Relating organic fouling of reverse osmosis membranes to intermolecular adhesion forces

Organic fouling of reverse osmosis (RO) membranes and its relation to foulant--foulant intermolecular adhesion forces has been investigated. Alginate and Suwannee River natural organic matter were used as model organic foulants. Atomic force microscopy was utilized to determine the adhesion force between bulk organic foulants and foulants deposited on the membrane surface under various solution chemistries. The measured adhesion force was related to the RO fouling rate determined from fouling experiments under solution chemistries similar to those used in the AFM measurements. A remarkable correlation was obtained between the measured adhesion force and the fouling rate under the solution chemistries investigated. Fouling was more severe at solution chemistries that resulted in larger adhesion forces, namely, lower pH, higher ionic strength, presence of calcium ions (but not magnesium ions), and higher mass ratio of alginate to Suwannee River natural organic matter. The significant adhesion force measured with alginate in the presence of calcium ions indicated the formation of a crossed-linked alginate gel layer during fouling through intermolecular bridging among alginate molecules.     

Studying the role of common membrane surface functionalities on adsorption and cleaning of organic foulants using QCM-D

Adsorption of organic foulants on nanofiltration (NF) and reverse osmosis (RO) membrane surfaces strongly affects subsequent fouling behavior by modifying the membrane surface. In this study, impact on organic foulant adsorption of specific chemistries including those in commercial thin-film composite membranes was investigated using self-assembled monolayers with seven different ending chemical functionalities (-CH(3), -O-phenyl, -NH(2), ethylene-glycol, -COOH, -CONH(2), and -OH). Adsorption and cleaning of protein (bovine serum albumin) and polysaccharide (sodium alginate) model foulants in two solution conditions were measured using quartz crystal microbalance with dissipation monitoring, and were found to strongly depend on surface functionality. Alginate adsorption correlated with surface hydrophobicity as measured by water contact angle in air; however, adsorption of BSA on hydrophilic -COOH, -NH(2), and -CONH(2) surfaces was high and dominated by hydrogen bond formation and electrostatic attraction. Adsorption of both BSA and alginate was the fastest on -COOH, and adsorption on -NH(2) and -CONH(2) was difficult to remove by surfactant cleaning. BSA adsorption kinetics was shown to be markedly faster than that of alginate, suggesting its importance in the formation of the conditioning layer. Surface modification to render -OH or ethylene-glycol functionalities are expected to reduce membrane fouling.     

Mechanism involved in the evolution of physically irreversible fouling in microfiltration and ultrafiltration membranes used for drinking water treatment

Control of membrane fouling is important for more efficient use of membranes in water treatment. Control of physically irreversible fouling, which is defined as fouling that requires chemical cleaning to be cancelled, is particularly important for reduction of operation cost in a membrane process. In this study, a long-term filtration experiment using three different types of MF and UF membranes was carried out at an existing water purification plant, and the evolution of physically irreversible fouling was investigated. The experimental results demonstrated that the extent of physically irreversible fouling differed significantly depending on the membrane type. Cleaning of the fouled membranes with various chemical reagents demonstrated that organic matter was mainly responsible for physically irreversible fouling. Organic matter that had caused physically irreversible fouling in the long-term operation was desorbed from the fouled membranes and was subjected to Fourier transform infrared and 13C nuclear magnetic resonance analyses. These analyses revealed that carbohydrates were dominant in the membrane foulant regardless of the type of membrane. Based on measurements of molecular weight distribution of organic matter in the feedwater and the permeates from the membranes, a two-step fouling mechanism is proposed to explain the dominance of carbohydrates in the foulant: hydrophobic (humic-like) components with small molecular weight are first adsorbed on the membrane and, consequently, narrow the size of micro-pores of membranes, and then hydrophilic (carbohydrate-like) compounds with larger molecular weight plug the narrowed pores or the hydrophilic compounds are adsorbed onto the membrane surface conditioned by the hydrophobic components.     

处理L-苯丙氨酸发酵液污染膜的化学清洗研究

对处理发酵液后污染严重的聚偏氟乙烯(PVDF)中空纤维膜进行了化学清洗研究。实验中,通过电镜与红外定性分析了污染物成分,并确定了氧化剂高锰酸钾的使用条件,比较了氧化清洗的加酸前后及还原前后的清洗效果,并对清洗后的中空纤维膜进行了一系列的性能测试。最后进行了双向流工艺的在线中试研究。     

Affinity of functional groups for membrane surfaces: implications for physically irreversible fouling

Fouling in membranes used for water treatment has been attributed to the presence of natural organic matter (NOM) in water. There have been reports recently on the contribution of hydrophilic fractions of NOM (e.g., carbohydrate-like substances) to fouling, but there is still little information about the physicochemical interactions between membranes and carbohydrate-like substances. In this study, the affinity of carbohydrate-like substances to two different microfiltration (MF) membranes was investigated by using atomic force microscopy (AFM) and functionally modified microspheres. Microspheres were attached to the tip of the cantilever in an AFM apparatus and the adhesion forces working between the microspheres and the membranes were determined. The microspheres used in this study were coated with either hydroxyl groups or carboxyl groups to be used as surrogates of carbohydrate-like substances or humic acid, respectively. Measurements of adhesion force were carried out at pH of 6.8 and the experimental results demonstrated that the adhesion force to membranes was strong in the case of hydroxyl groups but weak in the case of carboxyl groups. The strong adhesion between the hydroxyl group and the membrane surface is explained by the strong hydrogen bond generated. It was also found that the affinity of the hydroxyl group to a polyvinylidenefluoride (PVDF) membrane was much higher than that to a polyethylene (PE) membrane, possibly due to the high electronegative nature of the PVDF polymer. The time course of changes in the affinity of hydroxyl group to a membrane used in a practical condition was investigated by repeatedly carrying out AFM force measurements with PE membrane specimens sampled from a pilot plant operated at an existing water treatment plant. Microspheres exhibited strong affinity to the membrane at the initial stage of operation (within 5 days), but subsequently exponential reduction of the affinity was seen until the end of operation, as a result of fouling development. However, the magnitude of affinity of hydroxyl-modified microspheres was much higher than that of carboxyl-modified microspheres even after the significant reduction of affinity of hydroxyl-modified microspheres to the membranes was seen. The results obtained in this study partially explain why hydrophilic NOM dominated over humic substances in foulants of membranes used for water treatment in recent studies on fouling.     

Nanofiltration membrane fouling by oppositely charged macromolecules: investigation on flux behavior, foulant mass deposition, and solute rejection

Nanofiltration membrane fouling by oppositely charged polysaccharide (alginate) and protein (lysozyme) was systematically studied. It was found that membrane flux decline in the presence of both lysozyme and alginate was much more severe compared to that when there was only lysozyme or alginate in the feed solution. The flux performance for the mixed foulants was only weakly affected by solution pH and calcium concentration. These effects were likely due to the strong electrostatic attraction between the two oppositely charged foulants. Higher initial flux caused increased foulant deposition, more compact foulant layer, and more severe flux decline. The deposited foulant cake layer had a strong tendency to maintain a constant foulant composition that was independent of the membrane initial flux and only weakly dependent on the relative foulant concentration in feed solution. In contrast, solution chemistry (pH and [Ca2?]) had marked effect on the foulant layer composition, likely due to the resulting changes in the foulant-foulant interaction. The mixed alginate-lysozyme fouling could result in an initial enhancement in salt rejection. However, such initial enhancement was not observed when there was 1 mM calcium present in the feedwater, which may be attributed to the charge neutralization of the foulant layer.     

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.     

Influence of flocculation and adsorption as pretreatment on the fouling of ultrafiltration and nanofiltration membranes: application with biologically treated sewage effluent

Membrane fouling is a critical limitation on the application of membranes to wastewater reuse. This work aims to understand the fouling phenomenon which occurs in ultrafiltration (UF; 17500 molecular weight cutoff (MWCO)) and nanofiltration (NF; 250 MWCO) membranes, with and without pretreatment. For this purpose, the molecular weight (MW) distribution of the organics has been used as a parameter to characterize the influent, the permeate, and the foulant on the membrane surface. The variation of foulant concentration on the membrane due to pretreatment of the influent by flocculation and/or adsorption was investigated in detail. With the UF membrane, the peak of the MW distribution of organics in the permeate depended on the pretreatment; for example, the weight-averaged MW (Mw) of 675 without pretreatment shifted down to 314 with pretreatment. In the case of the NF membrane, the Mw of organics in the permeate was 478 (without pretreatment) and 310 (with flocculation followed by adsorption). The Mw of the organics in the foulant on the membrane surface was 513 (UF) and 192 (NF) without pretreatment and 351 (UF) and 183 (NF) after pretreatment with flocculation followed by adsorption, respectively. Without the pretreatment, the foulant concentration was higher on both membranes. The difference was more significant on the UF membrane than on the NF membrane. For both membranes, the flocculation-and-then-adsorption pretreatment proved very effective.     

Polyelectrolyte and silver nanoparticle modification of microfiltration membranes to mitigate organic and bacterial fouling

Membrane fouling remains one of the most problematic issues surrounding membrane use in water and wastewater treatment applications. Organic and biological fouling contribute to irreversible fouling and flux decline in these processes. The aim of this study was to reduce both organic and biological fouling by modifying the surface of commercially available poly(ether sulfone) (PES) membranes using the polyelectrolyte multilayer modification method with poly(styrenesulfonate) (PSS), poly(diallyldimethylammonium chloride) (PDADMAC), and silver nanoparticles (nanoAg) integrated onto the surface as stable, thin (15 nm) films. PSS increases the hydrophilicity of the membrane and increases the negative surface charge, while integration of nanoAg into the top PSS layer imparts biocidal characteristics to the modified surface. Fouling was simulated by filtering aqueous solutions of humic acid (5 and 20 mg L(-1)), a suspension of Escherichia coli (10(6) colony-forming units (CFU) mL(-1)), and a mixture of both foulants through unmodified and modified PES membranes under batch conditions. Filtration and cleaning studies confirmed that the modification significantly reduced organic and biological fouling.     

Fouling and natural organic matter removal in adsorbent/membrane systems for drinking water treatment

Adsorbent particles added to ultrafiltration (UF) systems treating drinking water can remove natural organic matter (NOM) and some other contaminants from the water, but their effect on membrane fouling is inconsistent-in some cases, fouling is reduced, and in others, it is exacerbated. This research investigated the behavior of UF systems to which powdered activated carbon (PAC), heated iron oxide particles (HIOPs), or (nonadsorbent) SiO2 particles were added. On a mass basis, the PAC removed the most NOM from solution, the HIOPs removed less, and the SiO2 removed essentially none. However, in the case of both PAC and SiO2, increasing the dose of solids led to a steady increase in fouling, whereas the opposite trend applied when HIOPs were added. In the absence of NOM, none of the solids fouled the membrane significantly. Thus, even though NOM is a causative agent for fouling, removing it from solution does not necessarily reduce fouling; the mechanism of removal can be just as important as the absolute amount removed, if the removal occurs in a cake layer near the membrane surface. Scanning electron microscopy images of the cake layers formed in the three systems suggest that the NOM binds PAC or SiO2 particles to one another and to the membrane surface, so that the particles become part of the foulant in the system. By contrast, the NOM appears to bind HIOPs to one another but not to the membrane. This process leaves enough pore space in the cake layer for water to reach the membrane with minimal resistance, and it reduces the tendency for either the NOM or the HIOPs to foul the membrane surface.     

Fouling of microfiltration and ultrafiltration membranes by natural waters

Membrane filtration (microfiltration and ultrafiltration) has become an accepted process for drinking water treatment, but membrane fouling remains a significant problem. The objective of this study was to systematically investigate the mechanisms and components in natural waters that contribute to fouling. Natural waters from five sources were filtered in a benchtop filtration system. A sequential filtration process was used in most experiments. The first filtration steps removed specific components from the water, and the latter filtration steps investigated membrane fouling by the remaining components. Particulate matter (larger than 0.45 microm) was relatively unimportant in fouling as compared to dissolved matter. Very small colloids, ranging from about 3-20 nm in diameter, appeared to be important membrane foulants based on this experimental protocol. The colloidal foulants included both inorganic and organic matter, but the greatest fraction of material was organic. When the colloidal fraction of material was removed, the remaining dissolved organic matter (DOM), which was smaller than about 3 nm and included about 85-90% of the total DOM, caused very little fouling. Thus, although other studies have identified DOM as a major foulant during filtration of natural waters, this work shows that a small fraction of DOM may be responsible for fouling. Adsorption was demonstrated to be an important mechanism for fouling by colloids.     

Understanding Nanofiltration Fouling of Phenolic Compounds in Model Juice Solution with Two Membranes

Understanding membrane fouling mechanisms of key nutrition indicators in fruit juices during nanofiltration (NF) are important for quality control of products and manufacture processes. This study evaluated the effects of operating and molecular parameters of six phenolic compounds on fouling resistances during NF with two membranes. Results showed that fouling resistances and mechanisms were significantly different among the six representative phenolic compounds as a result of different molecular parameters such as acidity coefficient, molecular refractive index, octanol-water partition coefficient, and lipo-hydro partition coefficient. Operating time, solution concentration, and transmembrane pressure can also significantly affect the membrane fouling during nanofiltration of gallic acid solution. The images obtained by field emission scanning electron microscopy and atomic force microscopy on new, fouled, and cleaned membranes showed the fouling mechanisms intuitively. For phenolic compounds, a cake/gel layer as a reversible fouling was the main fouling resistance, and the adsorption was a significant role in the irreversible fouling resistance.     

A physicochemical investigation of membrane fouling in cold microfiltration of skim milk

The main challenge in microfiltration (MF) is membrane fouling, which leads to a significant decline in permeate flux and a change in membrane selectivity over time. This work aims to elucidate the mechanisms of membrane fouling in cold MF of skim milk by identifying and quantifying the proteins and minerals involved in external and internal membrane fouling. Microfiltration was conducted using a 1.4-μm ceramic membrane, at a temperature of 6 ± 1°C, cross-flow velocity of 6 m/s, and transmembrane pressure of 159 kPa, for 90 min. Internal and external foulants were extracted from a ceramic membrane both after a brief contact between the membrane and skim milk, to evaluate instantaneous adsorption of foulants, and after MF. Four foulant streams were collected: weakly attached external foulants, weakly attached internal foulants, strongly attached external foulants, and strongly attached internal foulants. Liquid chromatography coupled with tandem mass spectrometry analysis showed that all major milk proteins were present in all foulant streams. Proteins did appear to be the major cause of membrane fouling. Proteomics analysis of the foulants indicated elevated levels of serum proteins as compared with milk in the foulant fractions collected from the adsorption study. Caseins were preferentially introduced into the fouling layer during MF, when transmembrane pressure was applied, as confirmed both by proteomics and mineral analyses. The knowledge generated in this study advances the understanding of fouling mechanisms in cold MF of skim milk and can be used to identify solutions for minimizing membrane fouling and increasing the efficiency of milk MF.     

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.     

The effect of temperature on adhesion forces between surfaces and model foods containing whey protein and sugar

The formation of fouling deposit from foods and food components is a severe problem in food processing and leads to frequent cleaning. The design of surfaces that resist fouling may decrease the need for cleaning and thus increase efficiency. Atomic force microscopy has been used to measure adhesion forces between stainless steel (SS) and fluoro-coated glass (FCG) microparticles and the model food deposits (i) whey protein (WPC), (ii) sweetened condensed milk, and (iii) caramel. Measurements were performed over a range of processing temperatures between 30 and 90 °C and at contact times up to 60 s. There is a significant increase in adhesion force of both types of microparticle to WPC at 90 °C for all contact times. For confectionary deposits adhesion to SS was similar. Adhesion of confectionary deposits to FCG at 30 °C revealed a decrease in adhesion compared to SS; at higher temperatures the adhesion forces were similar.     

Role of lipopolysaccharides in the adhesion,retention, and transport of Escherichia coli JM109

The role of lipopolysaccharides (LPS) in bacterial adhesion was investigated via atomic force microscopy (AFM). Adhesion between a silicon nitride tip and Escherichia coli JM109 was measured in water and 0.01 M phosphate-buffered saline (PBS) on untreated cells and on a sample of E. coli treated with 100 mM ethylenediaminetetraacetic acid (EDTA), which removes approximately 80% of the LPS molecules. LPS removal decreased the adhesion affinity between the bacterial cells and the AFM tip from -2.1 +/- 1.8 to -0.40 +/- 0.36 nN in water and from -0.74 +/- 0.44 to -0.46 +/- 0.23 nN in 0.01 M PBS (statistically different, Mann-Whitney rank sum test, P < 0.01). The distributions of adhesion affinities between E. coli LPS macromolecules and the AFM tip could be described by gamma distribution functions. Direct measurements of the adhesive force between E. coil and a surface were compared with adhesion in batch and column experiments, and agreement was observed between the influences of LPS on adhesion in each system. Bacterial batch retention to glass or in packed beds to quartz sand decreased after LPS removal. When interaction forces were measured during the approach of the AFM tip to a bacterium, steric repulsive forces were seen for both treated and untreated cells, but the repulsion was greater when the LPS was intact A model for steric repulsion predicted a reduction of the equilibrium length of the surface polymers from 242 to 64 nm in water and from 175 to 81 nm in buffer, after removal of a portion of the LPS. DLVO calculations based on conventional and soft-particle DLVO theories predicted higher energy barriers to adhesion for all surfaces after LPS removal, consistent with experimental findings. Adhesion forces between the AFM tip and bacterial polymers were correlated with bacterial attachment and retention, while measurements of interaction forces during the approach of the AFM tip to the bacterium did not correlate with subsequent adhesion behavior to glass or quartz sand.     

Membrane fouling in pilot-scale membrane bioreactors (MBRs) treating municipal wastewater

The main obstacle for wider use of membrane bioreactors (MBRs) for wastewater treatment is membrane fouling (i.e., deterioration of membrane permeability),which increases operating costs. For more efficient control of membrane fouling in MBRs, an understanding of the mechanisms of membrane fouling is important. However, there is a lack of information on membrane fouling in MBRs, especially information on features of components that are responsible for the fouling. We conducted a pilot-scale experiment using real municipal wastewater with three identical MBRs under different operating conditions. The results obtained in this study suggested that the food-microorganisms ratio (F/M) and membrane filtration flux were the important operating parameters that significantly influenced membrane fouling in MBRs. Neither concentrations of dissolved organic matter in the reactors nor viscosity of mixed liquor, which have been thought to have influences on fouling in MBRs, showed clear relationships with membrane fouling in this study. Organic substances that had caused the membrane fouling were desorbed from fouled membranes of the MBRs at the termination of the operation and were subjected to Fourier transform infrared (FTIR) and 13C nuclear magnetic resonance (NMR) analyses. These analyses revealed that the nature of the membrane foulant changes depending on F/M. It was shown that high F/M would make the foulant more proteinaceous. Carbohydrates were dominant in membrane foulants in this study, while features of humic substances were not apparent.     

THE FOULING AND CLEANING OF ULTRAFILTRATION MEMBRANES DURING THE FILTRATION OF MODEL TEA COMPONENT SOLUTIONS

Proteins and polyphenols are the principal fouling constituents in the ultrafiltration (UF) of black tea liquor. The aim of this study was to determine the relative importance of individual components in the fouling process, to investigate any synergetic interactions that were occurring and to compare the cleaning characteristics of different fouled membranes. A 30‐kD molecular weight cutoff polysulfone UF membrane in dead‐end mode was challenged with model solutions of tea components. Model solutions consisted of tea proteins, theaflavins (TFs), thearubigins and caffeine. Sodium hydroxide was used as a cleaning reagent. Permeate flux decline curves were presented for single components and mixtures. Individual component transfer fluxes and rejections were also presented. An unexpected finding was that protein in a mixture with TFs could permeate the membrane to a degree, while a protein solution in the absence of the polyphenol was completely rejected. The inspection of membranes fouled by different solutions revealed different foulant morphologies. Membrane cleaning with 0.2 wt % sodium hydroxide was generally found to be effective.     

采用AFM法表征芳纶短切纤维和沉析纤维表面黏附力

采用原子力显微镜(AFM)探针修饰技术,用芳纶沉析纤维薄膜对探针进行修饰,在水中测定了芳纶短切纤维和沉析纤维的表面黏附力,探究了不同pH值对芳纶短切纤维和沉析纤维表面黏附力的影响.实验结果表明,芳纶沉析纤维薄膜修饰的探针与芳纶短切纤维和沉析纤维之间的黏附力分别为1.71 nN和9.20 nN,沉析纤维分子间黏附作用力大于其与芳纶短切纤维间的黏附力,认为探针针尖与芳纶短切纤维和沉析纤维-NH-之间的相互作用与pH值相关,芳纶沉析纤维修饰的探针与芳纶沉析纤维之间的黏附力受pH值的影响较大.     

Membrane fouling during filtration of milk––a microstructural study

The surface morphology and internal microstructure of a membrane are the result of membrane manufacturing processes and subsequent use during fluid processing in industry. Both these structural factors have a great effect on fouling and filtration performance.

In this study, scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy were used to comprehensively characterise the surface of unused microfiltration and ultrafiltration membranes, the fouled layer on the surface of membranes used for milk filtration and the internal fouling within the used membranes.

A simple and effective sample preparation method was developed to study the internal membrane structure using high-resolution field emission SEM with low-accelerating voltage. Various methods of structural characterisation were compared and the results showed that for flat sheet membranes AFM is an appropriate and convenient technique for examining the surface topography of membranes. In contrast SEM is a very appropriate technique for examining the cross-sectional and internal structure of a membrane, either unused or fouled.

Using these complimentary techniques it has been shown that internal fouling, during filtration of skim milk, proceeds by protein–polymer and protein–protein interactions. A gel layer forms on the surface of the membrane and has been imaged using SEM. This layer is slightly compressible and densifies as it grows. Fouling initiation commences after a very short filtration time.