Investigation of Catalytic Ozonation of Recalcitrant Organic Chemicals in Aqueous Solution over Various ZSM-5 Zeolites

Abstract

Catalytic ozonation processes (COPs) are an emerging technology for wastewater treatments. NaZSM-5 zeolites in three different SiO2/Al2O3 ratios (31, 45, and 120) and their metallic oxides loaded samples were compared for COP of nitrobenzene solution. NaZSM-5(120) showed high total organic carbon (TOC) removals (70.2–74.0%) by adsorption relative to NaZSM-5(45) (0.4–0.6%) at various initial pH conditions. NaZSM-5(31) was obtained by NaOH treatment of NaZSM-5(45) and displayed 20.9–23.8% of TOC removals by adsorption. In COPs, the different ZSM-5 zeolites exhibited various TOC removals and different reaction pathways. COP-NaZSM-5(120) showed high TOC removals compared to COP-NaZSM-5(45) and COP-NaZSM-5(31). The repeated uses of zeolites in COPs were performed to understand the reaction pathways and contribution of adsorption versus ozonation (i.e., catalytic oxidation and/or direct ozonation). Both adsorption and direct ozonation in COP-NaZSM-5(120) contributed TOC removal for the first use, whereas direct ozonation and •OH mediated oxidation dominated the process for eight repeated uses. Direct ozonation and •OH-mediated oxidation controlled the COP-NaZSM-5(45) process for the first and eight repeated uses. Adsorption and direct ozonation governed the COP-NaZSM-5(31) process for the first use, whereas the direct ozonation dominated it for eight repeated uses. In COPs, NaZSM-5(120) and NaZSM-5(45) showed the catalytic activity, whereas NaZSM-5(31) displayed negligible catalytic activity. The high catalytic activity of NaZSM-5(120) may be due to more Si-O bonds on zeolite surfaces. The results revealed that loading of Mg oxide on ZSM-5 zeolites can increase catalytic activity in COPs. These results show the application potential of ZSM-5 zeolites in ozonation of recalcitrant chemical wastewaters.