Inhibition mechanisms of sulfur-, nitrogen- and phosphorus- based inhibitors on the de novo synthesis of polychlorinated dibenzo-p-dioxins, and dibenzofurans (PCDD/F) were studied by exploring speciation evolution of carbon, chorine and copper in fly ash under laboratory-scale experiments. Significant inhibition of PCDD/Fs by thiourea (TUA) and ammonium dihydrogen phosphate (ADP) was observed as 97.2% and 98.2%, respectively, except for potassium dihydrogen phosphate (PDP). ADP and PDP exhibited better inhibition on PCDFs than on PCDDs, whereas TUA exhibited the opposite effect. After adding inhibitors, the proportion of C-O/C=O/O-C=O bonds at the surface of fly ash increased, and stronger oxidation of carbon occurred, together with the conversion from Cu2+ to Cu+ and the inhibition of organic chlorine formation. Kinetic model results indicated that TUA might either suppress the carbon gasification or promote the decomposition of PCDD/Fs, resulting in a remarkable inhibition of PCDD/Fs formation. Simulated chemical reaction equilibrium further comfirmed that catalytic metal could be deactivated into CuS and Cu2S by sulfur, and into Cu2P2O7 by phosphorus. Moreover, NH3, decomposed from TUA and ADP, was able to convert Cl2 into HCl, albeit with a weaker chlorination ability. This study of inhibition mechanisms is useful for the exploration and utilization of efficient inhibitors in full-scale incinerators.
Keywords: Chemical reaction simulation; Inhibition; Morphological characterization; PCDD/Fs; Phosphorus based compounds.
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