Efficiencies and mechanisms of ZSM5 zeolites loaded with cerium, iron, or manganese oxides for catalytic ozonation of nitrobenzene in water

Discharge of industrial wastewater causes water pollution. It is therefore necessary to treat wastewater prior to discharge. Catalytic ozonation processes (COP) using ZSM5 zeolites loaded with metallic (Ce, Fe, or Mn) oxides to remove nitrobenzene from water were investigated. The total organic carbon (TOC) removal by the COP treatment with NaZSM5-38, HZSM5-38, and NaZSM5-100 were increased by 6.7%, 23.1%, and 19.8%, respectively, in comparison with single ozonation efficiency (39.2%). The loadings of Ce, Fe, or Mn oxides increased the catalytic activity relative to ZSM5 zeolites alone. The Ce loaded material (Ce/NaZSM5-38) had the highest TOC removal (86.3%). The different-metallic-oxides loaded zeolites exhibited different chemical processes during the removal of nitrobenzene from water. During COP treatment, NaZSM5-38 zeolites removed nitrobenzene mainly via OH mediated oxidation. HZSM5-38 and NaZSM5-100 zeolites showed powerful adsorption toward nitrobenzene. Both adsorption and direct ozonation contribute the TOC removal in their early uses. The OH mediated oxidation dominates the TOC removal process as the adsorption became saturated after multiple uses. Surface SiO bonds and/or SiO(H)Al structures are the active sites for ZSM5 zeolites. Efficient surface dispersion of the metallic oxides enhances the catalytic activity. This study shows the high potentials of ZSM5 zeolites as catalysts in COP to efficiently treat refractory wastewaters. Comparison of 3 series of zeolites for adsorption, hydroxy radical mediated oxidation, and TOC removals for 10 sequential uses in catalytic ozonation processes (COP) of nitrobenzene in water. [Display omitted] •ZSM-5 zeolites were studied for the catalysis of ozonation of nitrobenzene.•Mechanisms of nitrobenzene and TOC removal vary among types of ZSM-5 zeolites.•Surface SiO bonds and SiO(H)Al structures are active sites of ZSM5 zeolites.•Efficient surface dispersion of the metallic oxides enhances the catalytic activity.•ZSM5 zeolites are potential catalysts in ozonation treatment of refractory wastewaters.