Evaluation of the Flexibility for Catalytic Ozonation of Dichloromethane over Urchin-Like CuMnOx in Flue Gas with Complicated Components.

The evaluation of the poisoning effect of complex components in practical gas on DCM (dichloromethane) catalytic ozonation is of great significance for enhancing the technique's environmental flexibility. Herein, Ca, Pb, As, and NO/SO2 were selected as a typical alkaline-earth metal, heavy metal, metalloid, and acid gas, respectively, to evaluate their interferences on catalytic behaviors and surface properties of an optimized urchin-like CuMn catalyst. Ca/Pb loading weakens the formation of oxygen vacancies, oxygen mobility, and acidity due to the fusion of Mn-Ca/Pb-O, leading to their inferior catalytic performance with poor CO2 selectivity and mineralization rate. Noticeably, the presence of As induces excessively strong acidity, facilitating the inevitable formation of byproducts. Catalytic co-ozonation of NO/DCM is achieved with stoichiometric ozone addition. Unfortunately, SO2 introduction brings irreversible deactivation due to strong competition adsorption and the loss of active sites. Unexpectedly, Ca loading protects active sites from an attack by SO2. The formation of unstable sulfites and the released Mn-O structure offset the negative effect from SO2. Overall, the catalytic ozonation of DCM exhibits a distinctive priority in the antipoisoning of metals with the maintenance of DCM conversion. The construction of more stable acid sites should be the future direction of catalyst design; otherwise, catalytic ozonation should be arranged together with post heavy metal capture and a deacidification system.

Catalytic ozonation of CH2Cl2 over hollow urchin-like MnO2 with regulation of active oxygen by catalyst modification and ozone promotion.

This paper firstly reported efficient catalytic ozonation of CH2Cl2 (dichloromethane, DCM) at low temperature over hollow urchin-like MnO2 with high chlorine resistance. Regulations on morphologies and Cu doping, as well as ozone promotion were conducted to optimize active oxygen of MnO2 catalysts, contributing to excellent catalytic behaviors. Cu doping MnO2 with hollow urchin-like morphology attained a stable 100% DCM conversion with O3/DCM molar ratio of 10 at 120 °C. The ozone utilization rate, final products, and byproducts distribution were discussed. Abundant crystal defects, low-valance Mn/Cu, Oads, and weak acidity, as well as better low temperature reducibility contributed to its superior performance. During DCM catalytic ozonation, DCM oxidation exhibited competitive effect on O3 decomposition due to the occupation of intermediates (CH2ClO3·, O-CH2Cl, and O-CH2 -O) over active sites that should belong to O3 originally. Nevertheless, O3 decomposition exhibited synergistic effects on DCM oxidation with promotion on active oxygen. Density functional theory (DFT) calculations confirmed the positive effect on oxygen vacancy formation and O3/DCM adsorption from Cu doping. The possible mechanism for DCM catalytic ozonation included four parts, including O3/DCM adsorption, O3 activation, DCM oxidation, and electron replenishment. This paper provides new insight for catalytic elimination of chlorinated alkanes at mild conditions.