Thermochemical behavior of lead adjusting formation of chlorinated aromatics in MSW fly ash

In this study, we examined the thermochemical role of Pb in the formation of chlorinated aromatics (aromatic-Cls) in MSW fly ash at 300-400 °C, a key temperature window for maximum yield. In the presence of lead oxide alone, aromatic-Cls formation was suppressed. One of the mechanisms of suppression was partial chlorination of PbO by an inorganic chlorine source in the solid phase, based on in situ Pb L3-edge X-ray absorption near-edge structure (XANES) data. In contrast, quantitative GC/MS measurements revealed that PbCl2 promoted aromatic-Cls formation to an extent that depends on the Pb concentration, the heating temperature, and the presence of other metal catalysts. We identified two mechanisms of aromatic-Cls formation triggered by PbCl2 in MSW fly ash. First, promotion can occur by the thermochemical partial oxidation of PbCl2. More specifically, real complex solid phase increases the thermochemical oxidation reactivity of PbCl2, based on in situ Pb L3-edge XANES data. Second, Cl K-edge X-ray absorption spectroscopy revealed a coexistent effect of PbCl2 with other metal catalysts such as CuCl2 and FeCl3. The presence of PbCl2 influences the balance of the bonding state of chlorine with Cu and Fe atoms at various temperatures. Thus, Pb in real MSW fly ash functions as an "adjuster" in the generation of aromatic-Cls, the nature of which depends on the lead oxide/chloride ratio and the presence of other metal catalysts.