Effect of nitrogen-containing compounds on polychlorinated dibenzo-p-dioxin/dibenzofuran formation through de novo synthesis

An experimental study was conducted to clarify the suppression effect of nitrogen-containing compounds, that is, ammonia and urea, on the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) through the de novo synthesis reaction. In the experiment, graphite and copper chloride contained in a mixture were used as sources of carbon and chlorine, respectively. The granulated sample mixture was charged as a packed-bed in the glass tube and heated at 300 degrees C in the flow of Ar-O2 gas mixture. In some cases, urea was added as aqueous solution to the sample, while ammonia was added to the gas flowed through the sample bed. The amount of PCDD/Fs formed decreases significantly by the addition of both ammonia and urea. Particularly, the addition of urea reduces the amount of PCDD/Fs discharged in the outlet gas by approximately 90%. The oxidation rate of carbon in the early stage of the experiment, that is, the heating period, is promoted bythe addition of nitrogen-containing compounds. However, soon afterthe temperature reaches 300 degrees C, the formation rate becomes lower than that of the case without the addition of nitrogen-containing compounds. On the other hand, organic compounds containing amino (-NH2) or cyanide (-CN) groups and those containing nitrogen within the carbon ring frame were detected in the outlet gas in the case of urea addition. Typically observed aromatic compounds are chlorobenzonitriles, chlorobenzeneamines, and chloropyridines. This suggests a possibility that hydrogen and/or chlorine combined with PCDD/Fs are also substituted by such nitrogen-containing groups, and this decreases the formation rate of their frame of carbon rings. This phenomenon was also consistent with the fact that a significant reduction was observed in the amount of PCDD/Fs released to the outlet gas when urea was added.