Effects of Different TiO2/CNT Coatings of PVDF Membranes on the Filtration of Oil-Contaminated Wastewaters.

Six different TiO2/CNT nanocomposite-coated polyvinylidene-fluoride (PVDF) microfilter membranes (including -OH or/and -COOH functionalized CNTs) were evaluated in terms of their performance in filtering oil-in-water emulsions. In the early stages of filtration, until reaching a volume reduction ratio (VRR) of ~1.5, the membranes coated with functionalized CNT-containing composites provided significantly higher fluxes than the non-functionalized ones, proving the beneficial effect of the surface modifications of the CNTs. Additionally, until the end of the filtration experiments (VRR = 5), notable flux enhancements were achieved with both TiO2 (~50%) and TiO2/CNT-coated membranes (up to ~300%), compared to the uncoated membrane. The irreversible filtration resistances of the membranes indicated that both the hydrophilicity and surface charge (zeta potential) played a crucial role in membrane fouling. However, a sharp and significant flux decrease (~90% flux reduction ratio) was observed for all membranes until reaching a VRR of 1.1-1.8, which could be attributed to the chemical composition of the oil. Gas chromatography measurements revealed a lack of hydrocarbon derivatives with polar molecular fractions (which can act as natural emulsifiers), resulting in significant coalescent ability (and less stable emulsion). Therefore, this led to a more compact cake layer formation on the surface of the membranes (compared to a previous study). It was also demonstrated that all membranes had excellent purification efficiency (97-99.8%) regarding the turbidity, but the effectiveness of the chemical oxygen demand reduction was slightly lower, ranging from 93.7% to 98%.

Spin-Label Electron Paramagnetic Resonance Spectroscopy Reveals Effects of Wastewater Filter Membrane Coated with Titanium Dioxide Nanoparticles on Bovine Serum Albumin.

The accumulation of proteins in filter membranes limits the efficiency of filtering technologies for cleaning wastewater. Efforts are ongoing to coat commercial filters with different materials (such as titanium dioxide, TiO2) to reduce the fouling of the membrane. Beyond monitoring the desired effect of the retention of biomolecules, it is necessary to understand what the biophysical changes are in water-soluble proteins caused by their interaction with the new coated filter membranes, an aspect that has received little attention so far. Using spin-label electron paramagnetic resonance (EPR), aided with native fluorescence spectroscopy and dynamic light scattering (DLS), here, we report the changes in the structure and dynamics of bovine serum albumin (BSA) exposed to TiO2 (P25) nanoparticles or passing through commercial polyvinylidene fluoride (PVDF) membranes coated with the same nanoparticles. We have found that the filtering process and prolonged exposure to TiO2 nanoparticles had significant effects on different regions of BSA, and denaturation of the protein was not observed, neither with the TiO2 nanoparticles nor when passing through the TiO2-coated filter membranes.

Enhancing ultrafiltration performance for dairy wastewater treatment using a 3D printed turbulence promoter.

Dairy factories annually generate an increasing amount of wastewater, which can cause eutrophication due to high concentrations of amino acids and lipids. To address this issue, membrane technology has emerged as a promising solution, but membrane fouling remains a significant challenge, since it can cause decreased flux, decrease membrane rejection performance, and increased energy demand. This study aimed to reduce membrane fouling by integrated a three-dimensional printed (3DP) turbulence promoter into an ultrafiltration dead-end cell and varying stirring speeds. Two mathematical models, Hermia and resistance-in-series, were used to analyze the fouling process. According to both models, the cake layer formation model indicated the most prevalent fouling mechanism. Specific energy demand, permeate flux, membrane rejection, and membrane reversible and irreversible resistances were measured, calculated, and compared. The results suggest that the combination of an integrated 3DP turbulence promoter and high stirring speeds can effectively reduce membrane fouling in a dairy wastewater treatment module.

Investigation of Photocatalytic PVDF Membranes Containing Inorganic Nanoparticles for Model Dairy Wastewater Treatment.

Membrane separation processes are promising methods for wastewater treatment. Membrane fouling limits their wider use; however, this may be mitigated using photocatalytic composite materials for membrane preparation. This study aimed to investigate photocatalytic polyvinylidene fluoride (PVDF)-based nanocomposite membranes for treating model dairy wastewater containing bovine serum albumin (BSA). Membranes were fabricated via physical coating (with TiO2, and/or carbon nanotubes, and/or BiVO4) and blending (with TiO2). Another objective of this study was to compare membranes of identical compositions fabricated using different techniques, and to examine how various TiO2 concentrations affect the antifouling and cleaning performances of the blended membranes. Filtration experiments were performed using a dead-end cell. Filtration resistances, BSA rejection, and photocatalytic cleanability (characterized by flux recovery ratio (FRR)) were measured. The surface characteristics (SEM, EDX), roughness (measured by atomic force microscopy, AFM), wettability (contact angle measurements), and zeta potential of the membranes were also examined. Coated PVDF membranes showed higher hydrophilicity than the pristine PVDF membrane, as evidenced by a decreased contact angle, but the higher hydrophilicity did not result in higher fluxes, unlike the case of blended membranes. The increased surface roughness resulted in increased reversible fouling, but decreased BSA retention. Furthermore, the TiO2-coated membranes had a better flux recovery ratio (FRR, 97%) than the TiO2-blended membranes (35%). However, the TiO2-coated membrane had larger total filtration resistances and a lower water flux than the commercial pristine PVDF membrane and TiO2-blended membrane, which may be due to pore blockage or an additional coating layer formed by the nanoparticles. The BSA rejection of the TiO2-coated membrane was lower than that of the commercial pristine PVDF membrane. In contrast, the TiO2-blended membranes showed lower resistance than the pristine PVDF membrane, and exhibited better antifouling performance, superior flux, and comparable BSA rejection. Increasing the TiO2 content of the TiO2-blended membranes (from 1 to 2.5%) resulted in increased antifouling and comparable BSA rejection (more than 95%). However, the effect of TiO2 concentration on flux recovery was negligible.

Outstanding Separation Performance of Oil-in-Water Emulsions with TiO2/CNT Nanocomposite-Modified PVDF Membranes.

Membrane filtration is an effective technique for separating micro- and nano-sized oil droplets from harmful oil-contaminated waters produced by numerous industrial activities. However, significant flux reduction discourages the extensive application of this technology; therefore, developing antifouling membranes is necessary. For this purpose, various titanium dioxide/carbon nanotube (TiO2/CNT) nanocomposites (containing 1, 2, and 5 wt.% multi-walled CNTs) were used for the modification of polyvinylidene fluoride (PVDF) ultrafilter (250 kDa) membrane surfaces. The effects of surface modifications were compared in relation to the flux, the filtration resistance, the flux recovery ratio, and the purification efficiency. TiO2/CNT2% composite modification reduced both irreversible and total filtration resistances the most during the filtration of 100 ppm oil emulsions. The fluxes were approximately 4-7 times higher compared to the unmodified PVDF membrane, depending on the used transmembrane pressure (510, 900, and 1340 L/m2h fluxes were measured at 0.1, 0.2, and 0.3 MPa pressures, respectively). Moreover, the flux recovery ratio (up to 68%) and the purification efficiency (95.1-99.8%) were also significantly higher because of the surface modification, and the beneficial effects were more dominant at higher transmembrane pressures. TiO2/CNT2% nanocomposites are promising to be applied to modify membranes used for oil-water separation and achieve outstanding flux, cleanability, and purification efficiency.