Hydrothermal oxidation degradation of dioxins in fly ash with water-washing and added Ce–Mn catalyst

A comprehensive analysis of the effects of the temperature, reaction time, liquid-solid ratio (L/S), and initial pH on the hydrothermal degradation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) (which are both PCDD/Fs) in municipal solid waste incineration (MSWI) fly ash is presented. Consequently, the hydrothermal degradation reaction is catalyzed using Ce-Mn catalyst under low-temperature conditions to study the effect of the catalyst on the degradation efficiency of PCDD/Fs. The experimental results show that temperature is the most critical factor for the reaction. When the hydrothermal oxidation temperature reaches 280 °C (reaction time = 120 min, original pH = 8.5, L/S = 4 mL/g), the toxicity equivalent (I-TEQ) of PCDD/Fs is only 5.4 ng TEQ/kg, and the degradation efficiency reaches 99.71%. Under these conditions, 2,3,4,7,8-P5CDF makes the highest contribution to I-TEQ degradation, reaching 37.4%. There are four main pathways for the reaction of 2,3,4,7,8-P5CDF with hydroxyl radicals. A comparison of the PCDD/F concentrations of different products shows that the addition of 0.5%, 1.0%, and 1.5% of the Ce-Mn catalyst reduces the degradation efficiency by 8.79%, 1.40%, and 0.07%, respectively, which indicates that the addition of a small quantity of Ce-Mn catalyst does not facilitate the degradation of PCDD/Fs. The addition of the catalyst significantly decreases the degradation efficiency of low-chlorinated homologs but has a relatively small effect on that of high-chlorinated homologs. Therefore, it is concluded that Ce-Mn catalysts are more likely to promote resynthesis than degradation of PCDD/Fs.