Heterogeneous catalytic ozonation of ciprofloxacin in aqueous solution using a manganese-modified silicate ore

Manganese modified silicate ore (MnSO) prepared using an impregnation method was used as a heterogeneous ozonation catalyst, and the catalytic activity was evaluated by the degradation of ciprofloxacin (CIP). The results showed that the manganese oxide was successfully loaded onto natural silicate ore (SO). The degradation and mineralization efficiencies of CIP were considerably improved in the presence of MnSO. Under optimal conditions, the CIP removal process followed the pseudo-first-order reaction model well. The degradation rate constant of MnSO/O₃ was 1.7 times and 3.3 times higher than those of SO/O₃ and only O₃, respectively. During the ozonation of the CIP aqueous solution in the presence of MnSO, the TOC removal rate reached 61.2% at 60 min, but was only 30.8% using ozonation alone. The addition of tert-butanol (TBA) significantly inhibited the degradation efficiency of CIP, which indicated that catalytic ozonation of MnSO followed a hydroxyl radical (·OH) reaction mechanism. Furthermore, MnSO showed great stability and durability over several reaction cycles.