Effect of flux (transmembrane pressure) and membrane properties on fouling and rejection of reverse osmosis and nanofiltration membranes treating perfluorooctane sulfonate containing wastewater

Perfluorooctane sulfonate (PFOS) is an emergent contaminant of substantial environmental concerns. In this study, reverse osmosis (RO) and nanofiltration (NF) membranes were used to remove this toxic and persistent compound from PFOS-containing wastewater. Five RO membranes and three NF membranes were tested at a feed concentration of 10 ppm PFOS over 4 days, and the PFOS rejection and permeate flux performances were systematically investigated. PFOS rejection was well correlated to sodium chloride rejection. The rejection efficiencies for the RO membranes were > 99%, and those for the NF membranes ranged from 90-99%. Improvement in PFOS rejection, together with mild flux reduction (< 16%), was observed at longer filtration time. Such shifts in rejection and flux performance were probably due to the increased PFOS accumulation at longer duration, as shown by X-ray photoelectron spectroscopy and liquid chromatograph and tandem mass spectrometry results. A fraction of PFOS molecules might be entrapped in the polyamide layer of the composite membranes, which hindered the further passage of both water and other PFOS molecules. In a similar fashion, PFOS rejection and fouling were enhanced for greater initial flux and/or applied pressure, where PFOS accumulation was promoted probably due to increased hydrodynamic permeate drag. Flux reduction was also shown to correlate to membrane roughness, with the rougher membranes tend to experience more flux reduction than the smoother ones.     

PROCESSING OF CRUDE PALM OIL WITH CERAMIC MICROFILTRATION MEMBRANE

Membrane separation technology offers a potential application in the processing of crude palm oil. Ceramic membranes with different pore diameters (0.45 and 0.2 micron) were used to conduct the study on micromembrane process. Quality parameters of membrane-processed oils examined included free fatty acid (FFA), carotene, fatty acid composition (FAC), phosphorus and iron contents. The effect of operating parameters such as transmembrane pressure, feed flow and time on permeate flux were evaluated. It was found that 'Ceraflo'ceramic membrane with a pore size of 0.45 micron was only able to reject 14% of phosphorus from the crude oil. Ceramic membrane with pore size of 0.2 micron showed a better phosphorus rejection of 56.8%. The permeate was found to contain 7.13 ppm of phosphorus. The 0.2 micron membrane was also able to remove more than 80% of the iron from crude palm oil. Pore sizes for both membranes were not small enough to remove other components such as FFA, and carotene. Both membranes showed a similar trend in which the permeate flux increased with transmembrane pressure and feed flow until a certain limit where the flux declined with increasing pressure and feed flow. The limits in transmembrane pressures for membrane with pore sizes of 0.45 and 0.2 micron were 1.65 and 1.25 bar, respectively. Whereas the limits in feed flow for 0.45 micron and 0.2 micron membranes were 9.2 and 9.8 L/min     

Performance of forward (direct) osmosis process: membrane structure and transport phenomenon

The performance of a forward (direct) osmosis (FO) process was investigated using a laboratory-scale unit to elucidate the effect of membrane structure and orientation on waterflux. Two types of RO membrane and a FO membrane were tested using ammonium bicarbonate, glucose, and fructose as the draw solution to extract water from a saline feed solution. The FO membrane was able to achieve higher water flux than the RO membranes under the same experimental conditions while maintaining high salt rejection of greater than 97%. Increasing operating temperature increased the water flux in FO process. To investigate the effect of membrane orientation on water flux, the FO membrane was tested normally (dense selective layer facing draw solution) and reversely (dense selective layer facing feed solution). Explanations on transport phenomenon in FO process were proposed which explain the observation that the FO membrane, when used in the normal orientation, performed better due to lesser internal concentration polarization. This study suggests that an ideal FO membrane should consist of a thin dense selective layer without any loose fabric support layer.     

Evaluation of membrane fouling for in-line filtration of oil sands process-affected water: the effects of pretreatment conditions

Membrane filtration is an effective reclamation option for oil sands process-affected water (OSPW). However, fresh OSPWs contain suspended solids and inorganic constituents in suspended and dissolved forms that can severely foul membranes. Pretreatment of OSPW with coagulation-flocculation (CF) was investigated to determine the effects of different coagulant aids (anionic, cationic, and nonionic polymers) on membrane surface properties and fouling. Our results showed that CF pretreatment effectively enhanced nanofiltration (NF) and reverse osmosis (RO) membrane permeate flux and salt rejection ratio through reducing membrane fouling. It was shown that coagulants and coagulant aids applied to OSPW feedwater can affect membrane physicochemical properties (surface hydrophilicity, zeta potential, and morphology), membrane performance, and the fouling indexes. Membrane rejection of ionic species increased significantly with the inclusion of an anionic coagulant aid and slightly with a cationic coagulant aid. Among three coagulant aids tested, anionic coagulant aids led to the most enhanced membrane performance through increasing membrane surface negativity and decreasing the formation of a fouling layer. Conversely, although cationic coagulant aids were the most effective in reducing OSPW turbidity, the application of cationic coagulant aids promoted the adsorption of foulants on membrane surfaces.     

Role of soluble microbial products (SMP) in membrane fouling and flux decline

Soluble microbial products (SMP), a significant component of effluent organic matter (EfOM), play an important role in membrane fouling and flux decline in wastewater reclamation/reuse applications. The SMP compounds of a microbial origin are derived during biological processes of wastewater treatment. They exhibit the characteristics of hydrophilic organic colloids and macromolecules. These high molecular weight compounds play an important role in creating high resistance of the membrane, leading to a reduction of permeate flux. The SMP fouling of RO, NF, and tight UF membranes is associated with formation of a cake/gel layer due to size (steric) exclusion. FTIR spectra of SMP- and EfOM-fouled membranes exhibited foulants' composition, consisting of polysaccharides, proteins, and/or aminosugar-like compounds. This finding reveals the important role of the SMP components as factors in membrane fouling and flux decline associated with EfOM source waters. Solids retention time (SRT) affects the characteristics and amounts of SMP, however, SRT did not affect flux decline trends of RO and NF membranes.     

Ultrafiltration and Reverse Osmosis Recovery of Limonene from Citrus Processing Waste Streams

Commercial ultrafiltration (UF) and reverse osmosis (RO) membranes were used to concentrate the terpene, limonene, present in cold pressed oil centrifuge effluent and molasses evaporator condensate. UF membrane rejections were 78–97% for mixtures with initial limonene concentrations from 0.04–0.6%v/v. RO membrane rejection of limonene ranged from 87–99% for feed streams containing 0.06–0.23% limonene. Initial membrane flux rates for centrifuge effluents were in the range 10–100 kg/m²/hr. Evaporator condensate fluxes were higher, 25–400, while pure water rates ranged from 25 (RO) to 1000 kg/m²/hr (UF). Contact with limonene adversely affected membrane flux rates in decreasing order of severity: polysulfone > cellulose acetate > teflon-type.     

Ion implantation: effect on flux and rejection properties of NF membranes

Nanofiltration (NF) membranes typically carry a net electric charge, enabling electrostatic interactions to play a pivotal role in the rejection of species such as metals, nitrates, and other charged contaminants. In this study, two types of polymeric NF membranes, polyamide and cellulose acetate, were modified by ion implantation to increase the effective surface charge of the membranes. The modified membranes contain implanted ions in the membrane matrix, inducing a discrete, permanent charge in the active membrane layer. The presence of a permanent charge in the membrane matrix allows for increased electrostatic repulsive forces throughout the entire pH range. Streaming potential measurements were conducted as a function of pH for the modified and unmodified membranes to determine the effect of ion implantation on the zeta potential of the membranes. Rejection experiments were performed in order to quantify the effect of increased electrostatic repulsion on ion rejection, and flux measurements quantified the effect of the modification on permeability. Results indicate that electrostatic interactions near the membrane surface can affect rejection; however, the extent of the effect of increased membrane charge depends on physical-chemical characteristics of the membrane. Increased negative zeta potential of the modified membranes resulted in slightly higher rejection of salts with divalent co-ions from the membrane, with less increase observed with salts of monovalent co-ions. Modified membranes were less permeable than the unmodified membranes. Results of this research hold implications in membrane synthesis and modification studies as well as choice of membranes for water treatment applications.     

Comprehensive bench- and pilot-scale investigation of trace organic compounds rejection by forward osmosis

Forward osmosis (FO) is a membrane separation technology that has been studied in recent years for application in water treatment and desalination. It can best be utilized as an advanced pretreatment for desalination processes such as reverse osmosis (RO) and nanofiltration (NF) to protect the membranes from scaling and fouling. In the current study the rejection of trace organic compounds (TOrCs) such as pharmaceuticals, personal care products, plasticizers, and flame-retardants by FO and a hybrid FO-RO system was investigated at both the bench- and pilot-scales. More than 30 compounds were analyzed, of which 23 nonionic and ionic TOrCs were identified and quantified in the studied wastewater effluent. Results revealed that almost all TOrCs were highly rejected by the FO membrane at the pilot scale while rejection at the bench scale was generally lower. Membrane fouling, especially under field conditions when wastewater effluent is the FO feed solution, plays a substantial role in increasing the rejection of TOrCs in FO. The hybrid FO-RO process demonstrated that the dual barrier treatment of impaired water could lead to more than 99% rejection of almost all TOrCs that were identified in reclaimed water.     

Characterization of humic acid fouled reverse osmosis and nanofiltration membranes by transmission electron microscopy and streaming potential measurements

Reverse osmosis and nanofiltration membranes fouled by humic acid were systematically characterized by transmission electron microscopy. All fouled membranes, except those with very low initial flux, were completely covered by a layer of humic acid whose thickness and density were greatly affected by the feedwater composition ([H+] and [Ca2+]) and initial flux. A low-density humic layer (about 0.1 g of purified Aldrich humic acid (PAHA)/cm3) was formed at low initial flux (2 m/day or less) at pH 7 without calcium. It was several times denser at a higher initial flux, pH 4.5, or 1 mM Ca2+. Corresponding to the denser foulant layers under these conditions, PAHA accumulation was greatly increased. The denser foulant layers together with the greater PAHA accumulations were responsible for the severe flux reductions. Both virgin and fouled membranes were characterized by streaming potential measurements. While considerable differences existed for virgin membranes, humic acid fouled membranes exhibited identical surface charge properties. The zeta potential of the fouled membranes was controlled by the humic acid layer due to its complete coverage of the membrane surfaces.     

Ultrafiltration/Reverse Osmosis Concentration of Lobster Extract

A membrane concentration system consisting of tubular polysulphone ultrafiltration (UF) and polyamide reverse osmosis (RO) was evaluated for concentrating key water soluble flavor compounds from lobster extracts. Major flavor-giving compounds in the extract were glutamic acid, glycine, arginine, uridine 5′-monophosphate (UMP), succninic acid and glucose. Factors affecting performance of the UF/RO systems, such as flow rate, feed solid level, temperature and pressure, on permeate flux and solids rejection were measured. The optimum UF conditions were 1.5% feed solid level, 15 L/min feed flow rate, 50°C feed temperature and 1 MPa log mean transmembrane pressure. The RO system retained all dissolved flavor components and its ideal operating conditions were 40°C, 2.8 MPa log mean transmembrane pressure and a flow rate of 15 L/min.     

Decolorization of vegetable oils by membrane processing

Membrane decolorization studies of chlorophyll added sunflower oil and crude soybean oil were conducted in a batch membrane cell using two polymeric composite membranes (NTGS-2100 and NTGS-1100), and one polyethylene microfiltration membrane (PE-30). NTGS-2100 membrane could remove up to 96% and 72% chlorophyll from the undiluted and oil-hexane (50 wt%) solutions, respectively. Permeate oil flux was very low when undiluted oil was used as feed, but improved many fold by diluting with hexane. NTGS-1100 membrane gave higher permeate flux compared to NTGS-2100, but showed reduced rejection. Absorbance spectra of crude soybean oil and the permeate in the 350-550 nm range showed a greater degree of decolorization by polymeric composite membranes. PE-30 membrane showed insignificant rejection of color compounds. The permeate of conventionally bleached soybean oil showed a reduction in extinction coefficients at 232 and 270 nm, indicating possible rejection of dienes and trienes by the composite polymeric membranes. The membrane process was effective in reducing the color compounds in crude vegetable oils besides offering many advantages over the conventional process.     

Recovery and purification of potato proteins from potato starch wastewater by hollow fiber separation membrane integrated process

Potato starch wastewater contains high-concentration potato proteins which have great potential in the fields of food and health care. Most researches on potato protein recovery by membrane separation technique are focused on flat sheet or tubular ultrafiltration (UF) and reverse osmosis (RO) membranes and lack the further protein purification and the in-depth discussions on the fouling behavior. In this laboratory-scale study, potato proteins were recovered and purified from the simulated potato starch wastewater by the self-made hollow fiber (HF) UF and nanofiltration (NF) separation membrane integrated process. 85.62% potato proteins with high molecular weight in the potato starch wastewater could be retained by UF membrane and 92.1% potato proteins with low molecular weight were rejected by NF membrane. The concentrated solution after UF and NF filtration was desalinated and purified by diluting the solution eight times and filtering the diluted solution with UF membrane. Both types of HF membranes, UF and NF, suffered the inevitable membrane fouling. After the traditional physical washing and chemical cleaning, water flux of UF and NF membranes can be effectively recovered. The corresponding recovery rates of UF and NF membranes can reach 93.5% and 84.7%, respectively. The hollow fiber UF-NF separation membrane integrated process was proved to be a promising technique of high-purity potato protein recovery from potato starch wastewater.     

Boric acid permeation in forward osmosis membrane processes: modeling, experiments, and implications

Forward osmosis (FO) is attracting increasing interest for its potential applications in desalination. In FO, permeation of contaminants from feed solution into draw solution through the semipermeable membrane can take place simultaneously with water diffusion. Understanding the contaminants transport through and rejection by FO membrane has significant technical implications in the way to separate clean water from the diluted draw solution. In this study, a model was developed to predict boron flux in FO operation. A strong agreement between modeling results and experimental data indicates that the model developed in this study can accurately predict the boron transport through FO membranes. Furthermore, the model can guide the fabrication of improved FO membranes with decreased boron permeability and structural parameter to minimize boron flux. Both theoretical model and experimental results demonstrated that when membrane active layer was facing draw solution, boron flux was substantially greater compared to the other membrane orientation due to more severe internal concentration polarization. In this investigation, for the first time, rejection of contaminants was defined in FO processes. This is critical to compare the membrane performance between different membranes and experimental conditions.     

超滤技术处理甘薯淀粉生产废水的应用效果

为了选择适宜的超滤膜对甘薯淀粉废水进行处理,以3种甘薯淀粉废水为研究对象,比较了无机陶瓷膜N50、N100和N200以及有机膜PVDF和PES的膜通量及其处理效果。结果表明:膜通量在超滤进行到第15~25 min时下降明显,之后基本保持稳定,其中陶瓷膜N200与N50具有较高的稳定膜通量,有机膜PVDF膜通量高于PES。废液经处理后,透光性显著加强,可溶性固形物去除率为39.8%~64.6%、可溶性蛋白质去除率为73.7%~99.0%、化学需氧量降低32.3%~73.2%,其中N50、PVDF和PES处理效果更好。综合膜通量及运行成本指导实际生产,实际生产中宜用N50或PVDF对甘薯淀粉废水进行超滤处理,以减轻后续处理压力,提高废水中有机物质的回收利用。     

Fouling of nanofiltration, reverse osmosis, and ultrafiltration membranes by protein mixtures: the role of inter-foulant-species interaction

Protein fouling of nanofiltration (NF), reverse osmosis (RO), and ultrafiltration (UF) membranes by bovine serum albumin (BSA), lysozyme (LYS), and their mixture was investigated under cross-flow conditions. The effect of solution chemistry, membrane properties, and permeate flux level was systematically studied. When the solution pH was within the isoelectric points (IEPs) of the two proteins (i.e., pH 4.7-10.4), the mixed protein system experienced more severe flux decline compared to the respective single protein systems, which may be attributed to the electrostatic attraction between the negatively charged BSA and positively charged LYS molecules. Unlike a typical single protein system, membrane fouling by BSA-LYS mixture was only weakly dependent on solution pH within this pH range, and increased ionic strength was found to enhance the membrane flux as a result of the suppressed BSA-LYS electrostatic attraction. Membrane fouling was likely controlled by foulant-fouled-membrane interaction under severe fouling conditions (elevated flux level and unfavorable solution chemistry that promotes fouling), whereas it was likely dominated by foulant-clean-membrane interaction under mild fouling conditions. Compared to nonporous NF and RO membranes, the porous UF membrane was more susceptible to dramatic flux decline due to the increased risk of membrane pore plugging. This study reveals that membrane fouling by mixed macromolecules may behave very differently from that by typical single foulant system, especially when the inter-foulant-species interaction dominates over the intra-species interaction in the mixed foulant system.     

再生纤维素纳米纤维膜的制备及其蛋白质分离性能

为将纳米纤维膜应用于蛋白质分离处理,用静电纺丝和化学改性方法制备聚丙烯腈/再生纤维素（PAN∕ RC）复合纳米纤维膜,通过扫描电镜、红外光谱、比表面积及孔径分析等对制备的复合纳米纤维膜进行了表征,并将制备的再生纤维素复合纳米纤维膜作为分离层,构建膜分离系统并分离纯化血清白蛋白,通过调节操作压力和过滤时间等影响因素,确定其分离纯化过程的最佳条件。研究结果表明：在操作压力为0.10 MPa、过滤时间为1.5h条件下,再生纤维素复合纳米纤维膜对蛋白质的截留率达到80.04%,膜通量达到1.85L ∕ （m²?min）,与商用聚醚砜超滤膜相比,在截留率差异不大的情况下,膜通量有了数倍的提升;同时再生纤维素复合纳米纤维膜具有优异的重复使用能力,并在使用的过程中保持良好的纳米纤维形态结构。     

Feed substrates influence biofilm formation on reverse osmosis membranes and their cleaning efficiency

The dairy industry is increasingly using reverse osmosis (RO) membranes for concentration of various fluid feed materials such as whey and ultrafiltration (UF) permeate. This study compared the effect of UF permeate and whey on membrane biofilm formation. A Bacillus sp., previously isolated in our laboratory from a cleaning-resistant membrane biofilm, was used to develop 48-h-old static biofilms on RO membrane pieces, using the different feed substrates (UF permeate, whey, and an alternating whey/UF feed). Biofilms were analyzed for viable counts by the swab technique, and we used scanning electron and atomic force microscopy for microstructure imaging. The membrane cleaning process included 6 sequential steps. We observed differences in the resistance pattern of the 3 types of biofilms to the typical cleaning process. The mean pretreatment counts of the 48-h UF permeate biofilms were 5.39 log cfu/cm², much higher than the whey biofilm counts of 3.44 log, and alternating whey/UF biofilm counts of 4.54 log. After a 6-step cleaning cycle, we found 2.54 log survivors of the Bacillus isolate on UF biofilms, whereas only 1.82 log survivors were found in whey biofilm, and 2.14 log survivors on whey/UF permeate biofilms. In conclusion, the UF permeate biofilms was more resistant to the biofilm cleaning process compared with the whey or whey/UF permeate biofilms. Scanning electron micrographs showed different microstructures of biofilms based on the type of feed. For UF permeate and whey/UF permeate biofilms, bacilli were present in multilayers of cells in aggregates or irregular clusters with foulant layers. In contrast, those in whey biofilms were in monolayers, with a smoother, flatter appearance. Atomic force microscopy analysis indicated that UF permeate biofilms had the greatest surface roughness among the biofilms, reflecting intensified bacterial colonization. The biofilm micro- and nanostructure variations for the 2 feed substrates and their combination may have resulted in differences in their resistance to the cleaning process.     

Swelling and morphology of the skin layer of polyamide composite membranes: an atomic force microscopy study

The paper introduces a new methodology for studying polyamide composite membranes for reverse osmosis (RO) and nanofiltration (NF) in liquid environments. The methodology is based on atomic force microscopy of the active layer, which had been separated from the support and placed on a solid substrate. The approach was employed to determine the thickness, interfacial morphology, and dimensional changes in solution (swelling) of polyamide films. The face (active) and back (facing the support) surfaces of the RO films appeared morphologically similar, in agreement with the recently proposed model of skin formation. Measured thickness and swelling data in conjunction with the intrinsic permeability of the membranes suggest that the selective barrier in RO membrane constitutes only a fraction of the polyamide skin, whereas NF membranes behave as nearly uniform films. For NF membranes, there was reasonable correlation between the changes in the swelling and in the permeability of the membrane and the salinity and pH of the feed.     

Cake-enhanced concentration polarization: a new fouling mechanism for salt-rejecting membranes

Results from well-controlled colloidal fouling experiments with reverse osmosis (RO) and nanofiltration (NF) membranes suggest the existence of a new source of flux decline for salt-rejecting membranes-cake-enhanced osmotic pressure. The physical mechanisms leading to this enhanced osmotic pressure are a combination of hindered back-diffusion of salt ions and altered cross-flow hydrodynamics within colloidal deposit layers, which lead to an enhanced salt concentration polarization layer. A model that accounts for both hindered diffusion of salt ions and altered hydrodynamics within colloidal deposit ("cake") layers is presented. The model successfully links permeate flux and salt rejection to cake-enhanced concentration polarization and provides new insight into the mechanisms through which salt-rejecting membranes foul. Experimental data support the model calculations and highlight the role of enhanced concentration polarization phenomena in the performance (i.e., water flux and salt rejection) of polymeric thin-film composite RO/NF membranes in environmental applications.     

Removal of the natural hormone estrone from aqueous solutions using nanofiltration and reverse osmosis

The ability of a variety of nanofiltration and reverse osmosis membranes to retain the natural hormone estrone are examined here as a function of solution conditions. While size exclusion dominates retention with the tighter membranes, both size exclusion and adsorptive effects appear to be instrumental in maintaining high retention on nanofiltration membranes that otherwise exhibit relatively low ion retentions. These adsorptive effects may be driven by hydrogen bonding between estrone and the membrane. Electrostatic attraction appears to aid retention with an apparent slight decrease in retention at high NaCl concentrations. Deprotonation of estrone leads to a significant decrease in retention, most likely as a result of the effect of strong electrostatic repulsive forces decreasing the proximity of the negatively charged estrone to the negatively charged membrane surface and thus lowering the potential for adsorptive retention. This deprotonation effect is absent for tight RO membranes. The results reported here indicate that while open nanofiltration membranes may be effective in retaining estrone under some conditions, the extent of retention may be very susceptible to maintenance of adsorptive capacity at the membrane surface and depend on solution chemistry.