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PCDD/Fs’ suppression by sulfur–amine/ammonium compounds

Fu, Jian-Ying, Li, Xiao-Dong, Chen, Tong, Lin, Xiao-Qing, Buekens, Alfons, Lu, Sheng-Yong, Yan, Jian-Hua, Cen, Ke-Fa
Chemosphere 2015 v.123 pp. 9-16
ammonia, ammonium compounds, ammonium thiosulfate, aqueous solutions, dibenzofuran, gas emissions, hydrogen cyanide, incinerators, nitrogen, polychlorinated dibenzodioxins, polychlorinated dibenzofurans, sulfur dioxide, temperature, thiourea
Three distinct –S and –NH2 or NH4+ containing compounds, including ammonium thiosulfate, aminosulfonic acid and thiourea, were studied as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) inhibitors. All these three –S and –N containing compounds tested show strong suppression of PCDD/Fs formation, especially for thiourea which has not been studied before. With a (S+N)/Cl molar ratio of only 0.47, thiourea could inhibit 97.3% of PCDD/Fs and even 99.8% of I-TEQ. At an unusually high de novo test temperature (650°C), the PCDD/Fs’ formation was still very low but also the inhibition capacity of thiourea was weak, with an efficiency of 59% for PCDD/Fs when with a (S+N)/Cl molar ratio of 1.40. The results also revealed that the inhibition capability of the combined –S/–NH2 or –S/NH4+ suppressant was strongly influenced by both the nature of the functional group of nitrogen and the value of the molar ratio (S+N)/Cl. The amine functional group –NH2 tends to be more efficient than ammonium NH4+ and within a certain range a higher (S+N)/Cl value leads to a higher inhibition efficiency. Moreover, the emission of gases was continuously monitored: the Gasmet results revealed that SO2, HCN and NH3 were the most important decomposition products of thiourea. Thiourea is non-toxic, environment-friendly and can be sprayed into the post-combustion zone in form of powder or aqueous solution. The cost of thiourea at least can be partially compensated by its high inhibition efficiency. Therefore, the application of thiourea in a full-scale incinerator system is promising and encouraging.