Development of phosphorus-based inhibitors for PCDD/Fs suppression

Abstract

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.