Electrophilic chlorination of dibenzo-p-dioxin and dibenzofuran over composite copper and iron chlorides and oxides in combustion flue gas

Abstract

Dibenzo-p-dioxin (DD) and dibenzofuran (DF) chlorination mediated by Cu and Fe chlorides can make a direct contribution to the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in combustion flue gas. In this study, a kind of composite Cu and Fe chlorides and oxides (CuFe₉O_9.5Cl₁₀) was prepared by impregnating oxides with HCl solution to imitate the coexistence status of Cu and Fe species in combustion flue gas. Composite CuFe₉O_9.5Cl₁₀ was active in promoting the electrophilic chlorination of DD/DF at 150-300 °C, with the highest activity at 200 °C. DD/DF chlorination could occur under inert atmosphere, and 5% O₂ atmosphere was most favorable for DD/DF chlorination. Electrophilic chlorination of DD/DF primarily favored at 2,3,7,8 positions. Hybridization of Cu and Fe chlorides and oxides not only decreased the starting temperature and activation energy of DD/DF chlorination, but also induced a synergistic effect for accelerating the chlorination of DD/DF. The measured activities of composite CuFe₉O_9.5Cl₁₀ for promoting the chlorination of DD/DF were near to those of composite Cu chloride and oxide (CuO_0.2Cl_1.6), whereas 2 orders of magnitude higher than those of composite Fe chloride and oxide (FeO_0.3Cl_2.4). Comparison of PCDD/F congener distribution patterns indicated that DD/DF chlorination should be a main source of Cl_1-3DFs and Cl_1-2DDs in combustion flue gases.

Keywords: Chlorination; Combustion flue gas; Dioxins; Fe and Cu chlorides.