Effect of urea on chlorinated aromatics formation mediated by copper and iron species in combustion flue gas

Urea ((NH₂)₂CO) is widely applied to the reduction of NO_X in modern full-scale solid waste incineration systems, but there is a lack of knowledge about how urea affects the formation and emission of Cl-aromatics. In this study, we investigated the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polychlorinated polychlorinated naphthalenes (PCNs) via electrophilic chlorination and precursor pathway mediated by model fly ashes containing Cu and Fe species with or without urea addition. The results indicated that the addition of urea promoted the direct chlorination of parent aromatics over Cu (Ⅱ) chlorides and the coupling reaction of chlorophenols over Fe species, while suppressed the catalytic chlorination of parent aromatics over Fe (Ⅲ) chlorides and the coupling reaction of chlorophenols over Cu species. The diverse effects should be mainly attributed to the formation of complex salts containing NH₃ and NH₄⁺. The formation of complex salts of Fe chlorides and NH₄Cl could hinder the oxidization of Fe chlorides, and thus maintain the high activity of Fe species for catalyzing the coupling reaction of chlorophenols. The formation of complex salts of Cu (Ⅱ) chloride and NH₃ could prevent the chemical sorption of phenoxyl groups, and thus suppress the coupling reaction of chlorophenols. NH₃ released from the thermal decomposition of urea could not only react with Cl₂ to suppress the catalytic chlorination of aromatics, but also neutralize HCl to accelerate the direct chlorination of aromatics. In general, urea should act as inhibitor for suppressing the formation of Cl-aromatics in solid waste incineration systems.