Treatment of shale gas produced water by magnetic CuFe2O4/TNTs hybrid heterogeneous catalyzed ozone: Efficiency and mechanisms

Abstract

Magnetic spinel ferrite (CuFe₂O₄) has been applied to catalyze ozone for treating the practical shale gas produced water (PW) in our previous study. In this work, CuFe₂O₄/titanium nanotubes (TNTs) catalyst was successfully prepared by an impregnation-calcination method. Characterization results revealed that the crystal form of CuFe₂O₄ was bound to the surface of TNTs, the particle size is much smaller than the pure CuFe₂O₄ crystal particle, which could weaken the influence of the internal diffusion process on its catalytic efficiency. The experimental results showed that the removal ratio of COD_Cr in the CuFe₂O₄/TNTs/O₃ system was approximately 14% higher than that of the CuFe₂O₄/O₃ system. The dissolution of metal elements decreased to one-third that of the CuFe₂O₄/O₃ system. The inhibition ratio of PW on the growth of E. coli K12 decreased 68% after the CuFe₂O₄/TNTs catalytic oxidation process. Experimental results of complete capture experiments illustrated that the yield of HO• of the CuFe₂O₄/TNTs/O₃ system was 10-19% higher than that of the CuFe₂O₄/O₃ system. The elemental valence analysis revealed that the transition of Cu(II)-Cu(III) and Fe(II)-Fe(III) coexisted in the catalytic system. Besides, the surface hydroxyl groups promoted the electron transfer process and enhanced the ozone adsorption affinity. The proposed catalytic mechanisms of the CuFe₂O₄/TNTs/O₃ system were proposed via the above analysis.

Keywords: CuFe(2)O(4)/titanium nanotubes; Heterogeneous catalysis; Hydroxyl radicals; Ozone; Shale-gas produced water.