Jin Guo

There is limited research on the relationship between membrane fouling and microbial metabolites in the nitrogen removal process coupled with membrane bioreactors (MBRs). In this study, we compared anoxic-oxic (AO) and partial nitritation–anammox (PNA), which were selected as representative heterotrophic and autotrophic biological nitrogen removal–coupled MBR processes for their fouling behavior. At the same nitrogen loading rate of 100 mg/L and mixed liquor suspended solids (MLSS) concentration of 4000 mg/L, PNA-MBR exhibited more severe membrane fouling compared to AO-MBR, as evidenced by monitoring changes in transmembrane pressure (TMP). In the autotrophic nitrogen removal process, without added organic carbon, the supernatant of PNA-MBR had higher concentrations of protein, polysaccharides, and low-molecular-weight humic substances, leading to a rapid flux decline. Extracellular polymeric substances (EPS) extracted from suspended sludge and cake sludge in PNA-MBR also contributed to more severe membrane fouling than in AO-MBR. The EPS subfractions of PNA-MBR exhibited looser secondary structures in protein and stronger surface hydrophobicity, particularly in the cake sludge, which contained higher contents of humic substances with lower molecular weights. The higher abundances of Candidatus Brocadia and Chloroflexi in PNA-MBR could lead to the production of more hydrophobic organics and humic substances. Hydrophobic metabolism products as well as anammox bacteria were deposited on the hydrophobic membrane surface and formed serious fouling. Therefore, hydrophilic membrane modification is more urgently needed to mitigate membrane fouling when running PNA–MBR than AO–MBR.

Polyethylene glycol (PEG) non-covalent-functionalized multi-walled carbon nanotubes (MWCNT) membrane were prepared by vacuum filtration. The dispersion and stability of MWCNT non-covalent functionalized with PEG were all improved. TEM characterization and XPS quantitative analysis proved that the use of PEG to non-covalent functionalize MWCNT was successful. SEM image analysis confirmed that the pore size of PEG–MWCNT membrane was more concentrated and distributed in a narrower range of diameter. Contact angle measurement demonstrated that PEG non-covalent functionalization greatly enhanced the hydrophilicity of MWCNT membranes. The results of pure water flux showed that the PEG–MWCNT membranes could be categorized into low pressure membrane. PEG-MWCNT membrane had a better effect on the removal of humic acid (HA) and a lower TMP growth rate compared with a commercial 0.01-μm PVDF ultrafiltration membrane. During the filtration of bovine serum albumin (BSA), the antifouling ability of PEG-MWCNT membranes were obviously better than the raw MWCNT membranes. The TMP recovery rate of PEG–MWCNT membrane after cross flushing was 79.4%, while that of raw MWCNT–_COOH and MWCNT membrane were only 14.9% and 28.3%, respectively. PEG non-covalent functionalization improved the antifouling ability of the raw MWCNT membranes and reduced the irreversible fouling, which effectively prolonged the service life of MWCNT membrane.

The effect of carbon nanotubes (CNT) modification on ultrafiltration membrane fouling control was explored. Three kinds of base membrane were chosen in the study: 20 kDa polysulfone (PS) membrane, 20 kDa and 100 kDa polyethersulfone (PES) membrane. Besides, the effect of pre-ozonation on the three CNT modified membranes for fouling alleviation was further studied. CNT modification presented antifouling properties at the beginning of filtration, while the recoverability of the CNT modified membranes are relatively lower as for the blocking of CNT layer by foulants. Pre-ozonation with a lower ozone concentration (0.25 mgO₃/mgDOC) did not efficiently alleviate the fouling of CNT modified membranes. With the ozone concentration increased to 0.81 mgO₃/mgDOC, the CNT modified membranes exhibited their higher antifouling properties. Water quality analysis results showed that CNT modification presented a higher capture ability for the humic-like and protein-like substances. After pre-ozonation, more organic materials could be retained in the interior of CNT layer, which decreased the fouling of base membranes and increased the permeate quality as well. Base membrane with large molecular size cut-off is more helpful for the synergistic effect of pre-ozonation and CNT modification.

To resolve membrane fouling in the ultrafiltration process of sewage effluent, the impact of activated carbon catalytic ozonation (AC/O₃) on fouling control was investigated. The influence of initial pH on AC/O₃ for fouling alleviation was further explored. The results revealed that AC/O₃ pretreatment greatly mitigated the membrane fouling. The total fouling, reversible fouling, and irreversible fouling were all decreased. The initial pH influenced the alleviation effect of AC/O₃ on fouling control obviously, although it only slightly impacted the AC adsorption pretreatment on fouling alleviation. Besides, there was no obvious impact of pH on the ultrafiltration process. Compared with the adjustment of initial pH during ultrafiltration and the pretreatment methods such as AC adsorption and preozonation, AC/O₃ displayed the greatest effect on both fouling alleviation and permeate quality improvement under all pH conditions. It was the component transformation of sewage effluent after AC/O₃ pretreatment that caused the alleviation of membrane fouling. With the increase in initial pH, the high-MW biopolymers as well as humic substances in the effluent organic matter could be preferentially removed by AC/O₃, which mitigated the flux decline during the ultrafiltration process and decreased the reversible and irreversible fouling.