Role of zinc in MSW fly ash during formation of chlorinated aromatics.
In this study, we determined the thermochemical role of zinc in municipal solid waste (MSW) fly ash. Zinc's role depended on its chemical form and the presence of other metal catalysts. When only zinc was present or it dominated other metal elements, chlorinated aromatic compound (aromatic-Cl) formation was promoted by zinc chloride but blocked by zinc oxide. When only zinc was present, such as in zinc metallurgical plants, some aromatic-Cls were generated and contaminated the environment. When zinc coexisted with other metal promoters in a thermal postcombustion solid phase, such as MSW incineration, Fourier-transform Zn K-edge extended X-ray absorption fine structure (EXAFS) analysis showed that the chemical forms of zinc were primarily chloride and/or oxide, and zinc chloride (ZnCl(2)) was thermally stable in the solid phase. Thus, we used ZnCl(2) in coexistence experiments as a promoter to generate aromatic-Cls. Zinc chloride acted as a coexistent inhibitor of metal catalysis and precursor dimerization to generate aromatic-Cls. There were two coexistent inhibition mechanisms. First, a low-temperature transition of chlorine to the gas phase (low-Cl(g)) occurred with metal catalysts such as CuCl(2) and FeCl(3), confirmed by Cl K-edge near-edge X-ray absorption fine structure (NEXAFS) analysis. Second, X-ray photoelectron spectroscopy (XPS) analysis of the surface or near-surface concentration of ZnCl(2) indicated weak reactivity between the catalysts and the carbon matrix.