Treatment of high-salinity brine containing dissolved organic matters by vacuum membrane distillation: A fouling mitigation approach via microbubble aeration.

In this study, a laboratory-scale vacuum membrane distillation (VMD) system coupled with microbubble aeration (MBA) was developed for the treatment of high-salinity brine containing organic matters. Herein, at the beginning, feedwater only containing model organics such as humic acid (HA), bovine serum albumin (BSA) and sodium alginate (SA) was utilized to investigate the organic-fouling behavior, results indicated that the permeate flux was not affected by a thin and loose contaminated layer deposited on the membrane surface. Furthermore, dissolved organics in the feed brine inhibited the occurrence of membrane wetting due to the existence of a compact and protective crystals/organic-fouling layer, which can prevent the intrusion of scaling ions into membrane substrates. Besides, organics in the feedwater have a high tendency to adsorb on the membrane surface based on molecular dynamics simulations, thus, forming an organic-fouling layer prior to inorganic scaling. Finally, the effect of MBA on fouling alleviation was evaluated in VMD system, nearly 50% of salt precipitation from fouled membrane was effectively removed with the introduction of MBA, which can be ascribed to a combination of mechanisms, including surface shear forces and electrostatic attractions induced by microbubbles, meanwhile, about 2.2% of the total energy was only consumed, when using MBA. Together, these results demonstrated that MBA was a promising approach to alleviate membrane fouling in VMD.

Modification of the distribution of humic acid complexations by introducing microbubbles to membrane distillation process for effective membrane fouling alleviation.

Membrane fouling caused by inorganic ions and natural organic matters (NOMs) has been a severe issue in membrane distillation. Microbubble aeration (MB) is a promising technology to control membrane fouling. In this study, MB aeration was introduced to alleviate humic acid (HA) composited fouling during the treatment of simulative reverse osmosis concentrate (ROC) by vacuum membrane distillation (VMD). The objective of this work was to explore the HA fouling inhibiting effect by MB aeration and discuss its mechanism from the interfacial point of view. The results showed that VMD was effective for treating ROC, followed by a severe membrane fouling aggravated with the addition of 100 mg/L HA in feed solution, resulting in 45.7% decline of membrane flux. Analysis using the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory and zeta potential distribution of charged particles proved the coexistence of HA and inorganic cations (especially Ca2+), resulting in more serious membrane fouling. The introduction of MB aeration exhibited excellent alleviating effect on HA-inorganic salt fouling, with the normalized flux increased from 19.7% to 37.0%. The interfacial properties of MBs played an important role, which altered the zeta potential distributions of charged particles in HA solution, indicating that MBs adhere the HA complexations. Furthermore, this mitigating effect was limited at high inorganic cations concentration. Overall, MBs could change the potential characteristics of HA complexes, which also be used for other similar membrane fouling alleviation.

Effects of Alkaline Cleaning on the Conversion and Transformation of Functional Groups on Ion-Exchange Membranes in Polymer-Flooding Wastewater Treatment: Desalination Performance, Fouling Behavior, and Mechanism.

The aging effects of sodium hydroxide (NaOH) on ion-exchange membranes were systematically studied, including the membrane properties, desalination performance, and fouling behaviors. After aging in NaOH solution, there were minor changes in the cation-exchange membrane (CEM) properties; however, functional groups (i.e., quaternary amines) on the anion-exchange membranes (AEMs) were converted into benzylic alcohol, alkene, and tertiary amines, respectively, by nucleophilic substitution, Hofmann elimination, and ylide formation. These degradations rendered decreased ion-exchange capacity (IEC), increased electrical resistance, lost hydrophilicity, and weakened mechanical strength. Moreover, severe deteriorations of desalination performance were observed due to the little ion-exchange ability of the degraded AEMs. The desalination rates were restored after cultivating the aged AEMs in acid solution, mainly because the tertiary amines transformed from the hydroxide form (OH-form) to the ionic chlorine form (Cl-form). The restored desalination rates indicated that the main degradation products were tertiary amines. In addition, the antifouling performance decreased in the order of aged OH-form > aged Cl-form > original AEMs due to the reduction of foulant-membrane intermolecular interactions after aging in NaOH solution. The results contribute to establishing a more comprehensive understanding of the effects of alkaline cleaning on IEMs and provide new insights into cleaning-process optimization and membrane modification.

Identification of fouling mechanisms in MBRs at constant flowrate: model applications and SEM-EDX characterizations.

A fundamental understanding of fouling mechanisms is critical to improving filtration operations. The performance of four parallel membrane bioreactors (MBRs) with different sludge retention times (SRTs) was monitored during long-term constant flowrate filtration. The characteristics of the membrane and transmembrane pressure (TMP) profiles obtained were studied to demonstrate fouling mechanisms. Both classical blocking models and their combined models were evaluated. The intermediate model provided very good agreement with all the TMP data. However, the combined cake-intermediate and intermediate-standard models were more effective in the description of the experimental data. Contributions analysis indicated that the cake, intermediate and standard blocking models were the dominant fouling mechanisms. Scanning electron microscopy and energy dispersive X-ray (SEM-EDX) imaging showed that cake blocking by organic matter and standard blocking by inorganic matter made the main contributions to membrane fouling. The combined cake-intermediate and intermediate-standard models may be applicable to systems where these two models are consistent with the experimentally observed fouling mechanisms in an MBR.

Molecular Mechanisms of Ultrafiltration Membrane Fouling in Polymer-Flooding Wastewater Treatment: Role of Ions in Polymeric Fouling.

Polymer (i.e., anionic polyacrylamide (APAM)) fouling of polyvinylidene fluoride (PVDF) ultrafiltration (UF) membranes and its relationships to intermolecular interactions were investigated using atomic force microscopy (AFM). Distinct relations were obtained between the AFM force spectroscopy measurements and calculated fouling resistance over the concentration polarization layer (CPL) and gel layer (GL). The measured maximum adhesion forces (Fad,max) were closely correlated with the CPL resistance (Rp), and the proposed molecular packing property (largely based on the shape of AFM force spectroscopy curve) of the APAM chains was related to the GL resistance (Rg). Calcium ions (Ca(2+)) and sodium ions (Na(+)) caused more severe fouling. In the presence of Ca(2+), the large Rp corresponded to high foulant-foulant Fad,max, resulting in high flux loss. In addition, the Rg with Ca(2+) was minor, but the flux recovery rate after chemical cleaning was the lowest, indicating that Ca(2+) created more challenges in GL cleaning. With Na(+), the fouling behavior was complicated and concentration-dependent. The GL structures with Na(+), which might correspond to the proposed molecular packing states among APAM chains, played essential roles in membrane fouling and GL cleaning.

Comparison of the effects of extracellular and intracellular organic matter extracted from Microcystis aeruginosa on ultrafiltration membrane fouling: dynamics and mechanisms.

Algae organic matter (AOM), including intracellular organic matter (IOM) and extracellular organic matter (EOM), are major membrane foulants in the treatment of algae-polluted water. In this study, the effects of EOM and IOM (at dissolved organic concentrations of 8 mg/L) on the fouling of a poly(ether sulfone) ultrafiltration (UF) membrane were investigated using a dead-end down-flow UF unit. Changes in the membrane pore geometry and the interaction energy between the membrane and foulants were analyzed based on the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory. The data (relative standard deviation within 10%) showed that UF was able to retain 57% and 46% of IOM and EOM respectively, while the corresponding membrane fluxes rapidly reduced to 28% and 33% of their respective initial values after a specific filtration volume of only 3.75 mL/cm(2). The fouling model implied that cake formation was the major mechanism. Specifically, IOM foulant had a much greater free energy of cohesion (-59.08 mJ/m(2)) than EOM foulant (3.2 mJ/m(2)), leading to the formation of a compacted cake layer on the membrane surface. In contrast, small molecules of hydrophobic EOM tended to be adsorbed into the membrane pores, leading to significant reduction of the pore size and membrane flux. Therefore, the overall fouling rates caused by EOM and IOM were comparable when both of the above-mentioned mechanisms were considered.

Rapid cultivation of aerobic granular sludge by bone glue augmentation and contaminant removal characteristics.

To achieve a quick start-up and stable operation, aerobic granular sludge (AGS) was cultivated in a sequencing batch airlift reactor (SBAR) with the addition of bone glue augmentation. Adding an amount of bone glue (40 mg L(-1)) can accelerate granulation, which advanced by 10 d on average. Aerobic granules of size 0.5-3.0 mm were dominant in the SBAR and the settling velocity acquired a better correlation with the size of the AGS. In addition, the content of total polysaccharides was 19.54 mg gMLSS(-1) (grams of mixed liquor suspended solids) (an increase of 34.0%), the content of total protein was 60.59 mg gMLSS(-1) (an increase of a factor of 33) and the total proteins/total polysaccharides ratio was 3.3. The relatively high protein content was an essential feature for cultivation of AGS, which may indicate that extracellular polymeric substance was the mechanism for granulation due to the adhesion of microorganisms by bone glue. AGS possessed better chemical oxygen demand, NH4(+)-N and PO4(3-)-P removal efficiency (of 86.7, 90.6 and 93.8%, respectively) and no nitrite accumulation was observed in the whole process.

Fundamental characteristics study of anion-exchange PVDF-SiO(2) membranes.

A new type of poly(vinylidene fluoride)(PVDF)-SiO(2) hybrid anion-exchange membrane was prepared by blending method. The anion-exchange groups were introduced by the reaction of epoxy groups with trimethylamine (TMA). Contact angle between water and the membrane surface was measured to characterize the hydrophilicity change of the membrane surface. The effects of nano-sized SiO(2) particles in the membrane-forming materials on the membrane mechanical properties and conductivity were also investigated. The experimental results indicated that PVDF-SiO(2) anion-exchange membranes exhibited better water content, ion-exchange capacity, conductivity and mechanic properties, and so may find potential applications in alkaline membrane fuel cells and water treatment processes.

Preparation of single-walled carbon nanotubes/polyvinylchloride membrane and its antibacterial property.

Polyvinylchloride (PVC) ultrafiltration membranes were modified by blending with single-walled carbon nanotubes (SWCNTs) to improve the membranes' antibacterial property. Both modified and control samples were characterized for pore structure, roughness, hydrophilicity, permeability and mechanical properties. The membranes' antibacterial property was accessed with Escherichia coli as the model microbes by several methods. It was found that, after being blended with SWCNTs, the surface roughness of the modified membrane increased. Also, the surface hydrophilicity was improved. The membrane flux increased accordingly. But the membrane elongation decreased obviously with the SWCNTs addition. The modified membranes did not show the antibacterial property as expected in this research. There was no bacterial inhibition circle around the SWCNTs/PVC membrane coupons in the culture plates. There were no morphological differences of the cells on the control and the modified membranes. Hoechst 33342/propidium iodide stain test showed that there were more than 90% living bacterial cells which could grow on the SWCNTs/PVC membranes. This study suggests that the polymer wrapping may reduce the SWCNTs' antibacterial property greatly.

Improved anti-organic fouling and antibacterial properties of PVDF ultrafiltration membrane by one-step grafting imidazole-functionalized graphene oxide.

At present, membrane fouling is a thorny issue that limits the development of polyvinylidene fluoride (PVDF) composite membrane, which seriously affects its separation performance and service lifespan. Herein, an imidazole-functionalized graphene oxide (Im-GO) with hydrophilicity and antibacterial performance was synthesized, and it was used as a modifier to improve the anti-organic fouling and antibacterial properties of PVDF membrane. The anti-organic fouling test showed that the maximum flux recovery ratios against bovine serum albumin and humic acid were 88.9% and 94.5%, respectively. Conspicuously, the grafted imidazole groups could effectively prevent the bacteria from growing on the membrane surface. It was gratifying that the antibacterial modifier Im-GO was almost not lost from the hybrid membranes even by the ultrasonic treatment, which was different from the conventional release-killing antibacterial agents. Owing to the long-term anti-organic fouling and antibacterial properties, Im-GO/PVDF hybrid membranes exhibit a great application potential in the fields of rough separation and concentration of biomedical products.

Microbubble aeration enhances performance of vacuum membrane distillation desalination by alleviating membrane scaling.

Membrane fouling, especially inorganic fouling due to salt crystal formation and deposition on the membrane surface, is still a major technical issue in membrane distillation (MD) applications. In this study, microbubble aeration (MBA) was included in a laboratory-scale vacuum membrane distillation (VMD) rig and its effect on a desalination process was examined. Without MBA, serious membrane scaling occurred during desalination of simulated high-salinity sea water (100 g.L-1 salt concentration), which resulted in a dramatic reduction of permeate flux to essentially zero after 120 min. Scanning electron microscopy showed that a layer of large cuboid salt crystals uniformly covered the membrane surface. However, membrane scaling was mitigated with the introduction of MBA, resulting in the improved VMD desalination performance, which was positively correlated with pump pressure in the microbubble (MB) generator. Results showed that the effective processing time of the VMD desalination processing cycle was respectively prolonged to 150, 180, and more than 300 and 360 min (cf. 120 min without MBA) when the pump pressure was respectively at 0.1, 0.2, 0.3 and 0.4 MPa, leading to the increase of cumulative water production. Further studies found that larger numbers of MBs of smaller size were produced at higher pump pressure, which are more beneficial for increasing water vapor production and alleviating salt precipitation. The difference in zeta potential between the MBs in distilled water (about -30 mV) and that in SW100 solution (about -2 mV) demonstrated that MBA not only effectively mitigated the negative effect of concentration polarization by enhancing the surface shear rate at the membrane surface, but also reduced salt precipitation probably due to the MBs attracting counterions to the gas-water interface. Finally, energy consumption analysis of the modified VMD desalination process revealed that MBA, while itself only adding about 3% to the total energy consumption at varied pump pressures, was able to improve the specific energy consumption, especially at higher pump pressures. Together, these results demonstrate that MBA is an effective way of improving the performance of VMD desalination of water.

Reaction mode between Si and Fe and evaluation of optimal species in poly-silicic-ferric coagulant.

A kind of Fe-polysilicate polymer, poly-silicic-ferric (PSF) coagulant was prepared by co-polymerization (hydroxylation of mixture of Fe3+ and fresh polysilicic acid (PS)), in which PSF0.5, PSF1 or PSF3 denotes Si/Fe molar ratio of 0.5, 1 or 3, respectively. The effects of Si/Fe ratio and reaction time (co-polymerization time or aging time) on the reaction mode between Si and Fe were studies, and the optimal species of PSF was evaluated by pH change during the preparation of PSF and coagulation tests. The results showed that the characteristics of PSF are largely affected by both reaction time and Si/Fe ratio. PSF is found to be a essential complex of Si, Fe, and many other ions. The reaction mode between Si and Fe differs with various Si/Fe ratios. The pH of PSF0.5, PSF1 or PSF3 tended to be stable when reaction time is 10, 25 or 55 min, respectively, which is almost consistent with the time reaching the relative stable morphology that is just the optimal species of higher coagulation efficiency. The optimal reaction time reaching optimal species can be evaluated by measuring the pH change during the polymerization process.

Role of extracellular exopolymers on biological phosphorus removal.

Three sequencing batch reactors supplied with different carbon sources were investigated. The system supplied with glucose gained the best enhanced biological phosphorus removal although all of the three reactors were seeded from the same sludge. With the measurement of poly-beta-hydroxyalkanoate (PHA) concentration, phosphorus content in sludge and extracellular exopolymers (EPS) with scanning electron microscopy (SEM) combined with energy dispersive spectrometry (EDS), it was found that the biosorption effect of EPS played an important role in phosphorus removal and that the amount of PHA at the end of anaerobic phase was not the only key factor to determine the following phosphorus removal efficiency.

Flux enhancement during ultrafiltration of produced water using turbulence promoter.

Concentration polarization and membrane fouling remain one of the major hurdles for the implementation of ultrafiltration of produced water. Although many applications for ultrafiltration were already suggested, only few were implemented on an industrial scale. Among those techniques, turbulence promoter can be more simple and effective in overcoming membrane fouling and enhancing membrane flux. As for the result that turbulence promoter increase fluid velocity, wall shear rates and produce secondary flows or instabilities, the influence of turbulence promoter was investigated on permeate flux during produced water ultrafiltration and the potential application of this arrangement for an industrial development. Experimental investigations were performed on 100 KDa molecular weight cut-off PVDF single-channel tubular membrane module using four kinds of turbulence promoters. It is observed that the significant flux enhancement in the range of 83%-164% was achieved while the hydraulic dissipated power per unit volume of permeate decreased from 31%-42%, which indicated that the using of turbulence promoter is more efficient than operation without the turbulence promoter. The effects of transmembrane pressure and cross-flow velocity with and without turbulence promoter were studied as well. Among the four kinds of turbulence promoters, winding inserts with 20.0 mm pitch and 1.0 mm wire diameter showed better performances than the others did.

Effect of components in activated sludge liquor on membrane fouling in a submerged membrane bioreactor.

By a membrane bioreactor with a settle tank in long-term operation and batch experiments, the effects of flocs, soluble microorganism products (SMPs) and metal ions in activated sludge liquor on membrane fouling were investigated. The results showed that foulants absorbed each other and formed a fouling layer as a "second membrane" influencing the permeability of the membrane. The "gel layer" caused by SMPs and "cake layer" by flocs showed great differences in morphology by analysis of scanning electron microscope and atomic force microscope. The "gel layer" was more compact and of poor permeability. When the membrane flux was 40 L/(m(2) x h), the rate of membrane fouling caused by supernatant (0.011 MPa/h) was greater than that by sludge liquor (0.0063 MPa/h). SMPs played very important roles on membrane fouling. In the bulking sludge, with SMPs increasing, the rate of membrane fouling (0.0132 MPa/h) was faster. While after flocculation of the SMPs, the rate of fouling decreased to 0.0034 MPa/h. Flocs could keep holes in their overlaps. They could alleviate membrane fouling by preventing the SMPs directly attaching on membrane surface.

Effect of different temperatures on performance and membrane fouling in high concentration PAC-MBR system treating micro-polluted surface water.

A bench-scale immersed microfiltration coupled with 50 g/L PAC was developed to treat micro-polluted surface water (MPSW) under 10 and 20 °C and the effects of temperatures on the performance and the membrane fouling were also investigated. The low temperature (10 °C) delayed the time for the start-up by 9 days and the complete nitrification by 10 days. In the stable operation, two systems both had high NH3-N removal efficiency (above 90%) and better removal of organic matters (10% DOC, 5% UV254 and 4% SUVA) at 10 °C. Polysaccharides (SMP) were the main membrane fouling matters at low temperature (10 °C) and low temperature (10 °C) didn't cause serious chemical irreversible membrane fouling.

High concentration powdered activated carbon-membrane bioreactor (PAC-MBR) for slightly polluted surface water treatment at low temperature.

In this study, different concentrations of PAC combined with MBR were carried out to treat slightly polluted surface water (SPSW) at low temperature (10°C). Effects of PAC on the efficiencies of operation, treatment, and the performance of the process were investigated. It was found that the effluent quality, performance efficiency, resistance of shock load were all enhanced and chemical irreversible membrane fouling was reduced with increasing dosage of PAC in MBR. Only when the concentration of PAC which acted as biological carriers was high enough (i.g., 50 g/L), nitrification without initial inoculation in the filtration tank could start within 19 days and be completed within 35 days at 10°C. Fifty grams per liter PAC was the optimal dosage in MBR for stable and extended operation. Under this condition, mean removal efficiencies of ammonia nitrogen (NH(3)-N), dissolved organic carbon (DOC) and UV(254) were 93%, 75%, and 85%, respectively.

Comparative performance between intermittently cyclic activated sludge-membrane bioreactor and anoxic/aerobic-membrane bioreactor.

A process of intermittently cyclic activated sludge-membrane bioreactor (ICAS-MBR) was developed to enhance the performance of biological phosphorus removal (EBPR), which was constructed under sequencing anoxic/anaerobic/aerobic condition. The performance between ICAS-MBR and conventional anoxic/aerobic-membrane bioreactor (A/O-MBR) in terms of phosphorus removal, nitrification performance and microbial aspects were investigated in this study. The experimental results indicated that the phosphorus removal efficiency in ICAS-MBR process increased from 65% to 83% when compared with A/O-MBR. It was also found that the COD removal efficiencies of the two processes were over 94%, and NH(4)(+)-N and TN average removal efficiencies were 96% and 69% in ICAS-MBR and 96% and 78% in A/O-MBR, respectively. Furthermore, micrographs observation obtained confirmed the succession and diversification of microorganisms in the two systems followed a similar regularity.

[Quantitative investigation on flocculation and destruction of poly-silicic-ferric (PSF) coagulant].

An inorganic polymer, poly-silicic-ferric (PSF) coagulant was prepared using water glass, FeSO4 x 7H2O and NaClO3 by copolymerization. A comparison of coagulation performance, distribution of residual flocs in finished water and influence of turbulent shear force on the flocs between PSF and polyferric aluminum (PFA) was explored by jar tests and particle counter approach. The results indicate that PSF has superior removal of COD at higher dose to PFA. Flocculating speed should not be much higher or lower when using PSF as coagulant in treating surface water, and excellent coagulation efficiency can be obtained by the close cooperation of flocculation speed with flocculation time, that is, higher flocculation speed should be consistent with shorter flocculation time. The PFA flocs are much easier destructed than PSF flocs when increasing the turbulent shear force, and the destructed PSF flocs tend to be more easily re-coupled than PFA flocs. From the order magnitude, the flocculation coefficient KA of PSF is from 10(-2) to 10(-3), in comparison with the destruction coefficient KB from 10(-7) to 10(-8). For particles whose size is smaller than 2 microm, KA of PSF is 4 order magnitude more than that of PFA, and KB of PSF is almost the same to that of PFA; while for the other particles, KA of PSF is 2 order magnitude more than that of PFA, and KB of PSF is almost ten times smaller than that of PFA.

[Analysis of reaction process between Si and Fe in poly-silicic-ferric sulfate (PSF) coagulant].

A new inorganic polymer coagulant, poly-silic-ferric sulfate (PSF) with various Si/Fe ratios (PSF0.5, PSF1 and PSF denote Si/Fe molar ratios of 0.5, 1 and 3, respectively), was prepared using water glass, ferrous sulfate and sodium chlorate by co-polymerization, and pH value was measured during the preparation process. The influence of both Si/Fe ratio and reaction time (polymerization time) on the complexation process (bonding mode) between Si and Fe was explored with many analytical methods (such as X-ray diffraction (XRD), ultraviolet/visible absorption (UVA) scanning, transmission electron microscope (TEM), photon correlation spectra (PCS) and infrared spectrum (IR) using PSF samples taken from different reaction time at different Si/Fe ratios. The results show that the characteristics of PSF are largely influenced by both reaction time and Si/Fe ratios. PSF is found to be a complexation compound of Si, Fe and many other ions, instead of a simple mixture of raw materials. The complexation process between Si and Fe may be different from various Si/Fe ratios, namely, the bonding rate, bonding mode and the stability of the bond between Si and Fe are different from various Si/Fe ratios: the polymer based on Si-O-Fe-O-Fe-O-Si bond may be formed at low Si/Fe ratio, in comparison with that based on Si-O-Fe-O-Si-O-Si bond at high Si/Fe ratio; the formation rate of Fe-O-Fe bond is rapid and there may be a mutual acceleration between Fe-O-Fe bond and Si-O-Fe bond, while the formation rate of Si-O-Si is slow and maybe there is a mutual retardation between Si-O-Fe bond and Si-O-Si bond; the stability of Fe-O-Fe bond is weaker than that of Si-O-Fe or Si-O-Si bond.