MnO2@CS modified catalytic membrane for simultaneous organics removal and membrane fouling mitigation via peroxymonosulfate activation

Abstract

The integration of advanced oxidation process and ultrafiltration membrane has been regarded as an effective method to improve pollutants removal and mitigate membrane fouling simultaneously in the field of wastewater treatment. Hence, a novel catalytic membrane microreactor, referred to as MnO2@CS-UF, was synthesized via coupling MnO2 modified carbon spheres (MnO2@CS) with membrane. The mesoporous structure of MnO2@CS guaranteed adequate water transfer channels and also contributed to more exposure of active sites. With MnO2@CS uniformly dispersed, the MnO2@CS-UF membrane showed increased hydrophilicity, higher permeability and superior peroxymonosulfate (PMS)-activation capability. With synergistic effect of pore interception and catalytic degradation, MnO2@CS-UF showed excellent organic pollutants removal (MB removal of about 100 % in 5 min), and had a prominent mitigation effect on membrane fouling caused by model NOM. In addition, MnO2@CS-UF/PMS system showed excellent catalytic filtration performance in the treatment of actual secondary effluent (SE). MnO2@CS-UF/PMS system could effectively remove fluorescent organics, and the removal rates of I-V region were 36.3 %, 72.3 %, 67.7 %, 73.5 % and 71.4 %, respectively. The permeance decline of MnO2@CS-UF was also effectively alleviated, with irreversible and reversible resistances reduced by 61.0 % and 23.2 % than UF membranes, individually. High-valent manganese-oxo species and singlet oxygen played a leading role in contaminants elimination, whereas radical oxidation acted as auxiliary contributors. Standard blocking became the dominant fouling pattern for MnO2@CS-UF/PMS, demonstrating that the MnO2@CS catalytic layer ensured the synthesis of vast active substances, prevented foulant adhesion on pore walls and alleviated the growth of cake layer. These results illustrated that the integration of MnO2@CS catalytic degradation and membrane filtration was feasible to improve the permeate quality and mitigate membrane fouling in wastewater reclamation.