Takaoka Masaki, Shiono Atsuhiro, Yamamoto Takashi, Uruga Tomoya, Takeda Nobuo, Tanaka Tsunehiro, Oshita Kazuyuki, Matsumoto Tadao, Harada Hiroki
Department of Urban and Environmental Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8540, Japan.
Chemosphere. 2008 Aug;73(1 Suppl):S78-83. doi: 10.1016/j.chemosphere.2007.06.093. Epub 2008 Apr 28.
Only limited information on the chemical forms of copper in municipal solid waste incinerator (MSWI) fly ash is available in the literature. Therefore, we performed in situ X-ray absorption near-edge spectroscopy (XANES) experiments involving two types of real fly ash to confirm the behavior of copper in fly ash at secondary formation temperatures for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). CuCl(2).3Cu(OH)(2) was detected in both fly ash types before heating experiments. Cupric compounds in real fly ash were reduced to cuprous compounds or elemental copper at approximately 200 degrees C. The changes in the Cu XANES spectra observed for the two fly ash samples were similar to those observed previously. We also examined the behavior of copper in model fly ash using SiO(2) to investigate the effect of supporting materials and copper content in fly ash on the dynamic changes of copper and amount of dioxins generated. There was little difference between the use of boron nitride (BN) and SiO(2) as a supporting material. The formation mechanisms of PCDDs and PCDFs in both of the model fly ash types were basically the same. Thus, we conclude that the dynamic change of copper in MSWI fly ash during heating is a commonly observed feature, and no simple relationship between the composition of fly ash and the amount of PCDD/PCDF generated or dynamic change of copper is apparent. The dynamic change of copper explained the generated amount and homologue distribution of PCDDs and PCDFs.
关于城市固体废物焚烧炉(MSWI)飞灰中铜的化学形态,文献中仅有有限的信息。因此,我们对两种实际飞灰进行了原位X射线吸收近边光谱(XANES)实验,以确认在多氯二苯并对二噁英(PCDDs)和二苯并呋喃(PCDFs)二次生成温度下飞灰中铜的行为。在加热实验之前,在两种飞灰中均检测到CuCl₂·3Cu(OH)₂。实际飞灰中的铜化合物在约200℃时还原为亚铜化合物或元素铜。观察到的两种飞灰样品的Cu XANES光谱变化与之前观察到的相似。我们还使用SiO₂研究了模型飞灰中铜的行为,以探讨飞灰中载体材料和铜含量对铜的动态变化及二噁英生成量的影响。使用氮化硼(BN)和SiO₂作为载体材料几乎没有差异。两种模型飞灰中PCDDs和PCDFs的形成机制基本相同。因此,我们得出结论,MSWI飞灰在加热过程中铜的动态变化是一个普遍观察到的特征,飞灰组成与PCDD/PCDF生成量或铜的动态变化之间没有明显的简单关系。铜的动态变化解释了PCDDs和PCDFs的生成量及同系物分布。