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废钢电炉烟气二噁英全过程控制:从末端治理到协同减排

Full-process control of PCDD/Fs in flue gas from scrap-based electric arc furnace steelmaking: from end-of-pipe treatment to synergistic mitigation

  • 摘要: 电炉(electric arc furnace,EAF)短流程炼钢是钢铁行业低碳转型的重要路径,但废钢来源复杂,常夹带油污、塑料、橡胶、涂层及含卤添加剂等杂质,在废钢预热、熔化氧化和烟气冷却过程中可释放氯源、有机碳源和芳香族前驱体,增加多氯代二苯并-对-二噁英和多氯代二苯并呋喃(polychlorinated dibenzo-p-dioxins and dibenzofurans,PCDD/Fs)生成风险。本文综述了废钢电炉冶炼过程中PCDD/Fs的排放特征、生成路径及全过程控制技术。已有研究表明,一次烟气、废钢预热段及袋式除尘前高负荷区是PCDD/Fs生成与迁移的重要节点,其典型浓度为0.35~17 ng-TEQ/m3(标准态);PCDFs质量浓度通常高于PCDDs,2,3,4,7,8-PeCDF和1,2,3,7,8-PeCDD是毒性当量(toxic equivalent,TEQ)的主要贡献组分。从生成路径看,废钢电炉PCDD/Fs主要通过前驱体反应和从头合成形成,其中从头合成在含尘烟气冷却段占主导地位,受飞灰表面未燃碳、氯源及铜/铁等金属组分的异相催化作用影响。现有控制技术包括废钢清洁化、二次燃烧、快速冷却、抑制剂喷入、活性炭吸附和催化氧化等,其中活性炭喷射+袋式除尘是当前较成熟的末端保障技术,但本质上属于污染物相间转移,增加了含PCDD/Fs飞灰处置压力。未来废钢电炉PCDD/Fs控制应由单一末端治理向“源头削减-过程抑制-末端净化”协同控制转变,重点发展过程抑制与末端催化降解相结合的深度减排技术,为电炉短流程低碳冶炼与特征有机污染物控制协同推进提供支撑。

     

    Abstract: Scrap-based electric arc furnace (EAF) steelmaking is an important route for the low-carbon transition of the iron and steel industry. However, owing to the complex origins of scrap steel, impurities such as oil residues, plastics, rubber, coatings, and halogen-containing additives are often introduced into EAFs. During scrap preheating, melting-oxidation, and flue gas cooling, these impurities can release chlorine sources, organic carbon sources, and aromatic precursors, thereby increasing the formation risk of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The emission characteristics, formation pathways, and full-process control technologies of PCDD/Fs during scrap-based EAF steelmaking are reviewed. Existing studies show that primary flue gas, the scrap-preheating section, and high-load zones upstream of bag filtration are important nodes for PCDD/Fs formation and migration, with typical concentrations ranging from 0.35 to 17 ng-TEQ/m³. The mass concentrations of PCDFs are generally higher than those of PCDDs, and 2,3,4,7,8-PeCDF and 1,2,3,7,8-PeCDD are the major contributors to toxic equivalency (TEQ). In terms of formation pathways, PCDD/Fs in scrap-based EAFs are mainly formed through precursor reactions and de novo synthesis. De novo synthesis dominates in dust-laden flue gas cooling sections and is affected by heterogeneous catalysis involving unburned carbon, chlorine sources, and Cu/Fe-containing metal species on fly ash surfaces. Current control technologies include scrap cleaning, secondary combustion, rapid quenching, inhibitor injection, activated carbon adsorption, and catalytic oxidation. Among them, activated carbon injection coupled with bag filtration is a relatively mature end-of-pipe safeguard technology. However, it essentially transfers PCDD/Fs between phases and increases the disposal pressure of PCDD/Fs-containing fly ash. Future control of PCDD/Fs in scrap-based EAF steelmaking should shift from single end-of-pipe treatment toward coordinated control integrating source reduction, in-process inhibition, and end-of-pipe purification, with emphasis on deep mitigation technologies that combine in-process inhibition with end-of-pipe catalytic degradation. This strategy can provide support for the coordinated development of low-carbon EAF steelmaking and the control of characteristic organic pollutants.

     

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