Article(id=1212410687788327712, tenantId=1146029695717560320, journalId=1146031591421210625, issueId=1212410683682099946, articleNumber=null, orderNo=18, doi=10.3981/j.issn.1000-7857.2024.03.01088, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1709654400000, receivedDateStr=2024-03-06, revisedDate=1727366400000, revisedDateStr=2024-09-27, acceptedDate=null, acceptedDateStr=null, onlineDate=1766990833470, onlineDateStr=2025-12-29, pubDate=1762963200000, pubDateStr=2025-11-13, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766678400000, onlineIssueDateStr=2025-12-26, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766990833470, creator=13701087609, updateTime=1774080293306, updator=sys-migrate, issue=Issue{id=1212410683682099946, tenantId=1146029695717560320, journalId=1146031591421210625, year='2025', volume='43', issue='21', pageStart='1', pageEnd='136', issueExtLink='null', onlineDate='null', pubDate='1762963200000', pubDateStr='2025-11-13', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766990832490, creator='13701087609', updateTime=1774330578192, updator='13041195026', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1243195808502366441, tenantId=1146029695717560320, journalId=1146031591421210625, issueId=1212410683682099946, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1243195808502366442, tenantId=1146029695717560320, journalId=1146031591421210625, issueId=1212410683682099946, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=69, endPage=80, ext={EN=ArticleExt(id=1212410690145526599, articleId=1212410687788327712, tenantId=1146029695717560320, journalId=1146031591421210625, language=EN, title=Current situation and development trend of by−product gas utilization in China's steel industry, columnId=1150494642224591153, journalTitle=Science & Technology Review, columnName=Exclusive, runingTitle=null, highlight=null, articleAbstract=

As the world's largest steel producer, China's steel industry generates over 1.4 trillion cubic meters of by−product gas annually, which contains energy equivalent to 266 million tons of standard coal. However, currently, the by−product gas from China's steel industry is mainly used as fuel for combustion, remaining at a stage with high carbon emissions and low comprehensive utilization rate. In view of this, to promote the improvement of the utilization efficiency of by−product gas in China's steel industry, this paper elaborates on the composition, calorific value and other characteristics and availability of three core by−product gases: blast furnace gas, coke oven gas and converter gas. It also analyzes the current utilization status and limitations mainly based on fuel combustion, and explores the high−value utilization pathways under the steel−chemical integration and hydrogen metallurgy approaches, including pressure swing adsorption (PSA) and chemical absorption for purifying CO/CO2, as well as biological fermentation of converter gas and reforming of coke oven gas to produce methanol/ethanol and hydrogen energy. It focuses on the application advantages and practices of coke oven gas in Midrex and Energiron−ZR direct reduction ironmaking. Research shows that by−product gas can be transformed from a single fuel to a chemical raw material through technological upgrades, such as reducing emissions by 10%~20% through high−pressure injection of coke oven gas into blast furnaces, and the feasibility of Baowu's HyCROFTM hydrogen−rich carbon cycle blast furnace technology has been verified. Based on this, it is concluded that the core directions for efficient and low−carbon utilization are steel−chemical integration and synergy, hydrogen metallurgy coupling, and the integration of CCUS technology, which can drive the industry to shift from "carbon metallurgy" to "hydrogen metallurgy" and provide technical support for the green and low−carbon transformation of the steel industry.

, authors=null, authorsList=Tian GAO, Peng SUI, Xingjian DENG, Jingsong WANG, Guang WANG, Xuefeng SHE, Haibin ZUO, Qingguo XUE, authorCompany=null, correspAuthors=Jingsong WANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=All rights reserved. Unauthorized reproduction is prohibited., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1212410695958831128, articleId=1212410687788327712, tenantId=1146029695717560320, journalId=1146031591421210625, language=CN, title=中国钢铁行业副产煤气利用现状和发展趋势, columnId=1150494642375586098, journalTitle=科技导报, columnName=特色专题, runingTitle=null, highlight=null, articleAbstract=

作为世界上第一大钢铁生产国,中国钢铁行业副产煤气年生产量总和超过14000亿Nm3,其蕴含的能量相当于2.66亿t标准煤。然而,目前中国钢铁行业副产煤气以作为燃料燃烧使用为主,仍处于碳排放较高、综合利用率较低的阶段。为促进中国钢铁行业副产煤气利用效率的提升,阐述了高炉煤气、焦炉煤气、转炉煤气3类核心副产煤气的成分、热值等特征及可用性,分析了以燃料燃烧为主的利用现状与局限,探讨了钢化联产、氢冶金路径下的高值化利用途径,含变压吸附法(PSA)、化学吸收法提纯CO/CO2,及转炉煤气生物发酵、焦炉煤气重整制甲醇/乙醇与氢能;重点论述了焦炉煤气在Midrex、Energiron−ZR直接还原炼铁中的应用优势及实践。研究表明,副产煤气经技术升级可从单一燃料转向化工原料,如焦炉煤气高炉喷吹减排10%~20%,中国宝武钢铁集团HyCROFTM富氢碳循环高炉技术验证了其可行性。据此总结出,钢化联产协同、氢冶金耦合、CCUS技术融合是其高效低碳利用核心方向,可推动行业从“碳冶金”转向“氢冶金”,为钢铁行业绿色低碳转型提供技术支撑。

, authors=

高天,硕士研究生,研究方向为煤气加热新技术,电子信箱:

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王静松(通信作者),研究员,研究方向为低碳冶金,电子信箱:
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CO/%H2/%CH4/%N2/%CO2/%O2/%密度/(kg/m³)热值/(MJ/m³)
25.0~30.01.5~3.00.2~0.555.0~60.015.0~19.00.2~0.41.29~1.303~3.8
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高炉煤气气体成分特征

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CO/%H2/%CH4/%N2/%CO2/%O2/%密度/(kg/m³)热值/(MJ/m³)
25.0~30.01.5~3.00.2~0.555.0~60.015.0~19.00.2~0.41.29~1.303~3.8
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CO/%H2/%CH4/%N2/%CO2/%O2/%密度/(kg/m³)热值/(MJ/m³)
60.0~70.00.0~3.00.0~1.010.0~20.015.0~20.00.0~2.01.69~1.766.8~10
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转炉煤气成分及特征

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CO/%H2/%CH4/%N2/%CO2/%O2/%密度/(kg/m³)热值/(MJ/m³)
60.0~70.00.0~3.00.0~1.010.0~20.015.0~20.00.0~2.01.69~1.766.8~10
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H2/%CH4/%CO/%N2/%CO2/%O2/%CmHn/%密度/(kg/m³)热值/(kJ/m³)
55.0~60.022.0~28.06.5~10.03.0~5.01.0~3.00.3~0.82.0~3.00.45~0.4817580~18420
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焦炉煤气成分及特征

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H2/%CH4/%CO/%N2/%CO2/%O2/%CmHn/%密度/(kg/m³)热值/(kJ/m³)
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中国钢铁行业副产煤气利用现状和发展趋势
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高天 1 , 隋鹏 2 , 邓行健 1 , 王静松 1, * , 王广 1 , 佘雪峰 1 , 左海滨 1 , 薛庆国 1
科技导报 | 特色专题 2025,43(21): 69-80
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科技导报 |特色专题 2025 , 43 (21) : 69 -80
中国钢铁行业副产煤气利用现状和发展趋势
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高天1 , 隋鹏2, 邓行健1, 王静松1, * , 王广1, 佘雪峰1, 左海滨1, 薛庆国1
作者信息
  • 1北京科技大学绿色低碳钢铁冶金全国重点实验室,北京 100083
  • 2中钢设备有限公司,北京 100080
通讯作者:
王静松(通信作者),研究员,研究方向为低碳冶金,电子信箱:
Current situation and development trend of by−product gas utilization in China's steel industry
Tian GAO1 , Peng SUI2, Xingjian DENG1, Jingsong WANG1, * , Guang WANG1, Xuefeng SHE1, Haibin ZUO1, Qingguo XUE1
Affiliations
  • 1National Key Laboratory of Green Mild Steel Iron Metallurgy, University of Science and Technology Beijing, Beijing 100083, China
  • 2Sinosteel Equipment & Engineering Co., Ltd., Beijing 100080, China
出版时间: 2025-11-13 doi: 10.3981/j.issn.1000-7857.2024.03.01088
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作为世界上第一大钢铁生产国,中国钢铁行业副产煤气年生产量总和超过14000亿Nm3,其蕴含的能量相当于2.66亿t标准煤。然而,目前中国钢铁行业副产煤气以作为燃料燃烧使用为主,仍处于碳排放较高、综合利用率较低的阶段。为促进中国钢铁行业副产煤气利用效率的提升,阐述了高炉煤气、焦炉煤气、转炉煤气3类核心副产煤气的成分、热值等特征及可用性,分析了以燃料燃烧为主的利用现状与局限,探讨了钢化联产、氢冶金路径下的高值化利用途径,含变压吸附法(PSA)、化学吸收法提纯CO/CO2,及转炉煤气生物发酵、焦炉煤气重整制甲醇/乙醇与氢能;重点论述了焦炉煤气在Midrex、Energiron−ZR直接还原炼铁中的应用优势及实践。研究表明,副产煤气经技术升级可从单一燃料转向化工原料,如焦炉煤气高炉喷吹减排10%~20%,中国宝武钢铁集团HyCROFTM富氢碳循环高炉技术验证了其可行性。据此总结出,钢化联产协同、氢冶金耦合、CCUS技术融合是其高效低碳利用核心方向,可推动行业从“碳冶金”转向“氢冶金”,为钢铁行业绿色低碳转型提供技术支撑。

高炉煤气  /  焦炉煤气  /  转炉煤气  /  钢化联产  /  氢冶金

As the world's largest steel producer, China's steel industry generates over 1.4 trillion cubic meters of by−product gas annually, which contains energy equivalent to 266 million tons of standard coal. However, currently, the by−product gas from China's steel industry is mainly used as fuel for combustion, remaining at a stage with high carbon emissions and low comprehensive utilization rate. In view of this, to promote the improvement of the utilization efficiency of by−product gas in China's steel industry, this paper elaborates on the composition, calorific value and other characteristics and availability of three core by−product gases: blast furnace gas, coke oven gas and converter gas. It also analyzes the current utilization status and limitations mainly based on fuel combustion, and explores the high−value utilization pathways under the steel−chemical integration and hydrogen metallurgy approaches, including pressure swing adsorption (PSA) and chemical absorption for purifying CO/CO2, as well as biological fermentation of converter gas and reforming of coke oven gas to produce methanol/ethanol and hydrogen energy. It focuses on the application advantages and practices of coke oven gas in Midrex and Energiron−ZR direct reduction ironmaking. Research shows that by−product gas can be transformed from a single fuel to a chemical raw material through technological upgrades, such as reducing emissions by 10%~20% through high−pressure injection of coke oven gas into blast furnaces, and the feasibility of Baowu's HyCROFTM hydrogen−rich carbon cycle blast furnace technology has been verified. Based on this, it is concluded that the core directions for efficient and low−carbon utilization are steel−chemical integration and synergy, hydrogen metallurgy coupling, and the integration of CCUS technology, which can drive the industry to shift from "carbon metallurgy" to "hydrogen metallurgy" and provide technical support for the green and low−carbon transformation of the steel industry.

blast furnace gas  /  coke oven gas  /  converter gas  /  steel−chemical co−production  /  hydrogen metallurgy
高天, 隋鹏, 邓行健, 王静松, 王广, 佘雪峰, 左海滨, 薛庆国. 中国钢铁行业副产煤气利用现状和发展趋势. 科技导报, 2025 , 43 (21) : 69 -80 . DOI: 10.3981/j.issn.1000-7857.2024.03.01088
Tian GAO, Peng SUI, Xingjian DENG, Jingsong WANG, Guang WANG, Xuefeng SHE, Haibin ZUO, Qingguo XUE. Current situation and development trend of by−product gas utilization in China's steel industry[J]. Science & Technology Review, 2025 , 43 (21) : 69 -80 . DOI: 10.3981/j.issn.1000-7857.2024.03.01088
现代工业发展与人口增长背景下,全球资源短缺、环境质量下降问题日益凸显,资源环保高效利用成为可持续发展核心议题。中国作为全球第一钢铁生产与消费大国,2023年粗钢产量10.19亿t、生铁产量8.71亿t,占世界总产量50%以上,在行业中具有重要影响力[1]。钢铁产能扩张伴随大量污染颗粒与温室气体排放,作为《巴黎协议》成员国,中国提出2030 年碳达峰、2060年碳中和的“双碳”目标[23],是践行可持续发展的重要举措。
当前中国钢铁长流程生产占主导,炼焦、高炉炼铁、转炉炼钢等流程能耗巨大。2023年中国钢铁协会会员企业吨钢综合能耗558.3 kgce/t,全行业总能耗超6.5亿t标准煤,占全国能耗12%;全国年碳排放量超120亿t,钢铁行业占比约16%,其CO2排放多与副产煤气逸散、燃烧利用相关[4]。为此,中国[56]、欧洲各国[711]、日本[12-13]、美国[14]及印度[15]等均在大力研发钢铁冶金低碳新技术。
中国粗钢生产能耗约23~25 GJ/t,其中14~16 GJ满足生产热化学能需求,7~10 GJ转化为副产煤气化学能(占总能耗 30%),加之生产过程中产生的废热,传统炼焦—高炉—转炉流程约70%总能源转化为副产煤气和余热等低品位二次能源。相较于欧美日韩企业,中国钢铁企业对这类二次能源的利用效率普遍偏低。
本研究聚焦焦炉煤气、转炉煤气、高炉煤气3类核心副产煤气,分析其性质与利用现状。目前多数钢铁企业将副产煤气用作加热燃料辅助生产,如每年约1/3高炉煤气(3000亿m3 以上)用于高炉热风炉加热,剩余部分主要用于加热与发电;中国独立焦化厂及大型钢铁联合企业年产冶金焦超4亿t,对应焦炉煤气约1600亿m3,其高氢特性可作为直接还原炼铁的优良还原剂。但煤气单纯作为燃料的利用方式综合效率低,在副产煤气基数巨大的背景下,研发高效利用技术对钢铁行业低碳转型具有重要意义。
高炉煤气为钢铁长流程工艺的典型副产物,据中国钢铁工业协会数据,2023年产量超 14000亿m3,吨铁产气量约1400~1500 m3,应用潜能显著。该气体无色无味、CO含量高且毒性强,主要成分为CO、CO2、N2、H2、CH4,热值3~3.8 MJ/m3,属低热值煤气,具体成分特征如表1所示,典型产生流程见图1
高炉煤气从炉顶逸出时压力约0.15 MPa,夹带60~80 g/m3的粉尘及挥发分,直接排放或循环利用均存在较大危害,需经除尘处理后方可满足后续使用需求[1617]。当前高炉煤气除尘以湿法除尘与干式除尘为主,其中干式除尘所得煤气具有含水量低、余热损失小、余压透平发电装置(TRT)发电量大等优势[1819]
据统计,2024年中国钢铁工业协会会员企业高炉煤气利用率达98%以上,但该数据未涵盖小型钢铁企业,这类企业因技术能力不足,8%~12%的高炉煤气直接排空或放散燃烧。高炉煤气主要用作气体燃料,应用于高炉热风炉、炼焦炉、铁矿石球团焙烧等场景[20],其中热风炉加热为核心应用,消耗占年产量33%左右。该方式成本低、适用性强,但存在综合燃烧效率低、烟气排放量大等问题[2123],企业多采用富氧燃烧技术改善其燃烧效率与温度偏低的问题[2426]。实际生产证实,当助燃气体氧气含量>20.9%时,可降低高炉煤气燃点、提升燃烧温度与效率。
高炉煤气发电主要包括余压发电与燃烧发电两类。余压发电借助煤气自身压力推动透平膨胀机带动发电机发电,属二次能源回收工艺[27]。结合干式除尘技术(煤气含水量低、余热余压损失小),与余压发电机组配合可实现能源优化利用,理想状态下,TRT机组发电量可达50 kWh/t生铁以上,能源利用率显著提升[2829]。燃烧发电分为蒸汽轮机发电与燃气蒸汽联合循环发电(CCPP):蒸汽轮机发电技术成熟、成本低廉,自1903年GE公司(美国通用电气公司)建成5000 kW蒸汽涡轮发电站后持续发展,但能量转化效率偏低,即便发展至超临界煤气发电阶段,最高效率也仅40%左右[3031];20世纪50年代发展的CCPP技术,通过高温燃气膨胀与蒸汽推动协同做功,发电效率高于蒸汽轮机,已逐步成为高炉煤气发电的首选技术[3233]
转炉煤气产自转炉吹氧炼钢流程,喷吹氧气与铁水中的碳剧烈反应生成CO、CO2等气体,经收集处理后获得[3435]。其气体组成及含量如表2所示,N2含量低,CO等可燃成分占比远高于高炉煤气,热值6800~10 MJ/m3,属中等热值气体,利用价值更高。转炉煤气回收量约90~110 m3/t钢,最高超140 m3/t钢[36],2023年中国年产量达900亿m3以上。
目前,中国转炉煤气主要直接用作炼钢流程燃料,如钢包烘烤、合金烘烤、混铁炉保温、连铸中间包烘烤等[3738],部分用于轧钢加热炉、石灰窑燃烧,或与高炉煤气混合用于CCPP发电。将其用于CO/CO2高值转化(如CO富集提纯、合成甲醇乙醇),是当下的研究重点。
转炉煤气出炉温度高达1450~1500℃,夹带大量氧化铁粉尘,需经降温、除尘后方可使用,其除尘原理与高炉煤气一致,现代企业多采用干式除尘以最大化回收显热。高温显热利用除加热水蒸气发电、原料烘干等传统方式外,热化学储能(显热转化学能)为新研究方向。Ren等[3941]采用转炉煤气与焦炉煤气混合重整技术,利用转炉煤气高温余热将CO2和CH4转化为CO和H2,重整过程中35%~40%余热转化为化学能,总热量回收率达60%~65%,远高于传统回收效率(25%~37%),能量转换及效率对比如图2所示。
焦炉煤气源于焦炭生产过程,是3类副产煤气中含氢量最高的品种。由于短时间内高炉炼铁工艺仍占主导地位,焦炉煤气产量将持续维持高位。2023年中国焦炭产量达4.92亿t,对应焦炉煤气总量约1970亿m3。其主要成分为CH4、H2、CO、CO2表3),其中 H2占比55%~60%、CH4占比22%~28%,属高热值煤气,热值约17~18 MJ/m3[42]
目前,焦炉煤气主要用作钢铁企业内部燃料[43],凭借高热值常掺混其他煤气以弥补低热值煤气的燃烧温度不足,如用于球团带式焙烧机及CCPP发电等。但该利用方式未能充分发挥其高氢、高CH4特性,因此发展纯氢、甲醇、氨、天然气等高值产品生产,是当下研究重点与资源高效利用的必然要求。
对比焦炉煤气发电,将焦炉煤气用于高炉喷吹,性价比更高。由于焦炉煤气氢含量高,具有以下4方面优势[4446]:(1) 焦炉煤气中的氢为优质还原剂,可替代焦炭中的碳以达到节约焦炭目的;(2) 焦炉煤气中氢气还原产物为H2O,与其他还原剂相比,CO2排放量低,其综合减排效果为10%~20%;(3) 与用于发电相比,焦炉煤气能量利用率提高约80%,总能量利用效率得到提高;(4) 焦炉煤气高炉喷吹技术已成熟,生产设备投资较小。
自20世纪60年代起,鞍钢集团有限公司、承德钢铁集团有限公司、济钢集团有限公司等企业已开展实践并积累经验,后因经济、工艺等因素未深入推广。近年在“双碳”与可持续发展背景下,该工艺重新受重视,焦炉煤气也成为富氢高炉的低碳能源。
副产煤气高值利用打破钢铁与化工行业独立发展格局,是钢化联产的核心发展方向,目前已有国内外大量研究基础[4748]。郭占成等[4951]对钢铁−化−电−建材多联产、烟气净化联产等进行理论分析与模拟,张琦、郭玉华等[5254]开展相关研究并评估联产系统减排效果。
研究表明,通过耦合钢−化−电过程,充分利用副产煤气热能(发电、原料加热),净化后经提纯或化学合成制得氢气、甲醇等化工产品,可显著提高能量与资源利用率,为钢铁企业多元化转型提供支撑。
高炉煤气含20%左右CO2与55%~60% N2,燃烧时未参与反应的2类气体将以烟气形式带走大量热量,造成无效能量损失。因此,CO提纯与CO2脱除对高炉煤气增值利用具有重要意义,提纯后的CO、CO2小分子含碳气体,可作为化工原料生产甲醇、乙醇、醋酸等高值产品。高炉煤气CO提纯已成为中国钢铁企业的重要发展方向之一,相关流程简图如图3所示。
近年高炉煤气CO提纯以吸附法为主流,常用类型包括变压吸附法(PSA)、变温吸附法(TSA)及真空吸附法(VSA)。该工艺通过CO选择性吸附剂分离气体,且吸附可逆便于后续CO收集,兼具操作简单、无腐蚀、易调控等优点。其中TSA法因温度调控缓慢导致能耗较高,PSA法应用更为广泛。
PSA提纯CO的核心挑战是研发高性能、可逆再生、低成本的吸附材料。北京北大先锋科技股份有限公司(简称北大先锋)研发的Cu系吸附材料PU−1,CO实验纯度达90%以上;2013年6月,其设计的中国首个高炉煤气CO变压吸附工程在湖南衡阳钢管有限公司(简称衡钢)投产,煤气处理量67000 Nm3/h,CO产品浓度超70%,年回收量折合标准煤约38000 t[55]。该技术经济可行性良好,提纯后CO热值高于原煤气且可用于化工生产[56],但目前衡钢等企业出于经济性考虑,仍将其用作加热燃料以减少外购天然气消耗。
分离高炉煤气中CO2可提升其热值与利用效率、拓展应用场景,当前主流方法为化学吸收法,企业重点关注设备投资与运行成本。此外,脱除CO2后的高炉煤气可循环入炉,减少焦炭消耗与燃料比;宝武集团开发的富氢碳循环高炉炼铁技术(HyCROFTM),采用氧气鼓风,炉顶煤气脱除CO2后加热喷吹入炉循环利用,是当前高炉煤气最高效的利用方式之一。
高炉煤气CO2脱除以化学吸收法应用较广,主要包括胺法吸收与热钾碱法。
胺法吸收在部分钢铁企业得到应用,通过胺类溶剂与CO2的可逆化学反应实现吸收,加热后可解吸CO2并再生溶剂。该方法吸收效率高、技术成熟,适用于大规模煤气处理,但胺类溶剂存在腐蚀性,需强化设备选型与维护,且再生过程消耗能量,增加企业能源成本。
热钾碱法采用碳酸钾溶液吸收CO2,辅以催化剂提升吸收速率,适用于高浓度CO2脱除,成本较低可降低环保投入。但该方法再生温度高,对设备耐高温、耐腐蚀性能要求严格,需配套专用设备保障脱除过程稳定运行。
转炉煤气CO含量达60%~70%,富集提纯高品位CO后,可用于合成醋酸、醋酐、乙二醇等化工产品,或经光气合成制备TDI(甲苯二异氰酸酯)、MDI(二苯基甲烷二异氰酸酯)等。该技术突破传统煤化工煤制气前置限制,是转炉煤气燃烧发电之外的重要应用方向,其富集原理与高炉煤气成分富集基本一致,工业上以深冷分离法和PSA−CO法为主,典型 PSA−CO富集生产流程如图4所示。
转炉煤气PSA−CO提纯CO技术工业化始于日本,1989年日本神户制钢(KOBELCO)在加古川厂建成工业系统,1990年于神户复建同类系统[57]。其CO生产速率达150~200 m3/h,纯度超99%,实现了资源高值利用。随着PSA高性能吸附材料的发展,气体富集纯度普遍达90%以上,目前日本、韩国及欧美发达国家已将技术重点转向工艺模型优化。
中国因转炉煤气内部消耗量大、PSA−CO系统投资较高,该技术工业应用起步较晚,仅宝山钢铁股份有限公司、首钢集团有限公司、河钢股份有限公司等少数大型钢铁企业应用,其他企业受经济性制约,仍将转炉煤气直接用作燃料。
转炉煤气CO及CO2含量高,是制备甲醇、乙醇的优质原料,替代煤原料可降低能耗并补充产品产量缺口,同时可作为焦炉煤气制甲醇的补碳剂,调节其偏高的氢碳比[58]
转炉煤气制乙醇是近年重要利用方向,其中新西兰Lanza tech公司(LanzaTech New Zealand Limited)的合成气发酵法应用较广。相较于粮食(一代)、纤维素(二代)原料,该方法可减少生物质消耗、降低转炉煤气放散率,其简易工艺流程如图5所示。
转炉煤气发酵法生产乙醇,借助新西兰Lanza tech公司提供的特定微生物菌种以生物代谢方式消耗CO、H2等气体原料,进而可生产出乙醇、乙酸盐和其他产物。在此过程中CO、CO2等无机碳化物转变为有机碳化物,完成碳的生物固定和增值过程。图6为CO通过生物+Wood−Ljungdahl途径生成乙醇过程[59]。借助生物学理论表征,微生物生产代谢过程为
$ \mathrm{6CO+3H}_{ \mathrm{2}} \mathrm{O}\to{\mathrm{C}}_{ \mathrm{2}} \mathrm{H}_{ \mathrm{5}} \mathrm{OH+4CO}_{ \mathrm{2}} $
$ \mathrm{2CO+6H}_{ \mathrm{2}}\to \mathrm{C}_{ \mathrm{2}} \mathrm{H}_{ \mathrm{5}} \mathrm{OH+3H}_{ \mathrm{2}} \mathrm{O} $
反应方程式中,CO2为中间产物,随后与反应中的甲基结合,在生物酶作用下与CO结合为乙酰辅酶A,具体代谢过程机理及工艺过程见参考文献[5965]。
生物法固定回收CO兼具绿色环保特性,2010年起,中国部分大型钢铁企业已逐步应用生物发酵制乙醇技术。乙醇掺混汽车燃料的发展推动市场需求增长,成为钢铁企业利用副产煤气转型生产乙醇的重要动因。此外,中国与Lanza tech合资成立新能源科技公司,依托国内副产煤气资源优势,进一步推动该发酵技术的研发与应用。
氢能作为21世纪极具潜力的二次能源,具备绿色清洁、转化效率高、无温室气体排放等优势。中国当前煤制氢占比超60%,行业能耗偏高,而焦炉煤气(COG)含55%~60% H2与22%~28% CH4,氢含量丰富,制氢潜力显著。工业上以PSA为主要制氢技术,工艺流程如图7[66]所示。
21世纪初,新日本钢铁公司(简称新日铁)已开展焦炉煤气制氢技术研发,先后开发深冷分离法与PSA法,同期美国钢铁及炼焦企业也发展同类技术,所产氢气主要供燃料电池使用。中国宝钢、武钢、鞍钢、邯钢、首钢京唐等企业均已建成焦炉煤气PSA制氢装置,成本较电解水制氢降低2/3以上[6769]。需注意的是,未处理焦炉煤气含硫化物、油、萘等有害杂质,PSA制氢前须经净化处理,避免损耗吸附剂性能与寿命。
膜分离技术富集焦炉煤气中H2是当前研究热点,理论上具有能耗更低、环保性更佳的优势,借助无机或有机微孔材料的分子筛机制可获得富H2气流。目前国外膜分离技术已趋于成熟,已开发PRISM、ALaS、GENERON、Polysep等商业富氢膜,其提纯H2流程如图8[66]所示。
为充分挖掘焦炉煤气氢资源潜力,研究人员提出重整富氢再分离方法[7071]。该方法通过催化重整反应(如水煤气反应)将焦炉煤气中CH4、焦油等转化为富氢气体,提升氢资源回收率,其中利用外部CO2与焦炉煤气进行CH4干重整(DRM)制氢是当前研究热点。尽管该技术理论可行,但受催化剂、成本、能耗等因素制约。综合来看,中国钢铁企业应基于现有技术,推动焦炉煤气制氢与氢冶金或氢能商业应用相结合,构建现阶段低碳发展模式。
焦炉煤气含22%~28% CH4与7%~13% CO,净化后可用于生产天然气(主要成分为CH4),制取方法分为直接分离法(物理法)与甲烷化分离法(化学法)。原料气净化要求严格,尤其甲烷化工艺需脱硫至10−7级别,避免催化剂中毒失活。
直接分离法无CH4化学转化过程,预处理后可采用深冷分离、膜分离、PSA等方法提纯;甲烷化分离法可利用CO成分,通过催化剂实现CO+H2→CH4转化,提升甲烷回收率,分为补碳法(借助外部CO碳源如高炉煤气)与不补碳法(利用自身CO成分,简化流程并减少排放)。
焦炉煤气氢碳比偏高,直接用于甲醇合成难以充分利用,需借助高炉煤气或转炉煤气作为补碳剂调节氢碳比[72]
焦炉煤气制甲醇工艺流程包括预处理、压缩、精脱硫、转化、合成气压缩、低压合成、精馏存储及尾气处理等工序。甲醇合成的最佳氢碳比为2,因实际反应存在不完全转化,且为强化固碳效果,生产中氢碳比通常控制在2.05~2.15。净化后的焦炉煤气含较多CH4,而 CH4无法直接合成甲醇,需经重整转化为CO、CO2、H2等物质。当前甲烷干重整技术备受关注,通过消耗CO2生成目标产物,可直接获得氢碳比约2的合成气,减少氢碳比调节环节,且干重整消耗的CO2可视为甲醇使用过程中CO2的循环捕捉利用(图9[73])。目前国内钢铁企业中,采用高炉煤气或转炉煤气调节氢碳比仍是最可行的方案。
2022年3月《Nature》的News Feature专题讨论各类减碳举措[74],并报道中国河南省铜冶镇将建成全球最大焦炉煤气与CO2回收制甲醇设施,其CO2回收量约16万t/a,成为中国清洁生产领域的重要里程碑。该案例虽独立于钢铁企业,但可为行业内焦炉煤气应用提供参考,尤其未来高炉煤气、转炉煤气另有他用时,钢铁企业可考虑引入外部CO2源开展同类工艺。该工艺能将CO2以燃料形式短期封存,降低大气中CO2含量,即便合成燃料使用后仍会释放CO2,仍对中国“双碳”目标达成及全球气候变化减缓具有积极意义。
“双碳”背景下,传统“碳冶金”体系正向“氢冶金”转型,这是冶金行业大规模减碳的关键突破点。焦炉煤气氢含量超70%,是优质氢源,其在冶金企业内部利用可减少天然气外购、降低生产成本,具备显著经济性。
焦炉煤气用于直接还原铁(DRI)生产是近几十年的重要发展方向,伴随直接还原炼铁技术同步拓展。截至2021年,全球DRI产量超1.1亿t,主流技术为Midrex和Energiron,其中Midrex工艺产量占比超60%[75]
Midrex工艺由美国表面燃烧公司开发,1984年被日本神户制钢收购,1967年建成试点工厂,目前已在印度、伊朗、俄罗斯等多国应用[7677]。该工艺适配煤化工合成气、焦炉煤气等多元还原气体,神户制钢与普莱克斯有限公司合作开发焦炉煤气重整技术,将CH4、焦油转化为还原性气体,形成无烟示范流程并在中国、印度等地商业推广。
Energiron−ZR工艺为竖炉原位重整工艺,还原性气体在竖炉内完成加热、重整、反应等过程。焦炉煤气虽与天然气成分差异较大,但用于该工艺的冶金反应效果一致,且经济效益优于单纯发电。该工艺中CO2与CH4重整生成CO+H2还原性气体参与铁矿石还原,配合尾气处理装置,在能耗、环保及经济效益上均优于高炉炼铁[7880],其通用示意如图10[81]所示。
中国中晋太行矿业有限公司已建成30万t直接还原竖炉装置,以焦炉煤气为还原气,但开工后未再有后续报道。河钢集团55万t Energiron−ZR装置已投产,宝钢湛江钢铁有限公司100万t Energiron−ZR装置将于2023年底投产[8283],2套装置均采用焦炉煤气作为还原气以减少CO2排放。该类直接还原炼铁工艺的CO2减排成效,成为中国钢铁行业低碳发展的里程碑。
CO2利用主要包括捕获与封存(CCS)和捕获与利用(CCU)2大方向[84]。CCS技术通过将捕集的CO2永久储存于地下或海洋以减排,中国分为陆地(咸水层、驱油封存)与海上(水柱、沉积物封存)2类技术[8588],海上封存因地质条件优势具较大潜力;CCU技术则通过物理、化学或生物作用将CO2转化为甲烷、甲醇等产品或实现资源增采,兼具减排与经济效益[8991]。当前中国钢铁企业已开展多元实践。
中国宝武钢铁集团有限公司通过钢渣捕碳技术低成本捕集烟气CO2并转化为低碳水泥胶凝材料,同时以CO2替代氩气炼钢,实现内部循环利用[9293];鞍山钢铁集团有限公司首发690 MPa级CO2运输船液货舱用低温钢,填补液化CO2存储材料国际空白[94];首钢集团有限公司以尾气生物发酵法实现燃料乙醇商业化生产,配套CO2−O2混合喷吹及“水电共生”技术拓展利用路径[95];河北钢铁集团有限公司建成千吨级CCUS示范项目,贯通CO2制菌体蛋白路线,其120万t氢冶金示范工程实现源头减排[96];泰山钢铁集团联合研发顶底复吹CO2冶炼不锈钢技术并完成工业试验[97];包钢集团拟建200万t CO2捕集与封存利用基地[98];宝钢股份参与华东千万吨级CCUS项目,同步推进富氢碳循环氧气高炉示范,目标年减排CO2近60万t[99]。这些技术涵盖材料研发、工艺改进及跨行业合作,彰显了中国钢铁企业低碳转型的积极探索。
1) 高炉煤气产量大、应用潜能显著,国内主要用作气体燃料,部分小型企业因能力不足直接排空或放散燃烧,存在燃烧效率低、烟气排放量大等问题,少量用于余压发电及燃烧发电。高炉煤气利用需聚焦燃烧效率提升与CO2减排,CCPP技术发电效率优于蒸汽轮机,应作为发电首选;CO2脱除技术可拓展其利用空间,宝武集团富氢碳循环高炉炼铁技术(HyCROFTM)采用全氧鼓风、炉顶煤气脱碳后循环喷吹,是当前高效利用方式之一。
2) 转炉煤气CO含量高、热能资源丰富,其CO与热能的高效回收利用至关重要。国内因内部消耗量大、化工利用技术起步晚,多数企业仅将其直接用作炼钢流程燃料,而日本、韩国及欧美、新西兰等国已广泛应用于化工生产。国内钢铁企业需优化转炉煤气回收利用流程,实现热能—化学能逐级高效利用;采用热化学重整储能方式对转炉煤气与焦炉煤气进行混合重整,是提升热能回收效率、减少CO2排放的关键途径。
3) 焦炉煤气富含H2与CH4,是钢铁及化工行业重要原料气,国内主要用于企业内部燃料消耗,未能充分发挥其成分优势。国内多家企业已开展高炉喷吹焦炉煤气实践并积累经验,“双碳”与可持续发展背景下,其已成为富氢高炉低碳能源。因此,发展焦炉煤气用于直接还原炼铁生产,以及生产纯氢、甲醇、氨、天然气等高值产品,既是当下研究重点,也是资源高效利用的必然要求。
  • 中国宝武低碳冶金创新基金项目(BWLCF202104)
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2025年第43卷第21期
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doi: 10.3981/j.issn.1000-7857.2024.03.01088
  • 接收时间:2024-03-06
  • 首发时间:2025-12-29
  • 出版时间:2025-11-13
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  • 收稿日期:2024-03-06
  • 修回日期:2024-09-27
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中国宝武低碳冶金创新基金项目(BWLCF202104)
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    1北京科技大学绿色低碳钢铁冶金全国重点实验室,北京 100083
    2中钢设备有限公司,北京 100080

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2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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