再生铜冶炼过程中氯代和溴代多环芳烃的生成机理研究

Clorinated and brominated polycyclic aromatic hydrocarbons (Cl-PAHs and Br-PAHs, together abbreviated as X-PAHs) display similar toxic mechanism to that of dioxins, and the levels of X-PAHs are usually higher than that of dioxins in many environmental matrices. The unintentional formation and release during various industrial thermal processes are considered as the major sources of X-PAHs. Secondary metal smelting processes are speculated to be one of potential important sources of X-PAHs. However, study on the formation mechanism of X-PAHs during secondary metal smelting processes have not been carried out. In this project, secodary copper smeling processes will be selected for studying the formation mechanism of X-PAHs. The formation mechanism of X-PAHs during secondary copper smelting processes will be clarified by the combination of field investigation with laboratory simulation study. The formation characteristics of X-PAHs in stack gas and fly ash released from secondary copper smelting will be demonstrated. Fly ash is considered as very important matrix for catalyzing the formation of unintentional persistent organic pollutants. The potential precursors of X-PAHs in stack gas and fly ash will be indentified and quantified. Based on the results of field investigation, laboratory simulation studies that using fly ash as the reaction matrix and labeled precursors as model compounds will be performed to elucidate the formation mechanism and key influencing factors of X-PAHs, which will give helpful knowledge for guiding the emission control and reduction of X-PAHs during secondary copper smelting processes.

氯代和溴代多环芳烃（Cl-PAHs和Br-PAHs,通称简写为X-PAHs）具有和二恶英类似的毒性和比二恶英更高的环境污染水平，已引起广泛关注。再生金属冶炼被推断是X-PAHs的重要潜在源，然而，目前对再生金属冶炼过程X-PAHs生成机制的研究尚属空白。本项目将以再生铜冶炼工业为例，通过对实际再生铜冶炼的现场研究和实验室模拟研究的结合来揭示再生铜冶炼过程X-PAHs的生成机制。通过对实际再生铜冶炼的现场研究来揭示烟道气和飞灰中X-PAHs的生成特征和气固分配规律，飞灰是工业生产过程中有机污染物生成的重要催化基质，通过对实际飞灰的表征和分析来识别X-PAHs的潜在前驱体和关键催化元素。依据现场研究的结果，以实际飞灰为基质，以稳定同位素标记的典型前驱体为模型化合物开展实验室模拟研究，根据稳定同位素示踪原理，揭示X-PAHs生成的主要机理，为控制再生金属冶炼过程中X-PAHs的排放提供理论依据。

建立了工业源烟气和飞灰样品中Cl, Br-PAHs的定性定量分析方法，成果发表在J. Chrom. A。国际环境分析学家Ivan Španik教授在J. Sep. Sci.发文对我们的工作评价指出：我们以13C-标记的同类物为内标建立了重要的HRGC/HRMS方法，所建立的方法比文献中的氘代内标法检出限低两个数量级，比传统GC/MS方法检出限低3个数量级。利用建立的方法研究了再生铜及其他金属冶炼过程Cl, Br-PAHs的排放特征和生成机理，提出再生金属冶炼过程Cl, Br-PAHs的排放因子，所提出的指纹谱图可为识别环境中的Cl, Br-PAHs提供依据。研究了再生金属冶炼飞灰作用下Cl, Br-PAHs和其他POPs的热化学反应变化，根据Cl, Br-PAHs和其他POPs的热化学生成特征，提出了其可能的生成机理，为Cl, Br-PAHs和其他POPs的协同控制提供了理论依据。.项目顺利完成了预期目标，发表SCI收录论文13篇，包括2篇ES&T。培养三名硕/博士生顺利毕业，1名博士后顺利出站。