~持久性有机污染物（Persistent Organic Pollutants, POPs）所造成的环境污染已成为全球重大环境问题，源头减少POPs排放是控制POPs环境污染的根本所在。电弧炉炼钢等冶金过程是POPs的重要排放源，电弧炉炼钢行业近些年使用了废钢预热装置，在废钢入炉前对废钢进行预热，减少入炉后的升温时间，从而降低能耗，提高生产效率。预热阶段的温度、原料等反应条件适宜POPs的生成，因此电弧炉炼钢的预热阶段可能是电弧炉炼钢过程中POPs排放的重要工艺段。通过采集三个典型电弧炉冶炼厂预热阶段和冶炼阶段排放的烟道气和飞灰样品，分析了样品中多氯联苯（Polychlorinated Biphenyls, PCBs）、多氯萘（Polychlorinated Naphthalenes, PCNs）以及氯代和溴代多环芳烃（Chlorinated and Brominated Polycyclic Aromatic Hydrocarbons, Cl/Br-PAHs）的排放水平和特征，提出电弧炉炼钢预热过程中POPs形成的关键影响因素，为电弧炉炼钢过程中POPs的减排提供理论依据。获得的主要研究结果如下：
1. 阐明典型电弧炉炼钢企业预热阶段和冶炼阶段排放的典型POPs-PCBs的浓度水平和特征。典型电弧炉炼钢厂预热阶段烟气中类二噁英PCBs（dioxin-like PCBs, dl-PCBs）的浓度范围是0.67~81.66 ng Nm^-3，指示性PCBs的浓度范围是2.08~107.7 ng Nm^-3，预热阶段和冶炼阶段飞灰中dl-PCBs的浓度范围分别是18.4~1588和46.1~650.4 pg g^-1，指示性PCBs的浓度范围是36.6~1475和212.8~636.9 pg g^-1，结果表明电弧炉炼钢预热阶段是PCBs的重要生成工艺段。不同电弧炉炼钢厂的PCBs同类物分布特征具有相似性，以低氯代同类物为主，推断逐级氯化是电弧炉炼钢过程中PCBs生成的重要途径。
2. 阐明典型电弧炉炼钢企业预热阶段和冶炼阶段排放的新POPs-PCNs的浓度水平和特征。电弧炉炼钢预热阶段烟气中PCNs的浓度是92.44~3473 ng Nm^-3，预热过程和冶炼过程的飞灰中PCNs的排放水平分别为1.05~15.18 ng g^-1和3.44~6.32 ng g^-1，表明预热阶段是PCNs的重要生成阶段，PCNs的57种同类物中，2-MoCN和1-MoCN的浓度较高，PCNs同系物浓度水平表现为随着氯取代数目的增加而减少。此外，飞灰中PCNs和PCBs同系物浓度具有良好的线性关系（R=0.93），推断在电弧炉炼钢过程中PCBs和PCNs具有相似的生成机制。
3. 识别电弧炉炼钢是Cl/Br-PAHs的潜在重要排放源，阐明典型电弧炉炼钢企业预热过程和冶炼过程排放的新POPs-Cl/Br-PAHs的浓度水平和特征。典型电弧炉炼钢过程的预热阶段烟气中Cl-PAHs和Br-PAHs排放浓度范围分别是48.65~3164和2.93~258 ng Nm^-3；飞灰中Cl-PAHs和Br-PAHs的浓度最高达到69.1和10.05 ng g^-1。电弧炉炼钢过程中Cl/Br-PAHs的同类物分布特征与其它热过程中存在不一致性，烟气中Cl-PAHs同类物中贡献最高的是9-ClPhe/2-ClPhe，而垃圾焚烧过程的烟气中1-ClPyr占比最高，达到50%。飞灰中1-ClPyr是占比最高的Cl-PAHs，而再生铜冶炼厂的飞灰中，9-ClPhe/2-ClPhe是主要同类物。
 

~Environmental pollution caused by persistent organic pollutants (POPs) has become a major global environmental problem, and reducing POPs emissions from the source is the fundamental point of controlling POPs environmental pollution. Metallurgical processes such as electric arc furnace (EAF) steelmaking are important emission sources of POPs. In recent years, scrap preheating device has been used in EAF steelmaking industry to preheat scrap steel before it is put into furnace, so as to reduce the heating time after it is put into furnace, thus reducing energy consumption and improving production efficiency. The reaction conditions such as temperature and raw materials in the preheating stage are suitable for the generation of POPs. Therefore, the preheating stage of EAF steelmaking may be an important process section for POPs emission in the EAF steelmaking. The emission levels and characteristics of polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), chlorinated and brominated polycyclic aromatic hydrocarbons (Cl/Br-PAHs) were analyzed by collecting flue gas and fly ash samples from three typical EAF smelters during the preheating and smelting stages. The key influencing factors of POPs formation during the preheating process of EAF steelmaking are put forward. It provides a theoretical basis for the reduction of POPs in the EAF steelmaking. The main results are as follows:
1. The concentration level and characteristics of typical POPs-PCBs during preheating and smelting process of typical EAF steelmaking industry are expounded. The concentration range of dioxin-like PCBs (dl-PCBs) in the flue gas during the preheating phase from EAF steelmaking plant is 0.67~81.66 ng Nm^-3, and the concentration range of indicative PCBs is 2.08~107.7 ng Nm^-3. The concentrations of dl-PCBs in fly ash during preheating and smelting stages are 18.4~1588 and 46.1~650.4 pg g^-1, respectively. The concentrations of indicative PCBs are 36.6~1475 and 212.8~636.9 pg g^-1. The results show that the preheating stage of EAF steelmaking is an important stage for PCBs generation. The distribution characteristics of PCBs congeners in different EAF steelmaking plants are similar, and the low-chlorinated congeners are the main ones. It is concluded that chlorination is an important way to form PCBs in EAF steelmaking.
2. The concentration level and characteristics of new POP-PCNs emitted during the preheating and smelting process of EAF steelmaking are expounded. The concentration of PCNs in flue gas during the preheating stage from EAF steelmaking is 92.44~3473 ng Nm^-3. The emission levels of PCNs in fly ash during preheating and smelting are 1.05~15.18 ng g^-1 and 3.44~6.32 ng g^-1, respectively, indicating that the preheating stage is an important stage of PCNs formation. Among the 57 congeners of PCNs, 2-MOCN and 1-MOCN had higher concentrations. The concentration of PCNs homologues decreased with the increase of the number of chlorine substitutions. Moreover, there is a good correlation between the concentrations of PCNs and PCBs in fly ash (R=0.93), It is inferred that PCNs and PCBs have similar generation mechanisms in the EAF steelmaking.
3. EAF steelmaking was identified as a potential source of Cl/Br-PAHs, and the emission level and characteristics of new POPs-Cl/Br-PAHs during the preheating and smelting process from typical EAF steelmaking were clarified. The concentration of Cl-PAHs and Br-PAHs in flue gas during the preheating stage from EAF steelmaking is 48.65~3164 and 2.93~258 ng Nm^-3, respectively. The highest concentrations of Cl-PAHs and Br-PAHs in fly ash reached 69.1 and 10.05 ng g^-1. The characteristics of Cl/Br-PAHs in EAF steelmaking are not consistent with those in other thermal processes. 9-ClPhe/2-ClPhe contributes the highest among the Cl-PAHs congeners from the flue gas, while the 1-ClPyr from the waste incineration process accounts for the highest proportion, reaching 50%. 1-ClPyr is the highest proportion of Cl-PAHs in fly ash, while 9-ClPhe/2-ClPhe is the main congener in fly ash from secondary copper smelters.
 

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