钢铁渣中有价元素回收及其综合应用研究进展

基金项目

甘肃省自然科学基金26JRRA527);

全国大学生创新创业训练计划DC20250398DC20250034

中图分类号:

TF813TF804.2

文献标识码:

A

作者简介

肖明军(1992―),男,甘肃定西人,博士,副教授,研究方向:原位TEM、离子电池、光电催化、电解冶金、第一性原理计算、二次资源高值化利用等,E-mail:xiaomj@lut.edu.cn

通信作者

常海涛,正高级工程师,E-mail:haitao.chang@nanfu.com

流转信息

收稿日期 : 2026-05-06

修订日期 : 2026-07-10

引文格式

肖明军,卢熖忠,常海涛. 钢铁渣中有价元素回收及其综合应用研究进展[J]. 铜业工程,2026(4):104-117.

Research Progress on Recovery of Valuable Elements from Steel Slag and Its Comprehensive Application

Citations

Xiao Mingjun,Lu Yanzhong,Chang Haitao. Research progress on recovery of valuable elements from steel slag and its comprehensive application [J]. Copper Engineering,2026(4):104-117.

    第4期    104-117
doi10.3969/j.issn.1009-3842.2026.04.013
矿治固废资源综合利用与污染防治专题(Special Topic: Utilization of Mining and Metallurgical Solid Waste and Pollution Control)

钢铁渣中有价元素回收及其综合应用研究进展

  • 肖明军 1,2
  • 卢熖忠 2
  • 常海涛 2
1.兰州理工大学 冶金与环境学院 省部共建有色金属先进加工与再利用国家重点实验室甘肃 兰州 730050
2.南孚电池有限公司 福建省高效能电池重点实验室福建 南平 353000

作者简介

肖明军(1992―),男,甘肃定西人,博士,副教授,研究方向:原位TEM、离子电池、光电催化、电解冶金、第一性原理计算、二次资源高值化利用等,E-mail:xiaomj@lut.edu.cn

通信作者

常海涛,正高级工程师,E-mail:haitao.chang@nanfu.com

基金项目

甘肃省自然科学基金26JRRA527);

全国大学生创新创业训练计划DC20250398DC20250034

中图分类号:

TF813TF804.2

文献标识码:

A

流转信息

收稿日期 : 2026-05-06     修订日期 : 2026-07-10     

引文格式

肖明军,卢熖忠,常海涛. 钢铁渣中有价元素回收及其综合应用研究进展[J]. 铜业工程,2026(4):104-117.

摘要

钢铁工业是国民经济的支柱产业,但其生产过程伴随着巨量固体废弃物产生,其中钢铁渣是最主要的副产品。长期以来,钢铁渣的堆存和填埋不仅侵占大量土地资源,其渗滤液中的重金属离子及粉尘飘散更对土壤、水体及大气构成潜在威胁。然而,钢铁渣并非废料,而是一种亟待开发的二次资源,它富含钙、硅、铁、铝、镁等主要有价元素以及钒、钛、锰等有价金属元素。从矿物学角度看,其主要物相包括硅酸二钙、硅酸三钙及铁酸钙等。这些特性决定了钢铁渣的资源化潜力:一方面,通过磁选、重选或还原焙烧等技术,可回收其中的铁元素及稀有金属;另一方面,高钙硅含量使其具备替代天然矿产资源的潜力。实现钢铁渣中有价元素的高效回收与全组分的综合应用,对于推动钢铁工业的绿色循环低碳发展至关重要。本文系统梳理了钢铁渣的物理化学特性,重点阐述了从钢铁渣中回收铁、钙、硅等主要有价元素以及钒、钛等稀有金属的技术原理与研究进展;同时,全面梳理了钢铁渣在建材、环境修复、农业等领域的综合应用研究现状;最后,分析了当前技术面临的挑战,并对未来研究方向进行了展望,以期为钢铁渣的高附加值资源化利用提供理论参考和技术思路。

关键词

钢铁渣;有价元素回收;资源化利用;建筑材料;环境材料;

Research Progress on Recovery of Valuable Elements from Steel Slag and Its Comprehensive Application

  • Xiao Mingjun 1,2
  • Lu Yanzhong 2
  • Chang Haitao 2
1.State Key Laboratory of Advanced Processing and Recycling of Nonferrous MetalsSchool of Metallurgy and EnvironmentLanzhou University of TechnologyLanzhou 730050China
2.Fujian Key Laboratory of High-efficiency BatteryNanfu Battery Co.,Ltd.Nanping 353000China

Citations

Xiao Mingjun,Lu Yanzhong,Chang Haitao. Research progress on recovery of valuable elements from steel slag and its comprehensive application [J]. Copper Engineering,2026(4):104-117.

Abstract

The iron and steel industry is a cornerstone of the national economy, yet its production process generates a massive amount of solid waste, among which iron and steel slag is the primary by-product. For a long time, the stockpiling and landfilling of this slag have not only occupied vast land resources but also posed potential threats to the soil, water, and atmosphere due to heavy metal ions in leachate and dispersion of dust. However, steel slag is a secondary resource awaiting development, which is rich in valuable elements such as calcium, silicon, iron, aluminum, magnesium, and manganese, as well as rare metals like vanadium and titanium. Main phases of steel slag include dicalcium silicate, tricalcium silicate, and calcium ferrite. Resourcezation potential of steel slag comes from two aspects. On one hand, technologies such as magnetic separation, gravity separation, or reduction roasting can recover iron and rare metals. On the other hand, high calcium and silicon content endows it with the potential to substitute for natural mineral resources. Achieving efficient recovery of valuable elements from steel slag and comprehensive application of the overall material is crucial for promoting green, circular, and low-carbon development of the iron and steel industry. This review systematically summarized physicochemical properties of steel slag, focusing on technical principles and research progress in recovering major valuable elements like iron, calcium, and silicon, as well as rare elements such as vanadium and titanium. Simultaneously, it comprehensively outlined current status of steel slag utilization in fields such as building materials, environmental remediation, and agriculture. Finally, it analyzed current technological challenges and provided an outlook on future research directions, offering a theoretical reference and technological pathways for high value resources utilization of steel slag.

Keywords

steel slag;recovery of valuable element;resources utilization;building materials;environmental material;



钢铁工业是现代工业文明的基石,然而其高能耗、高排放的特性也使其成为重要的污染源  Liu Z D,Liu H J,Liu F Y,et al. Selective recovery of valuable phosphorus in phosphate iron slag by sodium salt roasting-water leaching procedure[J]. Separation and Purification Technology,2026,382:135718.
 Duan W J,Dong X Y,Gao L H,et al. Chemical utilization of slag waste heat for carbon emission reduction in the iron and steel industry[J]. Journal of Environmental Chemical Engineering,2025,13(4):117224.
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1-3
。据世界钢铁协会统计,2022年全球粗钢产量达到18.85亿吨,每生产1 t粗钢约产生0.11~0.25 t钢渣和0.20~0.60 t高炉矿渣  Gu W F,Diao J,Tao H R,et al. Effects of cooling methods on phase evolution,microstructure,and stability of steelmaking slag[J]. Metallurgical and Materials Transactions B,2025,56(4):3970-3979.
 Zhou Y F,Zhou G W,Fang L,et al. A novel resource utilization strategy for pelletized flue gas desulfurization ash from the steel industry:synergistic application with slaked lime in sintering flue gas desulfurization[J]. Journal of Environmental Chemical Engineering,2025,13(6):119816.
4-5
。综合估算,全球每年产生的钢铁渣总量超过10亿吨。中国作为世界第一钢铁生产大国,钢铁渣的年产生量已超过4亿吨,历史堆存量更是高达数十亿吨  He D F,Yang L,Luo Y B,et al. Synergistic calcium leaching and iron enrichment by indirect carbonation of thermally modified steel slag[J]. Construction and Building Materials,2024,411:134249.
 韦响,李源,蔡敏. 钢铁渣综合利用述评[J]. 山西冶金,2011,34(4):4-6.
6-7

传统的钢铁渣处理方式以堆存和低附加值填埋为主,这不仅侵占宝贵的土地资源,其中的重金属离子在雨水淋溶下可能溶出并渗入土壤和地下水,造成环境污染  Chen J,Xing Y,Wang Y,et al. Application of iron and steel slags in mitigating greenhouse gas emissions:a review[J]. Science of the Total Environment,2022,844:157041.
 Xi B D,Li R F,Zhao X Y,et al. Constraints and opportunities for the recycling of growing ferronickel slag in China[J]. Resources,Conservation and Recycling,2018,139:15-16.
8-9
。同时,堆存渣中的碱性物质的水解产物也易造成周边土壤盐碱化  Li X L,Zhou M,Chen F Y,et al. Clean stepwise extraction of valuable components from electrolytic manganese residue via reducing leaching-roasting[J]. ACS Sustainable Chemistry & Engineering,2021,9(24):8069-8079.
10
。面对日益严峻的资源环境约束,将钢铁渣视为放错地方的资源,实现其全组分、高附加值的资源化利用,已成为全球钢铁行业和学术界关注的焦点  Zhang X L,Chen J X,Jiang J J,et al. The potential utilization of slag generated from iron-and steelmaking industries:a review[J]. Environmental Geochemistry and Health,2020,42(5):1321-1334.
 Chandel S S,Singh P K,Katiyar P K,et al. A review on environmental concerns and technological innovations for the valorization of steel industry slag[J]. Mining,Metallurgy & Exploration,2023,40(6):2059-2086.
 Bejarano-Peña W D,Alcántar-Vázquez B,Ramírez-Zamora R M. Synthesis and evaluation in the CO2 capture process of potassium-modified lithium silicates produced from steel metallurgical slags[J]. Materials Research Bulletin,2021,141:111353.
11-13

近年来,国内外围绕钢铁渣资源化利用开展了大量研究,形成了若干热点方向:一是有价金属绿色提取,含钒钢渣提钒从传统钠化焙烧向钙化焙烧、直接酸浸及生物浸出等低排放工艺演进  Sahu N,Biswas A,Kapure G U. A short review on utilization of ferrochromium slag[J]. Mineral Processing and Extractive Metallurgy Review,2016,37(4):211-219.
 Fan C L,Wei R F,Cheng T,et al. The positive contributions of steel slag in reducing carbon dioxide emissions in the steel industry:waste heat recovery,carbon sequestration,and resource utilization[J]. Chemical Engineering Journal,2024,498:155379.
 Alcántar-Vázquez B C,Ramírez-Zamora R M. Lithium silicates synthetized from iron and steel slags as high temperature CO2 adsorbent materials[J]. Adsorption,2020,26(5):687-699.
 李志强. 钢棚-钢筋混凝土联合支护技术在铜矿斜井工程中的应用[J]. 铜业工程,2026(2):131-140.
14-17
;二是CO2矿化固定,利用钢铁渣的碱性组分捕集工业烟气中的CO2,同时改善其体积安定性  Liu C Y,Yang J P,Du C M,et al. Enhancing the dissolution of spent MgO-C refractory in steelmaking slag:towards utilization as a steelmaking flux[J]. Journal of Sustainable Metallurgy,2024,10(3):1608-1620.
18
;三是高值化建材开发,从传统水泥掺合料向微晶玻璃、陶瓷、3D打印材料等领域延伸  Han F H,Zhang H B,Li Y C,et al. Recycling and comprehensive utilization of ferronickel slag in concrete[J]. Journal of Cleaner Production,2023,414:137633.
19
。然而,现有研究仍存在明显的系统性缺陷:多数工作聚焦于单一元素回收或单一领域应用,对铁、钙、硅、钒、钛等多元素的梯级回收与全组分协同利用缺乏系统集成方案  Bildstein O,Claret F,Frugier P. RTM for waste repositories[J]. Reviews in Mineralogy and Geochemistry,2019,85(1):419-457.
20
;在技术评价层面,往往侧重于实验室层面的回收效率,对工艺能耗、药剂消耗、二次污染处理成本及工程放大可行性关注不足,导致大量技术止步于“论文可行、产业难行”的困境  Reddy K R,Gopakumar A,Chetri J K. Critical review of applications of iron and steel slags for carbon sequestration and environmental remediation[J]. Reviews in Environmental Science and Bio/Technology,2019,18(1):127-152.
21

钢铁渣资源化产业化落地面临三大核心技术瓶颈:1)体积安定性差。钢铁渣中游离CaO(f-CaO)和游离MgO(f-MgO)水化滞后引发的延迟膨胀,是其在建材领域规模化应用的首要障碍,现有陈化、热闷、碳酸化等稳定化技术的处理周期、成本与效果难以兼顾  Liu T,Duan X Q,Lu S Y,et al. Mineral phase reconstruction mechanism of forsterite refractory prepared from ferronickel slag[J]. Construction and Building Materials,2025,464:140191.
22
;2)成分波动性大。钢铁渣CaO、Fe2O3、MgO含量波动幅度可达±50%,严重制约钢铁渣基终端产品的品质均一性,亟须发展在线检测与智能配矿技术  Singh N,Singh A,Ankur N,et al. Reviewing the properties of recycled concrete aggregates and iron slag in concrete[J]. Journal of Building Engineering,2022,60:105150.
23
;3)多元素协同提取效率低。钒、钛等有价金属在钢铁渣中赋存形态复杂、分散度高,现有工艺回收率偏低,酸耗巨大,距经济性回收仍有较大差距  Chi L,Lu S,Li Z M,et al. Recycling of ferronickel slag tailing in cementitious materials:activation and performance[J]. Science of the Total Environment,2023,861:160706.
24

本文旨在系统梳理近年来钢铁渣资源化利用的研究进展,重点关注铁、钙、硅、钒、钛等有价元素的高效回收与综合利用路径;通过剖析火法富集、湿法浸出、生物冶金等主流技术,对比了其在回收效率、能耗与环境影响方面的优劣。同时,聚焦钢铁渣在建材化应用与环境修复等新兴领域的技术突破,并结合全球循环经济发展趋势,进一步探讨当前资源化技术面临的瓶颈与转型升级方向,为我国钢铁工业固废的零废弃管理与资源闭环提供理论支撑与实践路径,助力行业绿色转型与“碳中和”目标的实现。

1     钢铁渣的分类与基本特性

1.1     钢铁渣的分类

冶金废渣形貌如图1所示。根据冶炼工艺和炉型的不同,钢铁渣可分为高炉矿渣和钢渣两大类  Acharya P K,Patro S K. Utilization of ferrochrome wastes such as ferrochrome ash and ferrochrome slag in concrete manufacturing[J]. Waste Management & Research:the Journal for a Sustainable Circular Economy,2016,34(8):764-774.
 Mombelli D,Mapelli C,Barella S,et al. Characterization of cast iron and slag produced by red muds reduction via Arc Transferred Plasma (ATP) reactor under different smelting conditions[J]. Journal of Environmental Chemical Engineering,2020,8(5):104293.
 Das P,Upadhyay S,Dubey S,et al. Waste to wealth:Recovery of value-added products from steel slag[J]. Journal of Environmental Chemical Engineering,2021,9(4):105640.
25-27

图1     冶金废渣的SEM图像
Fig. 1     SEM image of metallurgical waste residue  Alcántar-Vázquez B C,Ramírez-Zamora R M. Lithium silicates synthetized from iron and steel slags as high temperature CO2 adsorbent materials[J]. Adsorption,2020,26(5):687-699.
16

高炉矿渣是在高炉炼铁过程中,由铁矿石中的脉石、燃料中的灰分以及所添加的熔剂在高温下相互反应,生成以硅酸钙和铝硅酸钙为主要成分的熔融物  He W C,Luo M S,Deng Y,et al. Preparation of high acidity coefficient slag wool fiber with blast furnace slag and modifying agents[J]. Journal of Iron and Steel Research International,2023,30(7):1440-1450.
 Ayano T,Fujii T,Okazaki K. Freeze-thaw resistance of concrete using ground granulated blast-furnace slag and blast-furnace slag sand in salt water[J]. Journal of Advanced Concrete Technology,2024,22(5):253-266.
28-29
。此熔融物经过水淬急冷或自然慢冷等工艺处理后,形成了玻璃体含量较高的固体副产品,其化学成分相对稳定均一,结构为快速冷却形成的亚稳态,具有较高的潜在水硬活性,是建材等领域中重要的再生资源  Xu Z L,Yao J B,Fu R B. Characteristic,resource approaches and safety utilization assessment of non-ferrous metal smelting slags:a literature review[J]. Journal of Central South University,2024,31(4):1178-1196.
30

钢渣是在转炉、电炉等炼钢过程中,为有效去除生铁中的碳、硅、锰、磷等杂质而加入的石灰、萤石等造渣剂材料,与杂质在高温下发生化学反应所形成的熔融体  Hashimoto R,Onoue K. Crack resistance under compressive stress of concrete made using granulated blast-furnace slag sand[J]. Journal of Advanced Concrete Technology,2023,21(1):17-24.
 Rondón-Quintana H A,Ruge-Cárdenas J C,Patiño-Sánchez D F,et al. Blast furnace slag as a substitute for the fine fraction of aggregates in an asphalt mixture[J]. Journal of Materials in Civil Engineering,2018,30(10):04018244.
31-32
。其化学成分受原料与工艺影响,波动性显著。此外,钢渣中常含有f-CaO和f-MgO,这些组分在后续遇水或环境变化时会发生体积膨胀,这种现象制约了其在建设工程中的直接应用  Xu B,Ma Y P,Gao W,et al. A review of the comprehensive recovery of valuable elements from copper smelting open-circuit dust and arsenic treatment[J]. JOM,2020,72(11):3860-3875.
33

1.2     物理与化学特性

物理特性。钢铁渣多呈现为表面粗糙、棱角分明的不规则颗粒状,整体硬度高且耐磨性能优异  Hwang E H,Ko Y S,Kim J M,et al. Mechanical/physical characteristics of polymer mortar recycled from rapid-chilled steel slag[J]. Journal of Industrial and Engineering Chemistry,2009,15(5):628-634.
 Mancini A,Lothenbach B,Geng G,et al. Iron speciation in blast furnace slag cements[J]. Cement and Concrete Research,2021,140:106287.
34-35
。其密度通常略高于天然石材,同时内部含有较多孔隙  Li P F,Ji J,Wen L,et al. Quantitative characterization and evaluation of key physicochemical characteristics of steel slag[J]. Construction and Building Materials,2024,414:134959.
36
。经水淬急冷处理的高炉矿渣,因快速冷却而形成以玻璃体为主的结构,具有较高的潜在胶凝活性;而缓慢冷却的钢渣,则因结晶程度较高,导致其胶凝活性相对较低  Davis C,Hall R,Hazra S,et al. Reuse,remanufacturing and recycling in the steel sector[J]. Philosophical Transactions of the Royal Society A:Mathematical,Physical and Engineering Sciences,2024,382(2284):20230244.
37

化学成分。钢铁渣的化学成分主要有CaO、SiO2、Al2O3、Fe2O3、MgO,同时含有少量的Mn、P、S以及微量V、Ti、Cr等元素。高炉矿渣的成分相对稳定,其CaO/SiO2质量比通常为0.9~1.5,体现出中低碱度的特征  Kuwahara Y,Hanaki A,Yamashita H. Direct synthesis of a regenerative CaO-Fe3O4-SiO2 composite adsorbent from converter slag for CO2 capture applications[J]. ACS Sustainable Chemistry & Engineering,2022,10(1):372-381.
38
;钢渣的碱度普遍更高,成分也更为复杂,其具体组成因炼钢原料和工艺条件的差异而呈现出较大的波动性  Luo Y B,He D F,Qing G L. Investigation into the impact of Fe2O3,MgO,and Al2O3 contents on the Ca ions leaching rate of steel slag[J]. JOM,2024,76(3):1356-1371.
39

矿物成分。矿物成分是决定钢铁渣理化性能与应用潜力的关键因素  Wendling L A,Binet M T,Yuan Z,et al. Geochemical and ecotoxicological assessment of iron-and steel-making slags for potential use in environmental applications[J]. Environmental Toxicology and Chemistry,2013,32(11):2602-2610.
 Luo Y B,He D F. Research status and future challenge for CO2 sequestration by mineral carbonation strategy using iron and steel slag[J]. Environmental Science and Pollution Research,2021,28(36):49383-49409.
40-41
。高炉矿渣的主要矿物成分为钙铝黄长石、硅酸二钙等,结构相对均匀。钢渣的矿物成分则更为复杂多样,主要包括硅酸二钙、硅酸三钙、铁镁固溶体、铁酸钙等活性矿物以及f-CaO和f-MgO。其中,f-CaO和f-MgO的存在易导致其体积安定性不良,而活性矿物相则赋予其潜在的胶凝特性,二者共同构成了钢渣资源化利用的核心挑战与潜力所在  Shekhar Samanta N,Das P P,Dhara S,et al. An overview of precious metal recovery from steel industry slag:recovery strategy and utilization[J]. Industrial & Engineering Chemistry Research,2023,62(23):9006-9031.
42
表1为钢铁渣的分类与特性对比。

表1     钢铁渣的主要分类与基本特征对比
Table 1     Main classification and basic characteristics of steel slag
类型 来源工序 产渣系数(粗钢)/(t/t) 主要化学成分特征 CaO/SiO2质量比 典型矿物相 潜在活性 主要应用限制 参考文献
高炉矿渣 高炉炼铁 0.20~0.60 CaO、SiO2、Al2O3为主,成分稳定 0.9~1.5(中低碱度) 钙铝黄长石、硅酸二钙、玻璃体 潜在活性需激发  Vijayaraghavan J,Jude A B,Thivya J. Effect of copper slag,iron slag and recycled concrete aggregate on the mechanical properties of concrete[J]. Resources Policy,2017,53:219-225.
43
转炉钢渣 转炉炼钢 0.11~0.20 CaO、Fe2O3、SiO2,波动大 1.5~3.5(高碱度) 硅酸二钙、硅酸三钙、铁酸钙、f-CaO/f-MgO 低-中 体积安定性不良、活性低  Tang H M,Peng Z W,Shang W X,et al. Preparation of refractory materials from electric furnace ferronickel slag and blast furnace ferronickel slag:a comparison[J]. Journal of Environmental Chemical Engineering,2022,10(3):107929.
44
电炉钢渣 电炉炼钢 0.12~0.25 受废钢成分影响大,含Cr、Ni等合金元素 1.2~2.5 与转炉渣类似,含合金相 重金属浸出风险、成分复杂  Sagadin C,Luidold S,Wagner C,et al. Melting behaviour of ferronickel slags[J]. JOM,2016,68(12):3022-3028.
45

2     钢铁渣中有价元素的回收技术

2.1     铁的回收

磁选法是目前从钢铁渣中回收铁最广泛、最成熟的技术,其原理是利用渣中铁磁性物质与非磁性硅酸盐矿物的磁性差异进行分选。通常需对钢铁渣进行破碎、磨矿等预处理以实现铁颗粒充分解离,而高效破碎设备及强磁场、高梯度磁选机的应用显著提升了微细粒铁的回收率,所得铁精粉可返回烧结或炼钢工序,实现铁元素闭路循环  Gu T,Zhang G Y,Wang Z Y,et al. Review:The formation,characteristics,and resource utilization of lithium slag[J]. Construction and Building Materials,2024,432:136648.
46

针对弱磁性氧化铁形式的铁,可采用深度还原与磁选联用技术。该技术通过在高温和还原性气氛下添加还原剂将氧化铁还原为金属铁,并使硅、钙等氧化物生成新矿物相,还原产物经磨矿后再通过磁选高效回收金属铁颗粒。该技术虽能实现铁的高效富集与回收,但存在能耗较高、工艺复杂的问题  Li L,Xiao Y,Lei Y,et al. An approach of cobalt recovery from waste copper converter slags using pig iron as capturing agent and simultaneous recovery of copper and tin[J]. Waste Management,2023,165:1-11.
47

酸浸法浸出钢渣过程中一般采用盐酸作为酸性浸出剂,以生成富含硅的固体残渣和富含钙的溶液。例如,Höllen等  Höllen D,Berneder I,Capo Tous F,et al. Stepwise treatment of ashes and slags by dissolution,precipitation of iron phases and carbonate precipitation for production of raw materials for industrial applications[J]. Waste Management,2018,78:750-762.
48
利用电弧炉间接碳酸化的方式回收铁金属,所得的水溶液中含有大量的重金属,如铅、钡、锌、铜和镍,以及高浓度的铁。

表2为三种铁回收技术的技术原理、适用对象、关键指标成熟度及环境特征。

表2     钢铁渣中铁回收主要技术路线对比
Table 2     Comparison of main technical routes for iron recovery from steel slag
技术路线 机理核心 适用对象 典型回收率 能耗 成熟度 主要环境风险 参考文献
磁选 磁性差异 含磁铁矿、金属铁的钢铁渣 50%~75% 电耗15~30 kWh/t 工业化成熟 粉尘  Gu T,Zhang G Y,Wang Z Y,et al. Review:The formation,characteristics,and resource utilization of lithium slag[J]. Construction and Building Materials,2024,432:136648.
46
还原焙烧-磁选 还原转化+磁选 低铁品位、弱磁性的铁钢铁渣 85%~95% 200~300 kgce/t 工业应用 废气、粉尘  Li L,Xiao Y,Lei Y,et al. An approach of cobalt recovery from waste copper converter slags using pig iron as capturing agent and simultaneous recovery of copper and tin[J]. Waste Management,2023,165:1-11.
47
酸浸-沉淀 化学溶解+选择性沉淀 铁分散均匀、无磁性的钢铁渣 >85% 酸0.5~1.0 t/t 实验室/中试 高盐废水、废酸  Höllen D,Berneder I,Capo Tous F,et al. Stepwise treatment of ashes and slags by dissolution,precipitation of iron phases and carbonate precipitation for production of raw materials for industrial applications[J]. Waste Management,2018,78:750-762.
48

2.2     钙、硅元素的回收

钢铁渣中钙、硅元素的回收主要有湿法化学提取、高温熔融重构,两者机理、边界条件和经济性差异显著。

湿法化学提取技术采用酸(盐酸、硝酸)或铵盐溶液(NH4Cl,NH4NO3)浸出钢铁渣,选择性溶出钙、硅等元素。其核心机理为:铵盐体系可选择性浸出钙而不溶解大部分硅(产物以硅胶或活性二氧化硅形式富集),而酸体系则同时溶出钙、铁、铝等。浸出液经净化、CO2碳化沉淀可制备纳米二氧化硅、沉淀碳酸钙(PCC)等高附加值产品(市场价1 500~3 000元/t)。该技术的优势是可联产高纯化工产品、实现CO2封存(每吨钢铁渣可固定CO2 100~300 kg);缺点是试剂消耗大(每吨渣铵盐耗量0.3~0.8 t)、产生的含盐废水(NH4Cl或CaCl2溶液)需后续处理或蒸发结晶,综合运营成本较高(每吨渣200~500元)。目前该技术以中试为主,经济可行性高度依赖PCC等产品售价  Wei L S,Xu H X,Wu J,et al. A review of research progress on the resource utilization of copper tailing[J]. Journal of Environmental Chemical Engineering,2025,13(3):116238.
49

高温熔融重构技术则通过添加硅质、铝质校正原料(如粉煤灰、煤矸石、废玻璃),在高温(1 400~1 600 ℃)下熔融并快速冷却,将钢铁渣中的游离氧化钙和硅酸二钙等重组为高活性玻璃体或矿棉纤维。其机理是通过高温破坏钢铁渣中原有物相,形成均质化熔体,淬冷后可制备高胶凝活性材料(活性指数>90%)或矿棉保温材料(附加值3 000~8 000元/t)。该技术实现了钙、硅元素的原位转化与大幅增值,且可消纳多种固废。但熔融过程能耗极高(每吨渣热耗400~600 kg标煤),设备投资大(熔炼炉系统需数千万元甚至上亿元),仅适用于大规模集中处理的场景及高附加值产品导向  Zhang C Y,Zhang Y Y,Zhang Z H,et al. Effective separation and recovery of valuable metals from copper slag:a comprehensive review[J]. Environmental Research,2025,283:122145.
 Triviño M L T,Raguindin R Q. Sustainable practices for carbon neutrality:catalytic applications of steel slag waste for carbon dioxide mitigation[J]. Journal of Environmental Chemical Engineering,2025,13(3):116995.
50-51

从钢铁渣中回收钙和硅的两条技术路线对比见表3

表3     钢铁渣中钙、硅回收技术路线对比
Table 3     Comparison of technology routes for calcium and silicon recovery from steel slag
技术路线 核心产物 反应条件 钙/硅利用率 能耗 成熟度 主要环境风险 参考文献
湿法浸出-碳化 PCC、SiO2 室温至80 ℃ Ca>70%,Si<30% 中试 含盐废水  Zhang C Y,Zhang Y Y,Zhang Z H,et al. Effective separation and recovery of valuable metals from copper slag:a comprehensive review[J]. Environmental Research,2025,283:122145.
50
高温熔融重构 矿渣棉/高活性材料 1 400~1 600 ℃ 近100%(物相转化) 极高 工业应用 废气、熔渣  Triviño M L T,Raguindin R Q. Sustainable practices for carbon neutrality:catalytic applications of steel slag waste for carbon dioxide mitigation[J]. Journal of Environmental Chemical Engineering,2025,13(3):116995.
51

2.3     稀散及有价金属的回收

钒的回收以含钒钢渣提钒为典型代表:传统钠化焙烧-水浸法通过将钢渣与钠盐混合焙烧使钒转化为可溶性钒酸钠,再经水浸、沉淀获得五氧化二钒,该工艺成熟但焙烧过程中会产生腐蚀性废气;新兴绿色提取技术则包括以钙盐替代钠盐的钙化焙烧-酸浸/碱浸法、可简化流程的直接酸浸/碱浸法,以及环境友好但周期较长的生物浸出法  Cirilli F,De Santis M,Di Sante L,et al. A comprehensive review of secondary carbon carriers for ironmaking and steelmaking processes:industrial utilization of non-biogenic materials in steel production[J]. Journal of Sustainable Metallurgy,2025,11(4):3343-3360.
 Liu X,Wang D Z,Li Z W,et al. Efficient separation of iron elements from steel slag based on magnetic separation process[J]. Journal of Materials Research and Technology,2023,23:2362-2370.
 Sun X,Hu C L,Li T G,et al. Research progress on iron-rich industrial waste as environmentally functional material[J]. Sustainable Chemistry and Pharmacy,2024,42:101772.
 Yu Y H,Du C M. A review on the P enrichment and recovery from steelmaking slag:towards a sustainable P supply and comprehensive utilization of industrial solid wastes[J]. Science of the Total Environment,2023,891:164578.
 Xiang L D,Zhang T A. Research progress on the recovery of strategic metals lithium and gallium from coal-based solid wastes:from mineral deconstruction to resource utilization[J]. Minerals Engineering,2026,235:109775.
 Li R,Liu K J,Zhang X X,et al. Comprehensive recycling of slag from the smelting of spent automotive catalysts[J]. Separation and Purification Technology,2024,350:127661.
52-57

钛的回收主要针对高钛型高炉渣中结构稳定的钙钛矿相  Hong S J,Moon S,Sim G,et al. Metal recovery from iron slag via pH swing-assisted carbon mineralization with various organic ligands[J]. Journal of CO2 Utilization,2023,69:102418.
 Ku J G,Zhang L,Fu W,et al. Mechanistic study on calcium ion diffusion into fayalite:a step toward sustainable management of copper slag[J]. Journal of Hazardous Materials,2021,410:124630.
 Wu J J,Tan Y,Li P,et al. Centrifugal-Granulation-Assisted thermal energy recovery towards low-carbon blast furnace slag treatment:state of the art and future challenges[J]. Applied Energy,2022,325:119835.
58-60
,采用选择性富集-分选(通过高温改性使钛富集后分选)或强化浸出(利用浓酸、高温等手段破坏结构)等方法  Duan W J,Li R M,Wang Z M,et al. Breaking boundaries in slag waste heat recovery:review and future perspective of dry centrifugal granulation technology[J]. Process Safety and Environmental Protection,2024,191:315-344.
61
。例如,He等  He M Y,Teng L M,Gao Y X,et al. Simultaneous CO2 mineral sequestration and rutile beneficiation by using titanium-bearing blast furnace slag:process description and optimization[J]. Energy,2022,248:123643.
62
提出了一种将CO2矿化与金红石选矿相结合的全新工艺。该工艺使用含钛的高炉矿渣和绿矾作为原料。将矿渣在550~750 ℃下焙烧后进行碳酸化处理,随后通过浮选和磁选分别回收金红石和赤铁矿(图2)。研究显示,引入Na2SO4后钛的转化率从53%显著提高到98%。

图2     钛的回收工艺
Fig. 2     Recycling process of titanium  He M Y,Teng L M,Gao Y X,et al. Simultaneous CO2 mineral sequestration and rutile beneficiation by using titanium-bearing blast furnace slag:process description and optimization[J]. Energy,2022,248:123643.
62

3     钢铁渣的综合应用

3.1     建筑材料领域

3.1.1     水泥材料

高炉矿渣经水淬急冷后磨细制成的颗粒化高炉矿渣粉,是优质的水泥混合材料和混凝土掺合料,其潜在水硬活性在水泥水化产物激发下可显著改善混凝土的长期强度、耐久性与工作性能  Heo J H,Chung Y,Park J H. Recovery of iron and removal of hazardous elements from waste copper slag via a novel aluminothermic smelting reduction (ASR) process[J]. Journal of Cleaner Production,2016,137:777-787.
 Tripathi A K,Das S K,Mustakim S M,et al. Integrated management of ferrochrome slag:metal recovery,Cr(VI) stabilization,and sustainable reuse in construction materials[J]. Journal of Environmental Management,2025,390:126268.
63-64
。钢渣因活性较低且含游离氧化钙,在此领域应用受限,但通过机械、化学或热力活化等预处理可激发其活性,实现部分替代水泥  Zhang L L,Cui J S,Chen Z H,et al. Recycling of carbonated steel slag in building materials:recycling pathways and recent advances[J]. Journal of Building Engineering,2025,104:112285.
 郝挺宇. 钢铁渣粉高性能混凝土的研究与应用[C]//中国硅酸盐学会固废分会成立大会第一届固废处理与生态环境材料学术交流会,2015:1.
65-66
。此外,将钢渣与少量水泥熟料、石膏等共同粉磨可制备钢渣硅酸盐水泥;以钢渣为主要骨料并辅以水泥、粉煤灰等胶凝材料,则可用于生产铺路砖、透水砖及砌块等建材产品  Li Y,Dai W B. Modifying hot slag and converting it into value-added materials:a review[J]. Journal of Cleaner Production,2018,175:176-189.
67
。在工业建筑加固工程中,采用碳酸化钢渣-水泥复合胶凝材料(钢渣掺量10%),28 d抗压强度达63.12 MPa,相较于纯水泥体系,强度提升明显,同时实现了固废资源化利用  Sun J R,Wang W Q,Liu C P,et al. Nonlinear response of silica fume-steel slag-cement composites:a quartic polynomial modeling of hydration kinetics,pore refinement,and mechanical enhancement[J]. Construction and Building Materials,2025,494:143145.
68

3.1.2     道路工程材料

钢渣作为一种性能优良的筑路材料,具有强度高、耐磨性强和抗滑性能突出的特点,能够有效替代天然碎石,广泛应用于道路的基层、底基层集料以及沥青混凝土面层中  Petousis M,Kalderis D,Michailidis N,et al. Sustainable high-density polyethylene/ferronickel slag composites for material extrusion additive manufacturing:engineering,morphological,rheological,thermal,and chemical aspects[J]. Sustainable Materials and Technologies,2025,43:e01227.
 Fu S T,Kwon E E,Lee J. Upcycling steel slag into construction materials[J]. Construction and Building Materials,2024,444:137882.
69-70
。钢渣中含有一定量的f-CaO和f-MgO,这些成分在后期遇水后可能发生水化反应,导致体积膨胀,进而引发路面胀裂、翘曲等工程病害,严重影响道路的耐久性与安全性。为确保道路工程质量的长期稳定性,必须对钢渣进行充分预处理,如自然陈化、蒸汽养护或压蒸处理等,促使游离组分提前消解和稳定化,从而使其体积变化在铺筑前基本完成  Wei Y L,Lin C Y,Cheng S H,et al. Recycling steel-manufacturing slag and harbor sediment into construction materials[J]. Journal of Hazardous Materials,2014,265:253-260.
 郝迎军. 钢铁渣复合粉在混凝土中的运用[J]. 中国建材科技,2020,29(1):50-51.
71-72
。然而,不同的预处理方式,其机理、工艺条件、处理效果和经济性差异显著  Zhao X J,Zhang Y M. Analyzing the mechanical and durability characteristics of steel slag-infused asphalt concrete in roadway construction[J]. Buildings,2024,14(3):679.
 Wang H L,Qian J S,Zhang H H,et al. Exploring skid resistance over time:steel slag as a pavement aggregate-comparative study and morphological analysis[J]. Journal of Cleaner Production,2024,464:142779.
 Yang C,Huang Z W,Wu S P,et al. Recycling steel slag as aggregate in developing an ultra-thin friction course with high comprehensive road performance[J]. Construction and Building Materials,2024,449:138539.
73-75

1)自然陈化法。将钢渣露天堆放,利用大气中的水分和CO2自然消解f-CaO和f-MgO。自然陈化法的机理为:f-CaO与H2O反应生成Ca(OH)2,Ca(OH)2进一步与CO2反应生成CaCO3。该方法操作简单、成本极低,但处理周期长、受气候影响大,且f-MgO消解极慢。此外,长期堆放需占用大量土地,存在二次扬尘和渗滤风险。因此,自然陈化法仅适用于土地充裕、环保要求不高的地区,正逐步被淘汰。

2)热闷法。将高温钢渣(800~900 ℃)置于密封容器中,以喷水产生的高温高压蒸汽(0.4~0.6 MPa,100~150 ℃)热闷6~12 h。热闷法的机理为:高温高压加速水化反应,f-CaO和f-MgO快速消解。该方法处理效率高,f-CaO可降至2%以下,f-MgO可部分消解,且在处理期间钢渣因热应力作用产生微裂纹,有利于后续粉磨,但该方法也存在设备投资大、能耗较高、f-MgO消解仍不彻底的问题。

3)蒸汽养护法。将冷却后的钢渣置于常压或微压蒸汽环境中(80~100 ℃,常压或0.1~0.3 MPa),处理12~48 h。蒸汽养护法的机理与热闷法类似但条件温和,可促进f-CaO水化,但对f-MgO效果有限。该方法投资和运营成本低于热闷法,但处理时间较长,且需配套蒸汽锅炉。此方法适用于钢渣掺量较低的应用场景。

4)碳酸化法。在含水条件下通入CO2气体(体积分数为10%~100%,压力为0.1~1.0 MPa,温度为20~80 ℃),处理1~6 h。碳酸化法的机理为:f-CaO、f-MgO以及Ca(OH)2直接与CO2反应生成稳定碳酸盐,体积膨胀可控,同时可实现CO2封存。该方法反应速率快、处理时间短,且可联产碳酸盐建材,环境效益显著,但CO2来源问题是主要制约因素,且该方法处理成本相对较高,目前处于中试和工业试验阶段,是极具潜力的绿色技术。

5)粒化法。将高温熔融钢渣用高压水流急冷粒化,形成玻璃体含量高的细小颗粒。粒化法的机理为:快速冷却抑制f-CaO和f-MgO析晶,将其“冻结”在玻璃体中,从而降低其水化膨胀风险。该法处理效率高,所得渣粒可直接用作骨料,但仅适用于熔融态钢渣,对已冷却的钢渣无效,且对钢渣流动性要求高,设备和场地投资大。

6)机械活化法。通过粉磨降低钢渣粒径,增加比表面积。机械活化法的机理为:机械力化学效应可加速f-CaO暴露和水化,同时破坏f-MgO的致密结构,促进其反应。此外,粉细后的钢渣在建材中分布更均匀,局部膨胀应力降低。该方法常与其他预处理方法联用,单独使用难以彻底消除膨胀,且能耗较高。

经过适当处理的钢渣,不仅能满足道路材料的技术要求,还可实现大宗固废的资源化利用,降低对天然石料的开采需求,具有显著的经济效益和环境效益,是推动绿色交通基础设施建设的重要途径之一  Zhou W T,Liu X,Lyu X J,et al. Extraction and separation of copper and iron from copper smelting slag:a review[J]. Journal of Cleaner Production,2022,368:133095.
76
。钢渣采用碳酸化法预处理后,与矿渣复配,可制备全固废碱激发道路基层材料  Wang Z M,Yang J J,Wu Y L. Durability performance of CGF stone waste road base materials under dry-wet and freeze-thaw cycles[J]. Materials,2024,17(17):4272.
77
。在优化条件(CO2体积分数为100%、碳化24 h、湿度为70%)下,仅掺加5%胶凝材料,混合料的7 d无侧限抗压强度达4.62 MPa,泡水CBR值为175.4%,7 d浸水膨胀率由未处理样的2.45%大幅降低至0.18%,可满足一级公路底基层技术要求。在甘肃某软土地区的一段高速公路采用机械活化法进行了试验:采用钢渣粉、矿渣粉、粉煤灰、电石渣和少量水泥组成固废基胶凝材料,以钢渣为集料,制备全固废混凝土用于桩体填充。研究结果表明:粉煤灰掺量12%时钢渣浸水膨胀性降低80%,固废基胶凝材料28 d专用胶砂强度达32.2 MPa。现场应用显示,复合地基承载力较普通水泥碎石桩最大提高45%。

3.1.3     微晶玻璃和陶瓷原料

钢铁渣的主要化学成分与玻璃和陶瓷的基础成分高度相似,富含SiO2、CaO、Al2O3等关键组分,基于这种特性,可将其作为微晶玻璃和陶瓷生产的重要替代原料  Xiang C J,Peng Z W,Fan W L,et al. Preparation of enstatite-spinel based glass-ceramics from ferronickel slag and iron ore tailings by microwave-assisted one-step crystallization[J]. Ceramics International,2024,50(21):41168-41179.
78
。通过烧结法或高温熔融法等工艺,对钢铁渣进行成分调控与结构重构,可制备出高性能的矿渣微晶玻璃、建筑陶瓷或工业陶瓷材料  Tang Q G,Mu X Z,Duan X H,et al. Potential of chambersite tailing as raw material for the preparation of glass ceramic:investigation on crystallization behavior and crystal structure[J]. Arabian Journal for Science and Engineering,2018,43(11):5919-5927.
79
。这类材料不仅继承了钢铁渣固有的高硬度与化学稳定性,更能通过工艺优化获得优异的机械强度、耐磨性、耐腐蚀性和热稳定性。同时,其外观质感可通过配比与工艺实现多样化,使制备产品具备良好的装饰性与市场应用价值,显著提升资源化产品的附加值。这一技术路径不仅实现了钢铁渣的大宗消纳与高值转化,也减少了对天然矿产资源的消耗,为推动建材行业绿色低碳转型提供了切实可行的方案,是实现固废资源化与产业协同发展的重要方向  Chen Y F,Lin G,Wang S X,et al. Ultrasonic-enhanced selective arsenic removal and sulfide conversion from iron slag[J]. Journal of Cleaner Production,2024,450:141885.
80
。内蒙古科技大学利用白云鄂博矿的尾矿、钢渣、铁渣及粉煤灰等固体废弃物,采用熔融-离心铸造法建成了日生产能力3 000 kg的微晶玻璃管材中试生产线。经国家建筑材料测试中心检测,该产线生产的微晶玻璃管材抗弯强度达192 MPa,耐酸性>99%,耐碱性>97%,莫氏硬度9级(接近金刚石),耐磨性<0.04 g/cm2。包头市天龙混凝土公司试用发现,以该微晶玻璃管材铺设的管道,使用寿命提高了3~4倍。

3.2     环境修复材料领域

3.2.1     废水处理吸附剂

钢渣因其内部具有多孔结构、比表面积较大且表面富含活性位点,对水体中的磷酸盐、多种重金属离子(如Pb2+、Cu2+、Cd2+)以及有机染料等污染物均表现出良好的吸附去除能力  Sahu J N,Kapelyushin Y,Mishra D P,et al. Utilization of ferrous slags as coagulants,filters,adsorbents,neutralizers/stabilizers,catalysts,additives,and bed materials for water and wastewater treatment:a review[J]. Chemosphere,2023,325:138201.
81
。其净化机制并非单一过程,而是化学沉淀、表面络合、离子交换与物理吸附等多种方式的共同作用。然而,原始钢渣在废水处理应用中存在两大核心风险:1)吸附饱和后重金属再释放。在酸性条件(pH<3)或高盐度环境下,已固定的重金属可能因化学沉淀溶解或离子交换逆反应而重新溶出,浸出率可达20%~60%,造成二次污染  Aryee A A,Liu Y,Han R P,et al. Bimetallic adsorbents for wastewater treatment:a review[J]. Environmental Chemistry Letters,2023,21(3):1811-1835.
82
。2)碱性物质溶出。钢渣中CaO、MgO的水化导致出水pH显著升高(可达10~12),需后续中和处理。

为降低上述风险,研究者开发了多种钢渣改性技术  Vialkova E,Korshikova E,Fugaeva A. Phytosorbents in wastewater treatment technologies:review[J]. Water,2024,16(18):2626.
83
。1)酸洗改性。采用稀HCl、H2SO4或HNO3对钢渣进行预处理,可溶解表面碱性氧化物、增加比表面积(可提升30%~50%)、暴露更多吸附位点,同时降低钢渣的碱度(出水pH降至8~9)。酸洗后钢渣对Pb2+的吸附容量可从50 mg/g提升至80~120 mg/g。机理:酸蚀刻去除表面致密氧化层,形成微孔结构,同时引入-OH、-COOH等活性官能团  De Gisi S,Lofrano G,Grassi M,et al. Characteristics and adsorption capacities of low-cost sorbents for wastewater treatment:a review[J]. Sustainable Materials and Technologies,2016,9:10-40.
84
。2)高温活化。在300~800 ℃下煅烧钢渣,可分解部分碳酸盐和氢氧化物,使矿物相重组,比表面积和孔容显著增加。机理:热分解产生的活性CaO、MgO可与重金属反应生成更难溶的氢氧化物或碳酸盐沉淀。高温活化钢渣对Cd2+的去除率可从65%提升至90%以上  Lamaming J,Saalah S,Rajin M,et al. A review on bamboo as an adsorbent for removal of pollutants for wastewater treatment[J]. International Journal of Chemical Engineering,2022,2022:7218759.
85
。3)复合改性。将钢渣与铝盐、铁盐或聚合物复配,制备复合吸附材料。例如,钢渣-海藻酸钠复合微球可通过包埋作用降低钢渣颗粒的直接暴露,有效抑制碱性物质溶出(出水pH<9),同时利用海藻酸盐的羧基络合作用增强重金属固定能力。复合改性的核心优势在于实现“吸附-稳定化-控碱”一体化  Kumari P,Alam M,Siddiqi W A. Usage of nanoparticles as adsorbents for waste water treatment:an emerging trend[J]. Sustainable Materials and Technologies,2019,22:e00128.
86
。4)表面包覆。以硅烷偶联剂或有机物对钢渣进行表面修饰,形成疏水或离子选择性屏障层,可显著降低酸性条件下重金属的再溶出率。这类处理能够有效优化材料的孔隙分布,增强表面反应活性,从而显著提高其对污染物的吸附容量与固定速率,同时改善其在动态水流条件下的使用稳定性和渗透性。通过上述改性方法,钢渣有望成为一种安全、高效、低成本的废水处理吸附材料,实现“以废治污”,同时有效规避二次污染风险  Zhou B,Wei J J,Gu Y C,et al. Utilization of graphene oxide for enhancing the heavy metal immobilization of limestone calcined clay cement containing ferronickel slag[J]. Construction and Building Materials,2024,439:137401.
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3.2.2     烟气脱硫剂

钢渣作为一种碱性工业固体废弃物,富含CaO、MgO等活性碱性氧化物,可有效应用于烟道气脱硫。在干法或半干法脱硫工艺中,经适当预处理的钢渣微粉与烟气充分接触,其中的碱性组分可与SO2发生化学反应,生成硫酸钙、硫酸镁等稳定硫酸盐,从而实现硫的高效固定与烟气净化  Ma M Y,Zhao H G,Hu P. Investigation into the dissolution kinetics of different MgO desulfurizers in flue gas desulfurization[J]. ACS Omega,2024:acsomega.3c08575.
88
。尽管与高纯度石灰等专用脱硫剂相比,钢渣的单位脱硫效率略低,但其本身属于大宗工业固废,原料成本极低,且无需经过复杂的煅烧过程,能显著降低脱硫系统的运行成本。该技术路径不仅实现了烟气中酸性污染物的治理,更同步消纳了钢铁生产过程中的固体废物,体现了“以废治废”和“废物资源化”的双重环境效益。在具备稳定钢渣来源的钢铁企业或邻近工业区,该技术展现出良好的经济性与综合环保优势,为工业污染协同治理提供了可行方案  Li Y,Liu L,Wang J S,et al. Preparation of active zinc oxide from zinc-containing dust and synergistic recovery process of valuable elements[J]. Separation and Purification Technology,2025,354:128820.
89
。Pei等  Pei S L,Pan S Y,Li Y M,et al. Environmental benefit assessment for the carbonation process of petroleum coke fly ash in a rotating packed bed[J]. Environmental Science & Technology,2017,51(18):10674-10681.
90
采用一种高重力碳酸化工艺,将石油焦粉渣和炼钢废水用于矿化处理CO2,以及去除烟气中氮氧化物和颗粒物。研究发现,经高重力碳酸化工艺处理后,CO2的去除效率为95.6%,对应的CO2日捕获量为600 kg。此外,氮氧化物和颗粒物的去除效率分别为99.1%和83.2%。碳酸化后经反应的粉渣,还被进一步用作混合水泥砂浆中的补充胶凝材料(图3)。

图3     铁矿渣和钢渣进行CO2矿化过程
Fig. 3     Processes of carbon dioxide mineralization involving iron slag and steel slag  Pei S L,Pan S Y,Li Y M,et al. Environmental benefit assessment for the carbonation process of petroleum coke fly ash in a rotating packed bed[J]. Environmental Science & Technology,2017,51(18):10674-10681.
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3.2.3     土壤改良剂与固碳材料

钢渣作为土壤改良剂,在农业与环境领域具有双重效益(图4  Chen J,Xing Y,Wang Y,et al. Application of iron and steel slags in mitigating greenhouse gas emissions:a review[J]. Science of the Total Environment,2022,844:157041.
8
。其碱性组分能够有效中和酸性土壤,调节pH值,同时补充土壤中缺乏的Ca、Mg、Si等中微量元素,改善土壤结构,增强养分供给能力。此外,钢渣中的活性钙镁硅酸盐矿物能够在自然或优化条件下与大气或富集来源的CO2发生矿化反应,将其转化为稳定的碳酸盐矿物,从而实现CO2的长期安全封存  Kong F Y,Ying Y Q,Lu S G. Heavy metal pollution risk of desulfurized steel slag as a soil amendment in cycling use of solid wastes[J]. Journal of Environmental Sciences,2023,127:349-360.
91
。这一过程不仅降低了钢渣自身的碱性潜害,更将碳固定于固态产物中。该技术路径创新性地将大宗工业固废的资源化利用与温室气体负排放技术相结合,为钢铁行业协同推进循环经济、改良土壤与应对气候变化提供了具有重要潜力的前沿方向,体现了工业生态系统与自然生态系统协同共生的可持续发展理念  Chen Y F,Zhu R,Zhu M Y,et al. High-efficiency extraction of indium from iron slag rich in insoluble zinc ferrite by ultrasonic enhancement[J]. Separation and Purification Technology,2026,382:135872.
92
。韩国田间试验表明,钢渣施用量8 t/ha时,土壤pH从6.6提升至7.5,SiO2有效含量显著增加,成熟水稻的谷粒达29.95 g/株(对照组约26 g/株),且土壤和稻谷中均未检出Cr、Cd、Pb、As等重金属。

图4     炉渣中碱性物质对土壤中CO2、CH4和N2O的排放量的影响
Fig. 4     Influence of alkaline substances in slag on emissions of carbon dioxide,methane and nitrous oxide in the soil  Chen J,Xing Y,Wang Y,et al. Application of iron and steel slags in mitigating greenhouse gas emissions:a review[J]. Science of the Total Environment,2022,844:157041.
8

3.3     农业及其他领域

3.3.1     农用硅肥

钢铁渣在农业领域作为硅肥施用,是其高附加值资源化的重要方向。渣中富含的硅元素多以稳定硅酸盐形态存在,难以被作物直接吸收。通过机械研磨细化、高温活化或与碱剂共焙烧等改性技术,可有效打破硅氧结构,将其转化为易被植物吸收的可溶性硅钙复合养分  Khoroshev A Y,Makarevich А N,Chernyshev S М,et al. Use of ferrosilicon slag in steel production[J]. Metallurgist,2022,66(5):525-528.
 Isteri V,Ohenoja K,Hanein T,et al. Production and properties of ferrite-rich CSAB cement from metallurgical industry residues[J]. Science of the Total Environment,2020,712:136208.
93-94
。这种活化硅肥施入土壤后,既能补充有效硅元素,又可调节土壤pH,促进团粒结构形成,改善耕性。对于水稻、甘蔗、小麦等喜硅作物,施用后可显著增强茎秆机械强度,提高抗倒伏与抗病虫害能力,进而提升作物产量与品质。然而,钢渣直接作为硅肥施用同样面临重金属累积和土壤盐碱化风险。针对这一问题,研究者采用以下安全改性方法:1)酸溶-重结晶法。用稀硫酸或柠檬酸溶解钢渣,过滤除去不溶残渣(重金属多富集于此),滤液经中和、沉淀后可制备出SiO2含量>30%、重金属含量低于国家肥料限量标准的高纯硅肥  Wang X B,Li X Y,Yan X,et al. Environmental risks for application of iron and steel slags in soils in China:a review[J]. Pedosphere,2021,31(1):28-42.
95
。2)微生物活化。利用硅酸盐细菌(如胶质芽孢杆菌)的代谢产物(有机酸、多糖)选择性溶出钢渣中的硅,同时钝化重金属。机理:细菌分泌的有机酸可络合Ca2+、Mg2+,破坏硅酸盐晶格,释放有效硅;细菌细胞壁表面的官能团可吸附固定重金属离子,降低其生物有效性。微生物活化钢渣硅肥的有效硅含量可提升2~3倍,而重金属有效态降低50%以上  Kim H,Ann K Y. Applicability of ferrosilicon slag for a cementitious binder in concrete mix[J]. Construction and Building Materials,2021,271:121873.
96
。3)复配稀释法。将钢渣与含低重金属的天然矿物或有机肥按(1∶3)~(1∶5)质量比复配,稀释有害组分浓度,同时利用黏土矿物的离子交换和吸附性能固定重金属。该方法操作简单、成本低,适用于大规模农田施用  Ning D F,Song A L,Fan F L,et al. Effects of slag-based silicon fertilizer on rice growth and brown-spot resistance[J]. PLoS One,2014,9(7):e102681.
97
。该应用路径将工业固废转化为具有改良土壤、增强作物抗性功能的农用肥料,不仅降低了硅肥生产成本,也推动了农业的绿色循环发展,实现了“以废治瘠、变废为肥”的生态循环目标  Palod R,Deo S V,Ramtekkar G D. Utilization of waste from steel and iron industry as replacement of cement in mortars[J]. Journal of Material Cycles and Waste Management,2019,21(6):1361-1375.
98

3.3.2     海洋工程人工鱼礁

将大块的稳定钢渣用于构建人工鱼礁,能够为海洋生物营造出结构复杂、空间丰富的立体生境。其表面粗糙多孔,易于藻类、贝类等附着生物定殖,从而快速形成局部生物群落,并为鱼类等提供躲避敌害、栖息繁衍的理想场所。这种应用方式,一方面,可实现钢铁固废的资源化利用,有效缓解陆地堆存带来的环境压力;另一方面,有助于修复受损的海底生境,促进局部海域生物多样性的恢复与海洋生态系统的正向演替。该模式将工业副产品转化为可促进海洋生态修复的宝贵资源,是一条兼具环保效益、生态价值与可持续发展意义的创新路径  Xia W Z,Zhou Y,Bao G D,et al. Recent research progress on recycling metallurgical waste slag and strengthening directional recovery of impurity elements by applied electric field[J]. Chemical Engineering Journal,2024,499:156562.
99

3.3.3     回填与井下充填材料

钢渣是一种理想的采空区充填材料,其颗粒级配良好,具备较高的抗压强度和长期稳定性,能够有效填充地下空洞,均匀承受上部岩层压力,从而显著抑制地表沉降与变形  Hao J S,Zhou Z H,Chen Z H,et al. Utilization of high-volume steel slag in sustainable low carbon cementitious composites for mine backfill:synergistic mechanisms and environmental benefits[J]. Process Safety and Environmental Protection,2025,202:107689.
100
。该应用可为钢铁行业的大量固废提供可持续的消纳途径,减少堆存带来的环境负荷,还能降低传统充填对天然砂石等材料的依赖,可节约开采成本与自然资源  Hao J S,Lin Z J,Wang Q,et al. Utilization of tunnel waste slurry and steel slag for preparation of backfill grouting materials:properties and hydration behavior[J]. Cleaner Materials,2025,18:100341.
101
。同时,钢渣回填有助于提升矿区的地质安全,并为后续生态修复创造良好条件。这一模式可实现工业固废资源化与矿山工程实际需求的高效结合,兼具环境、经济与工程协同效益,是推动绿色矿山建设与循环经济发展的重要途径  Xia W Z,Wang H C,Pang R P,et al. Optimizing removal and control of inclusions/impurities and recovery of valuable elements in metallurgical melts via electric field:toward circular economy and resource efficiency[J]. Chemical Engineering Journal,2025,520:166259.
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4     结论与展望

4.1     结论

钢铁渣资源化利用呈现显著的技术成熟度分层与路径分化。

磁选提铁(回收率50%~75%)、高炉矿渣生产矿渣粉(28 d活性指数≥95%)、热闷稳定化(f-CaO<2%)及道路集料应用已实现产业化,是当前大宗消纳的主体路径;铵盐浸出-碳化制备PCC、钢渣烟气脱硫、微晶玻璃制备处于中试或工业试验阶段,具备推广潜力但受制于成本或能耗;有价金属提取(钒回收率60%~80%,钛<70%)、废水吸附剂、生物浸出等技术仍处于实验室阶段,距工业化尚有较大距离。

矿渣粉生产(每吨渣收益100~200元)和还原焙烧提铁(每吨渣收益100~300元)经济性最佳;钠化焙烧提钒、钢渣过量施用农田及吸附剂饱和后处置存在较高环境风险。

体积安定性弱(f-CaO/f-MgO膨胀)是建材化应用的首要障碍。碳酸化快速稳定化是优先突破方向;有价金属提取效率低、成本高;CO2矿化协同提钛(转化率>90%)最具潜力。未来5~10年,突破上述瓶颈是实现钢渣从“低值消纳”向“高值利用”转型的关键。

4.2     展望

针对本文综述的三大核心瓶颈,未来研究应聚焦以下方向:

1)突破体积安定性瓶颈。当前,热闷法虽成熟但f-MgO消解不彻底,碳酸化法效果优但CO2来源受限。因此,需重点发展低成本碳酸化稳定化技术,利用工业副产物CO2或烟气直接矿化。目标:f-CaO<1%、f-MgO<2%、处理时间<2 h、吨渣成本<100元。同步建立f-CaO/f-MgO含量与膨胀率的定量关系模型,完善建材准入标准。

2)提升有价金属协同提取效率。钙化焙烧提钒回收率仅60%~80%,钛富集效率低于70%。应推进CO2矿化协同提钛/提钒(转化率>90%),探索微波/超声波外场强化浸出技术。目标:提钒回收率>85%、提钛回收率>80%、酸耗降低50%以上。构建“磁选提铁→铵盐提钙→酸浸提钒/钛→残渣建材化”的梯级利用平台。

3)强化LCA/TEA与工程验证。明确每条技术路线在能耗、药剂消耗、碳排放、产品价值及二次污染处理成本等方面的经济盈亏平衡点。优先推广如碳化钢渣道路基层(膨胀率0.18%)、钢渣烟气脱硫(年消纳2万吨)、全固废混凝土桩(承载力+45%)等已验证的工程案例。建立覆盖“预处理-资源化-产品应用”的全链条标准体系。

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