗压强度最低,为3 208 N/个,均满足氢基竖炉用高品质氧化球团的质量要求。
2)氢基竖炉直接还原工艺配置
围绕绿色低碳冶金技术创新工程,模拟现场氢基竖炉工艺,以现场球团为原料,开展了氢基竖炉不同还原温度及还原H2/CO比条件下,氧化球团还原性能、还原膨胀、还原黏结及还原后强度变化的机理研究,阐明了H2-CO对氢基竖炉冶炼过程的耦合作用机制,优化了氢基竖炉工艺配置。
随着H2含量增加,球团还原加快,还原膨胀率及黏结指数均降低,还原后抗压强度升高。在纯氢和950 ℃条件下,最大还原膨胀率、最大黏结指数及最终抗压强度分别为17.35%、5.82%和817 N。升高温度,还原加快,还原膨胀率及黏结指数明显增大,还原后抗压强度降低。当温度升高或还原气中CO增多时,球团中铁晶须明显生长,导致还原膨胀率及黏结指数升高。因此,可通过选择合理的还原温度、适当提高还原气中H2比例,来改善球团冶金性能。此外,还设计了氢基竖炉还原-电熔分工艺模型,如图9所示。通过改变模型中球团成分、还原气氛、还原温度、冷却气成分等数值,从而得到氢基竖炉不同的炉顶煤气成分,物料平衡结果及热平衡结果等。该工艺模型已成功应用于国内某大型钢铁企业,为氢基竖炉工艺优化提供理论依据。
3)氢基竖炉冶炼工艺参数优化
基于某钢铁企业氢基竖炉的冶炼参数,针对产品的金属化率、渗碳量、顶煤气温度等指标进行考察,开展高品位氧化球团氢基竖炉直接还原模拟研究,提出了氢基竖炉的结构优化方案。适宜的冶炼参数为:料速0.001 m/s;还原气流量2 582 Nm3/min,还原气温度1 000 ℃,H2/CO=8,风口直径130 mm;高径比1.8;冷却气流量810 Nm3/min;还原段高径比不宜过高,同时需要为球团膨胀及还原气裂解预留一定空间。此研究结果为现场氢基竖炉工艺优化提供了重要借鉴。
4)氢基竖炉短流程多维度评价
围绕不同氢源的氢基竖炉直接还原短流程的热经济成本、能耗、碳排放等指标,进行了工艺全流程多维度评价。同时,建立了系统环境排放指数模型和指标综合评价模型,以不同氢源的氢基竖炉短流程为对象进行评价,并与传统高炉流程进行了对比。在当前条件下,电解水-全氢竖炉的单位还原气热经济学成本以及单位DRI经济学成本均为最高,分别为0.39元/MJ、7 068元/t;天然气-竖炉的能耗最低,而电解水-全氢竖炉的碳排放最低,吨铁CO2排放仅为0.138 t,高炉流程的碳排放最高,高达1.75 t CO2/t产品。该研究为针对不同碳减排目标的氢冶金短流程工艺决策提供数据支撑。
5)中低品位矿氢基竖炉还原-电热熔分
以企业实际生产需求为导向,开展中低品位矿氢基竖炉直接还原-电热熔分基础研究。基于某中低品位矿进行氧化球团制备,并检测其冶金性能,在预热温度为925 ℃,预热时间为15 min,焙烧温度为1 300 ℃,焙烧时间为20 min条件下,球团的抗压强度为2 336 N,满足氢基竖炉生产要求;1 000 ℃、70% H2条件下,球团的各项还原指标均符合氢基竖炉生产标准,但是实际竖炉还原气氛中氢气比例为60%~65%,而60% H2条件下还原粉化指数LTD‒3.2为13.55%,难以满足竖炉的生产标准。因此,需要通过配加高品位铁精矿,改善中低品位矿球团低温还原粉化性能。
配矿优化结果表明,60%中低品位矿+40%高品位矿的氧化球团抗压强度为2673 N;在950 ℃,60% H2、18% CO、4% CO2、18% N2条件下,各项指标满足氢基竖炉冶炼要求。在此基础上进行电热熔分研究,最终Fe的收得率为98.42%,Ti的收得率为94.26%。该研究为氢基竖炉大规模使用中低品位矿并进行有价组元回收指明了方向。
6)万吨级氢气竖炉短流程中试基地建设
基于前期技术积累,围绕钢铁产业实现碳中和及高质化发展的战略目标,针对中国氢气竖炉技术体系中亟待突破的核心技术、关键装备和工程示范等重大需求,通过政产学研用协同创新,研发氢气竖炉-绿色电炉零碳钢铁冶金短流程前沿技术与重大装备,设计了具有自主知识产权的万吨级氢气竖炉系统,如图10所示。东北大学正在辽宁省沈抚改革创新示范区东北大学工业技术研究院建设全国首个基于氢气竖炉-绿色电炉-高端特钢的氢冶金零碳钢铁冶金短流程中试基地,目标是在氢气竖炉、高端精品钢生产、钢铁冶炼短流程等重大工艺和装备技术取得重大突破和形成示范应用。这是一项既符合中国国情又是国内亟需的氢冶金短流程新技术,具有广阔的应用前景和显著的节能减排优势。项目实施和成果转化应用对氢冶金短流程在钢铁行业的推广和实现钢铁产业低碳绿色化创新发展具有重要意义。目前,项目备案、评价、工程化设计、设备加工制造均已完成,正在办理施工许可证,预期将于2025年建成验收。
通过对比可以看出,国外氢冶金发展时间长,技术成熟,生产经验丰富,主要核心工艺掌握在HYL、MIDREX等公司手中;而国内氢冶金发展较晚,近些年通过引进技术,宝钢湛江钢铁有限公司、河钢集团、中晋太行矿业有限公司均已建成氢基竖炉装置并投产,填补了国内氢冶金氢基竖炉工艺的空白。但高额知识产权费用、核心科技保密等问题依旧存在。
此外,在技术层面仍存在较多问题制约着中国氢基竖炉直接还原工艺的发展与应用,这需要高校、企业、研究机构相联合,依托国家政策扶持,重点从铁矿选矿精料、炉料制备技术、氢能储运难题、氢基竖炉高效低成本冶炼等诸多方面着手开展研究,突破核心技术难关,实现氢冶金相关技术自主化,合理选择适合于中国国情的氢冶金工艺路线。
从国内外氢冶金工艺的发展现状不难看出,中国氢冶金技术发展的重点应为富氢竖炉直接还原工艺。考虑中国“缺油少气”的资源情况,而焦炉煤气主要成分为氢气(体积分数55%~60%)和甲烷(体积分数23%~27%),开发焦炉煤气用作还原剂来生产直接还原铁在缺乏廉价天然气的地区逐渐成为主流趋势。以焦炉煤气代替天然气,不装备重整炉,焦炉煤气直接通入竖炉,进行直接还原铁生产。此种工艺方法的优点是无须重整炉,不依赖昂贵的镍催化剂,煤气直接进入竖炉,并在竖炉里靠直接还原铁和新生成的金属铁作催化剂来完成CH4的裂化反应。经测算,基于焦炉煤气的氢基竖炉工艺,可实现碳减排40%以上,由于焦炉煤气相较氢气和天然气更加廉价,在钢铁厂副产焦炉煤气丰富的场景下,基于焦炉煤气的氢基竖炉工艺具有更加广阔的前景。
若完全实现碳中和目标,则氢基竖炉的氢源需由富氢气体转变为纯氢气,即工艺流程转变为全氢竖炉-电炉短流程。随着未来氢能产业的逐步成熟,全氢竖炉-电炉短流程将是中国未来氢冶金发展的主要方向。中国风能、太阳能等绿色能源充足,风电、光伏发电廉价制氢发展潜力巨大。按照规划,到2030年,中国非化石能源比例要达到20%,利用风电和光伏发电电解水制氢,将电能转化为可长期储存的氢气,既可为工业生产提供优质原料和二次能源载体,又可削峰填谷、消纳弃风弃光的电能、提高能源利用效率,是可再生电力利用的重要技术选择之一。鉴于全氢竖炉诸多技术难题和经济性,未来结合可再生能源制氢规模化、廉价化(绿氢成本和电价降至0.65元/Nm3和0.1元/(kW·h),DRI成本与富氢竖炉相当)和中国自主氢基竖炉技术成熟化,再逐步过渡到电解水制氢-全氢竖炉是中国未来钢铁行业的发展方向之一。
与传统高炉对原料的要求有所不同,铁矿石在氢基竖炉内还原时,含铁原料的主要化学变化是从铁氧化物中脱除氧,直接还原产品中几乎包含着含铁原料中全部的脉石和杂质。因此,氢基竖炉工艺要求原料的铁含量应尽可能高,脉石含量应尽可能低,这样才能使直接还原产品被下游用户所接受。
为使氢基竖炉产品DRI满足一级品(H92)的要求,氢基竖炉入炉球团需满足铁品位TFe>67%,因此,需使用TFe>69%、SiO2<2%的高品位铁精矿制备氢基竖炉用高品位氧化球团。中国铁矿资源特点是以贫矿为主,平均品位仅为32%,而且多为开采难度大的地下矿。2021年,中国铁矿对外依存率高达76.2%,进口铁矿品位大部分在60%左右,难以经济性地将普通铁矿品位提升至69%以上。
相比于传统的高炉炼铁,氢基竖炉工艺除了对氧化球团铁品位提出更高要求外,还对入炉球团还原性、粉化、膨胀、高温黏结等冶金性能要求更苛刻(表2)。
由于氢基竖炉用铁矿品位高、脉石含量少,氧化焙烧固结机理显著区别于普通球团,高品位铁精矿球团固结难、强度差、易膨胀粉化,难适用于氢基竖炉,高品位铁精矿与高品质球团制备的工艺技术尚未明确,经济性的生产手段未获得实际应用。
经济性和低碳性是制约选择制氢技术路线的关键因素。氢能市场前景广阔,当前制氢方式主要有4种:化石燃料制氢、工业副产物制氢、电解水制氢、生物质制氢及其他。
化石燃料制氢是中国的主要制氢方式,虽然技术成熟、成本相对低,但制氢的同时会导致大量碳排放,属于灰氢;利用太阳能、风能等可再生能源发电继而电解水制取氢气(电转气)技术立足于未来碳中性,属于绿氢;电解水制氢是未来发展重点,但目前其转化效率有待提高。氢气仍然是成本较高的二次能源。常见制氢工艺成本对比见表3
富氢气体/氢气加热是氢冶金竖炉短流程的关键环节之一。根据工艺的不同,在加热炉管内,富氢还原气中的CH4或被催化剂,或仅被加热不进行裂解。当CH4不发生裂解时,过多的甲烷在加热过程中会发生析碳反应——CH4=C↓+2H2,析出的碳与高温合金炉管中的铁元素极易渗碳生成FeC3,腐蚀损坏含铁的高温煤气加热炉炉管,使其开裂、脱落形成蚀坑,长期高温使用引起的腐蚀使炉壁局部减薄,甚至个别位置发生泄漏、爆燃导致设备损坏和安全事故。
当还原气为纯H2时,尽管加热炉炉管内避免了CH4、CO的析碳、渗碳问题,但合金炉管材料的抗高温、氢脆失效问题变得突出,不仅需考虑氢气流速快、加热难度大的问题,还需要考虑在临氢环境下,高温合金炉管的氢脆问题。
当还原气全为H2时,系统内部无法实现热量互补变换和参与反应的物质循环。在纯氢竖炉内,发生下列反应:
3Fe2O3+H2=2Fe3O4+H2O, ΔH 298 θ=-12.1 kJ/mol
Fe3O4+H2=3FeO+H2O, ΔH 298 θ=164.0 kJ/mol
FeO+H2=Fe+H2O, ΔH 298 θ=135.6 kJ/mol
Fe2O3+3H2=2Fe+3H2O, ΔH 298 θ=95.8 kJ/mol
其中,式(2)、式(3)为两个强吸热反应,导致整个氢还原过程的强吸热效应。
因此,在入炉煤气温度不变的条件下,纯氢气还原铁矿石会大量吸热,导致竖炉中散料层内的温度场急剧向凉,延缓了需要消耗大量热量的后续氢气还原氧化铁的化学反应,煤气利用率大幅下降。若要维持预定的生产率,必须增加作为载热体的入炉氢气量,如炉顶压力0.4 MPa、900 ℃条件下,全氢竖炉的入炉氢气量至少要达到2 201 Nm3/t DRI,才能满足竖炉还原的热量需求;而当入炉还原气H2/CO为2/5时,入炉还原气量仅为1 228 Nm3/t DRI。若采用相同的入炉煤气量,纯氢气基竖炉的DRI产量将大幅减少,单位DRI生产成本大幅提高。
另外,对于纯氢竖炉直接还原,为了使生产率不降低,有人提出提高入炉氢气温度而不必提高入炉氢气量。但提高入炉氢气温度需要有效解决如下技术难题,包括:①提高氢气的目标加热温度受限于加热炉炉管材质的耐高温氢蚀性能,采用耐更高温度氢蚀的材料必然增加加热炉制造成本;②氢气极易泄漏,氢气加热时对加热系统和输送管道的防泄漏能力要求极高,更高的加热温度则会大幅增加系统设备造价和生产安全隐患;③由于氢气密度小,逃逸速度快,若需将氢气加热至更高的目标温度,必须控制氢气在加热炉管内流速,将进一步增加加热炉的设计难度。
此外,氢基竖炉直接还原过程中,在入炉煤气温度一定的条件下,H2还原速度并非随H2含量线性增加,这主要是因为H2还原能力受反应器内部温度场的制约。当H2含量不高时,增加H2含量会加快还原进程并达到还原速率的最大值,最大值时的氢含量是该条件下的最佳比例。但是,当H2含量进一步增加后,H2还原铁矿石吸热将使铁矿石床层温度降低,而且这一效应逐渐占据主导地位,铁矿石还原速率将持续受到阻碍。这是移动床中温度场派生效应相互消长的结果。这时,若想提高还原反应的速率和保证产能,必须通过增加入炉H2流量,或者用其他物理方法向床层补充热量保持高温,才能达到氢气快速还原的效果。
H2密度小,导致其进入竖炉就会急剧向炉顶逃逸。与混合气体相比,氢气在炉内的路径、方向迅速改变,使H2不能很好地停留在竖炉下部的高温带完成含铁炉料还原的任务。由图11可知,从理论上讲,H2入炉压力达到1 MPa或H2入炉温度达到1 000 ℃以上时,产品也可以达到工艺产品的设计指标。鉴于H2是一种极其易燃易爆的气体,竖炉需要高效率长期稳定生产,若让竖炉反应器系统设备在高温、高压极限条件下长期工作,很难保障反应器设备和员工的安全,则不符合冶金工艺设计的目标。
虽然提高操作压力和温度可达设计指标,但受限于加热炉管材料耐高温氢蚀性能无法随意提高还原气温度。此外,H2极易泄漏,易燃易爆,对反应器及管道防泄漏能力要求极高,氢气逃逸速度快,加热炉设计难度增大。
纯H2还原生产的DRI反应活性大。若在竖炉内无渗碳,则极易发生再氧化,钝化特别困难,难以安全储存、运输和使用。而且,全氢无渗碳生产的DRI熔点高,送至电炉炼钢时电耗增加。实际上,炼钢生产不可避免地需要配碳。因此,在竖炉内对DRI进行部分渗碳,除了可以解决DRI再氧化和安全储运等问题以及降低电炉熔炼电耗之外,还有利于电炉不配碳或少配碳,同时提高钢水纯净度。
目前,氢基竖炉直接还原铁厂均建在天然气资源丰富且廉价的地区,如中东、拉丁美洲、北美洲等,大量使用天然气生产DRI的伊朗、美国、埃及的天然气市场价格仅为0.1美元/Nm3。天然气与煤相比具有非常好的环保优势和能效优势,而中国资源禀赋的特点是富煤、缺油、少气、价格较贵,若用于生产直接还原铁不仅气源不足,成本也高。
氢气竖炉生产1 t DRI约需600 m3氢气,这仅为化学需求量,同时考虑氢气净化回收过程中的损失,生产1 t DRI,氢气实际消耗量将达到700~800 m3,氢气单价按照3元/m3计算,仅氢气消耗的成本即达到2 000~2 400元/t DRI。据此计算,DRI的生产成本将达到3 500~4 000元/t。若采用电解水制氢,则成本将大幅提升。根据目前市场情形,高炉生铁成本约2 500~3 000元/t。可见,相比于传统高炉流程,氢基竖炉工艺生产成本高,经济性差。
1)精料技术与炉料成本控制
将精料扩展到选矿—炼铁—产品全流程效益来研究,用产业链的整体效益来确定合理的铁精矿标准。若氢基竖炉直接还原企业不能掌控进口优质铁矿石的价格,就应尽量建立基于企业及周边资源的选冶企业产业链,充分利用国产优质铁精矿制备专用球团,精心控制成本。
此外,还应着重对高品位、低脉石含量铁矿高效氧化固结、高品位球团化学成分-矿物结构-冶金性能一体化调控进行深入研究,形成可靠、经济的氢基竖炉炉料技术,为发展氢基竖炉提供基础保障。
2)制氢与用氢协同创新,提升经济性
从生产成本角度出发,提升氢基竖炉工艺经济性的途径主要包括:①降低制氢成本;②提升技术水平,降低入炉煤气量,从而减少生产过程中泄漏的氢气,以及循环回收过程中损失的氢气;③球团成本优化,在保障原料性能的前提下,着力开发精料技术,提升选矿水平,降低球团生产成本。
钢铁企业应联合上游制氢产业进行协同创新,加强对接交流,与上下游企业共同探索形成有效的氢能产业发展的可行路径。同时,钢铁行业可推动有关部门提供氢能政策支持,鼓励科研人员跨产业链合作,推动制氢、储氢、运氢、用氢等各个环节技术创新,推动氢能规模化发展与应用。
3)加大基础研发投入,突破关键共性技术
氢还原强吸热、加热炉析碳、炉管氢脆是困扰氢基竖炉高效安全生产的最大技术难题,加强基础研究,如基于富氢气体/氢气的介质特性,需深入研究腐蚀发生机理、析碳/渗碳行为、高温材质氢脆机理,提出有效抑制方法,优化加热方式和炉型结构,突破高效安全加热技术;研究氢气竖炉关键工艺参数对球团还原、黏结、膨胀、粉化、强度变化等冶金行为的影响机理,建立氢气竖炉数学模型,重构氢气竖炉全新反应体系,解析氢气竖炉多场多相多反应耦合机制,形成氢气竖炉直接还原的理论体系,突破氢基竖炉工艺技术。在此基础上,加大投入,提升核心装备研发能力,实现装备技术的自主创新。
4)开展工程示范,推进氢冶金关键技术的产业化应用
氢冶金技术应用仍然面临绿氢成本高、技术应用缺乏经验、氢基直接还原铁产品下游市场需求不足等一系列严峻挑战,亟待研究解决。随着氢冶金技术在中国的不断提升与发展,钢铁工业应逐步构建完善氢冶金技术体系。在产业政策方面,国家应持续推动优化产业政策,制定更加明细和具体的产业扶持政策,氢冶金新技术亟须各个层面的政策扶持,才能突破国外技术壁垒,激励氢冶金探索性研究和工程示范,推进氢冶金关键技术的产业化应用。
为实现“双碳”目标,基于氢基竖炉的氢冶金短流程是钢铁产业实现碳中和的重要途径之一。针对中国的资源和能源供应条件,合理选择适合于中国国情的氢冶金工艺路线对实现钢铁产业低碳绿色、可持续发展至关重要。总体而言,氢基竖炉用原料制备将逐步趋向于优质稳定化,还原气制备将逐步向绿色低成本、高效安全的方向发展。基于此,对中国氢冶金工艺的发展提出3点展望:①综合考虑纯氢气基竖炉存在吸热效应强、入炉H2气量增大、生产成本升高、H2还原速率下降、产品活性高和难以钝化运输等诸多问题,再加上目前制氢储氢尚待完善技术和降低成本,在今后一段时间中国发展氢冶金的重点应是富氢竖炉直接还原工艺。未来,随着氢能的大规模廉价供应,逐步过渡至全氢竖炉短流程。②钢铁行业与氢能产业的结合,是钢铁工业绿色低碳、高质量发展的重要路径。钢铁企业应因地制宜推动氢能应用,推动规模化发展,不断降低氢能利用成本,推动氢基竖炉工艺的发展与进步。③国内钢铁企业和院校应协同开展符合中国国情的氢基竖炉工程示范,推进氢冶金关键核心技术的成熟和产业化应用,助力中国钢铁产业低碳绿色化创新发展。
  • 国家自然科学基金(U23A20608)
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doi: 10.3981/j.issn.2097-0781.2024.04.004
  • 接收时间:2024-10-15
  • 出版时间:2024-12-20
  • 发布时间:2024-12-24
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  • 收稿日期:2024-10-15
  • 修回日期:2024-11-01
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国家自然科学基金(U23A20608)
作者信息
    1.东北大学冶金学院,沈阳 110819
    2.东北大学低碳钢铁前沿技术研究院,沈阳 110819

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表12种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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