Visualisation of polysaccharide fouling on microporous membrane using different characterisation techniques

Although many studies assessed fouling behaviour in microporous membrane processes like membrane bioreactors (MBRs), in situ or direct observation of the fouling layer has not yet been possible. The observation of the fouling layer resulting from the filtration of model solutions allowed better understanding of MBR fouling intensity and mechanisms. In this study, alginate has been used as a model for polysaccharide (one of the main foulants in MBRs). Three visualisation techniques, confocal laser scanning microscopy (CLSM), environmental scanning electron microscopy (ESEM), and direct observation (DO) have been tested to observe the alginate fouling. The work presented in this paper revealed the advantages and limitations of each technique used for this specific application. Although no coating is required for this technique, ESEM allowed distinct non-destructive observation of clean membrane. However, the lack of structure in the alginate fouling layer limited the use of this technique for fouled membranes. While CLSM requires the use of expensive fluorescent markers, DO appeared as the most promising technique for direct and in situ observation of MBR fouling. DO of alginate/bentonite and alginate/bacteria solutions revealed the creation of a well-structured dual fouling system (bentonite-concentrated layer of 50 μm embedded and covered by a concentration polarisation of alginate greater than 240 μm) on the surface of hollow fibre membrane.     

A microfluidic membrane chip for in situ fouling characterization

A new method for non-invasive in situ monitoring of a microfiltration process is described. In microfiltration systems, local information on the deposition characteristics can be used to determine the cake behavior during a filtration run. Typically, non-invasive methods of fouling study are restricted to specialized membranes, or require highly complex systems. This study employs the use of synthetic embedded channel membranes, with channels separated by a porous structure (active membrane). The characteristics of the active membrane have been analyzed. Deposition on the membrane surface can be observed and monitored optically across the width of the feed channel. This can be used to observe the liquid hydrodynamics in the channel as well as the local cake properties in time. In dead end filtration, it has been observed that with 6 μm particles, the cake initially deposits towards the end of the membrane. However, as filtration continues, the deposition changes with more local deposition towards the channel entrance, leading to a more homogeneous cake layer.     

In situ monitoring techniques for concentration polarization and fouling phenomena in membrane filtration

Membrane fouling and subsequent permeate flux decline are inevitably associated with pressure-driven membrane processes. Despite the myriad of studies on membrane fouling and related phenomena--concentration polarization, cake formation and pore plugging--the fundamental mechanisms and processes involved are still not fully understood. A key to breakthroughs in understanding of fouling phenomena is the development of novel, non-invasive, in situ quantification of physico-chemical processes occurring during membrane filtration. State-of-the-art in situ monitoring techniques for concentration polarization, cake formation and fouling phenomena in pressure-driven membrane filtration are critically reviewed in this paper. The review addresses the physical principles and applications of the techniques as well as their strengths and deficiencies. Emphasis is given to techniques relevant to fouling phenomena where particles and solutes accumulate on the membrane surface such that pore plugging is negligible. The relevance of the techniques to specific processes and mechanisms involved in membrane fouling is also elaborated and discussed.     

In situ 3D characterization of membrane fouling by yeast suspensions using two-photon femtosecond near infrared non-linear optical imaging

In situ non-invasive 3D characterization of membrane fouling was achieved using femtosecond near infrared non-linear optical imaging together with a novel crossflow filtration module. Washed fluorophore-labelled yeast suspensions were filtered through Millipore 0.22 μm mixed cellulose ester membranes and the fouling layer was imaged at different times throughout the experiment.

Based on the 3D femtosecond images, it has been possible to identify fine structural features of the cake and to measure the thickness of the filter cake formed on the microfiltration (MF) membranes. Our findings reveal that low concentration feeds result in the initial formation of a patchy monolayer of cells leading to a multilayered cake, whilst at higher concentrations a multilayer cake forms rapidly. For patchy cakes, the technique offers greater resolution than that which is achievable with the direct observation through membrane technique. Deposited cell aggregates and broken fragments of cells can clearly be imaged. For thick cakes, it has been possible to image up to depths 45 μm below the cake surface in the present work.     

Flow field-flow fractionation as an analytical technique to rapidly quantitate membrane fouling

The initial fouling behavior of a clean membrane surface was studied using flow field-flow fractionation (flow FFF), an analytical technique typically used to separate and characterize macromolecules and particulates. This work represents the first time flow FFF has been used to quantitatively evaluate membrane performance. Flow FFF is an ideal tool for expeditiously studying sample–membrane interactions for the following reasons: membranes can be quickly installed into the flow FFF channel, each analysis requires only microgram amounts of sample, and sample–membrane interactions can be rapidly quantitated for different flowrates and solution compositions.Suwannee River humic acids were used as a probe to investigate the initial fouling of an XLE reverse osmosis membrane and an NF-200 nanofiltration membrane. Flow FFF was successfully used to quantitate the fouling of each membrane and to demonstrate that the majority of sample loss was due to irreversible adsorption. The fouling on both membranes was enhanced by increasing the flowrate perpendicular to the membrane surface and by adding calcium ions to the solution. The NF-200 membrane was more resistant than the XLE membrane to fouling in the presence of calcium ions, whereas, the fouling resistance of both membranes improved to similar levels with the addition of EDTA to a solution containing calcium ions.     

Ultrasonic time-domain reflectometry as a non-destructive instrumental visualization technique to monitor inorganic fouling and cleaning on reverse osmosis membranes

Fouling is readily acknowledged as one of the most critical problems limiting the wider application of membranes in liquid separation processes. A better understanding of fouling layer formation and its monitoring is needed in order to improve on existing cleaning techniques. The overall objective of this research was to develop a non-destructive, real-time, in situ visualization technique or device for fouling layer monitoring. Ultrasonic time-domain reflectometry (UTDR) was employed as a visualization technique to provide real-time characterization of the fouling layer. The fouling experiment was carried out with 2 g/l calcium carbonate solution. Results confirmed that there is a correspondence between the flux decline behavior and the UTDR response from membranes in reverse osmosis (RO) modules. The ultrasonic technique could effectively detect fouling layer initiation and growth on the membrane in real-time at different axial velocities. In addition to the measurement of fouling, the ultrasonic technique was also successfully employed for monitoring membrane cleaning. The UTDR technique, due to its extremely powerful capabilities and its use in monitoring devices, can be of great significance in the membrane industry.     

Experimental study of ultrafiltration membrane fouling by sodium alginate and flux recovery by backwashing

Membrane fouling is the major limitation for a broader application of membrane technology. One of the main causes of membrane fouling in advanced wastewater reclamation and in membrane bioreactors (MBR) are the extracellular polymeric substances (EPS). Among the main constituents in EPS, polysaccharides are the most ubiquitous. This study aims at a better understanding of the fouling mechanisms of EPS and the efficiency of backwashing technique, which is applied in practice to restore membrane flux. For that purpose, the evolution of fouling by sodium alginate, a microbial polysaccharide, is studied in ultrafiltration. Fouling experiments are carried out in a single fiber apparatus, aiming at identifying the significance of distinct fouling mechanisms and their degree of reversibility by backwashing. An important parameter considered in the study is the concentration of calcium ions, which promote sodium alginate aggregation and influence the rate of flux decline, the reversibility of fouling and rejection. A rapid irreversible fouling takes place due to internal pore constriction, at the beginning of filtration, followed by cake development on the membrane surface. With increased calcium addition, cake development becomes the dominant mechanism throughout the filtration step. Furthermore, fouling reversibility is increased with the increase of calcium concentration. A unique behavior of sodium alginate solution in the absence of calcium is also noted, i.e. the formation of a labile layer on the membrane surface, which is affected by the small cross-flow that exists inside hollow fibers, even in the nominally dead-end mode of operation.     

In situ three-dimensional characterization of membrane fouling by protein suspensions using multiphoton microscopy

Fouling of microfiltration membranes leads to severe flux declines and the need to clean or replace the membrane. In situ 3D characterization of protein fouling both on the surface and within the pores of the membrane was achieved using multiphoton microscopy. Time-lapse images of the fouled membrane were obtained for single suspensions and mixtures of fluorescently labeled bovine serum albumin and ovalbumin. Deposited protein aggregates were visible on the membrane and evidently play an important role in fouling. A combination of 3D images and resistance versus time data was used to identify the dominant fouling mechanism. Fouling is initially internally dominated, but after 1 and 15 min for ovalbumin and bovine serum albumin, respectively, the fouling becomes externally dominated. This is in good agreement with two-stage protein fouling models.     

Periodic air/water cleaning for control of biofouling in spiral wound membrane elements

The main problem during the operation of nanofiltration or reverse osmosis membrane plants is fouling of feed spacers in membrane elements due to biofouling and particulate fouling. In order to control biofouling and particulate fouling in membrane elements, both daily air/water cleaning (AWC) and daily copper sulphate dosing (CSD) were investigated and compared to a reference without daily cleaning. A pilot study was carried out for 110 days with three parallel spiral wound membrane elements; AWC, CSD and the reference which were fed by tap water enriched with a biodegradable compound (100 μg acetate-C/L). The CSD element, which combined daily copper sulphate dosing and sporadically air/water cleaning, performed best with an increase in pressure drop of 18% and a biomass concentration of 8000 pg ATP/cm² within 110 days. This was followed by the AWC element with a pressure increase of 37% and biomass concentration of 20,000 pg ATP/cm² within 110 days. The reference element showed a pressure increase of 120% within 21 days. The presented approach is considered very successful in controlling particulate fouling and biofouling, especially when air/water cleaning is combined with copper sulphate dosing.     

Nuclear magnetic resonance microscopy studies of membrane biofouling

There is a substantial need for novel measurement techniques that enable non-invasive spatially resolved observation of biofouling in nanofiltration (NF) and reverse osmosis (RO) membrane modules. Such measurements will enhance our understanding of the key design and operational parameters influencing biofilm fouling. In this study we demonstrate the first application of nuclear magnetic resonance microscopy (NMR) to a spiral wound reverse osmosis (RO) membrane module. The presented NMR protocols allow the extraction of the evolution with biofouling of (i) the spatial biofilm distribution in the membrane module, (ii) the spatially resolved velocity field and (iii) displacement propagators, which are distributions of molecular displacement of a passive tracer (in our case, water) in the membrane. From these measurements, the effective membrane surface area is quantified. Despite the opaque nature of membrane design, NMR microscopy is shown to be able to provide a non-invasive quantitative measurement of RO membrane biofouling and its impact on hydrodynamics and mass transport. Minimal biofilm growth is observed to have a substantial impact on flow field homogeneity.     

Concentrating the extract of traditional Chinese medicine by direct contact membrane distillation

This study applies direct contact membrane distillation (DCMD) to concentrating the extract of traditional Chinese medicine (TCM). The trans-membrane flux under various operation conditions was measured in real-time during concentration process. By decoupling the factors affecting the trans-membrane flux decline, it was found that the observed flux decline throughout the process could be attributed to the membrane fouling, the reduction of water vapor pressure and the increase of transport resistance at feed side. Analysis of the combined factors was given to show in detail the mechanism of flux decline. Factors that may affect the flux level, such as feed velocity, feed temperature and pretreatment were experimentally examined. Gas bubbling or sparging was introduced into DCMD system for reducing membrane fouling, and it was found that both gas–liquid two-phase flow at the feed side and gas back-washing within membrane module are effective ways to control membrane fouling.     

Quantifying the effect of ionic strength on colloidal fouling potential in membrane filtration

Ultrafiltration experiments were conducted to study the fouling potential of colloidal suspensions under different ionic strengths and colloid concentrations. A linear relationship was found relating the colloidal fouling potential to the logarithm of the Debye-Huckel parameter, a characteristic for electrical double layers of colloids. This finding provided a useful quantitative linkage between the colloidal fouling potential and the water chemistry. Considering the linear dependence of colloidal fouling potential on the colloid concentration, a bilinear model was proposed to explain the coupling effects of colloid concentration and ionic strength of the suspension on the fouling potential. The model predictions of fouling potential were found to fit accurately with experimentally determined fouling potential values. Further analysis of the model showed that ionic strength can significantly affect colloidal fouling, for example, a 10-fold increase in ionic strength from 0.001 to 0.01 M for a given feed concentration has the same membrane fouling effect as doubling the feed concentration. The model allows for a quick and reliable assessment of fouling potential without even performing any experiments. This could then be used to design the membrane process or pretreatment stages required to mitigate membrane fouling.     

Impact of ultrafiltration operating conditions on membrane irreversible fouling

The main limitation of the ultrafiltration (UF) process identified in drinking water treatment is membrane fouling. Although adsorption of natural organic matter (NOM) is known to cause irreversible fouling, operating conditions also impact the degree of irreversible fouling. This study examined the impact of several operating parameters on fouling including flux, concentrate velocity in hollow fibers, backwash frequency, and transmembrane pressure. A hydrophilic cellulose derivative membrane and a hydrophobic acrylic polymer membrane were used to conduct these tests. Pilot testing showed that when short-term reversible fouling was limited during a filtration cycle by increasing the concentrate velocity, reducing the flux, and increasing the backwash frequency, the evolution of the membrane toward irreversible fouling could be controlled. It appeared that operating parameters should be adjusted to maintain the increase of transmembrane pressure below a certain limit, determined to be approximately 0.85 to 1.0 bar for the tested UF membrane, in order to minimize the rate of irreversible fouling. This threshold for transmembrane pressure was confirmed empirically by compiling data from over 36 pilot studies. Other testing results demonstrated that hydraulic backwash effectiveness decreased as the transmembrane pressure applied in the previous filtration cycle increased. Backwash efficiency in terms of membrane flux recovery after hydraulic backwash was reduced by 50% when the transmembrane pressure was increased from 0.4 bar to 1.4 bar.     

Chemical and physical aspects of organic fouling of forward osmosis membranes

The growing attention to forward osmosis (FO) membrane processes from various disciplines raises the demand for systematic research on FO membrane fouling. This study investigates the role of various physical and chemical interactions, such as intermolecular adhesion forces, calcium binding, initial permeate flux, and membrane orientation, in organic fouling of forward osmosis membranes. Alginate, bovine serum albumin (BSA), and Aldrich humic acid (AHA) were chosen as model organic foulants. Atomic force microscopy (AFM) was used to quantify the intermolecular adhesion forces between the foulant and the clean or fouled membrane in order to better understand the fouling mechanisms. A strong correlation between organic fouling and intermolecular adhesion was observed, indicating that foulant–foulant interaction plays an important role in determining the rate and extent of organic fouling. The fouling data showed that FO fouling is governed by the coupled influence of chemical and hydrodynamic interactions. Calcium binding, permeation drag, and hydrodynamic shear force are the major factors governing the development of a fouling layer on the membrane surface. However, the dominating factors controlling membrane fouling vary from foulant to foulant. With stronger intermolecular adhesion forces, hydrodynamic conditions for favorable foulant deposition leading to cake formation are more readily attained. Before a compact cake layer is formed, the fouling rate is affected by both the intermolecular adhesion forces and hydrodynamic conditions. However, once the cake layer forms, all three foulants have very similar flux decline rates, and further changes in hydrodynamic conditions do not influence fouling behavior.     

Fe3+对MBR减缓膜污染的研究进展

膜生物反应器(membrane bioreactor, MBR)作为一种高效的污水处理及回用工艺,比传统的活性污泥法具有更多优势。然而,膜污染问题是限制其广泛应用的关键性问题。众多研究者已证实Fe₃₊能有效的改善MBR中混合液的可滤性及减缓膜污染。本文简述了MBR污泥混合液中主要污染物—胞外聚合物(extracellular polymeric substances, EPSs),并总结Fe₃ 在去除混合液中污染物、减缓膜污染方面的效能及其对污泥混合液的影响。最后,对Fe₃ 在减缓MBR膜污染的未来研究方向进行展望。     

A review on hollow fiber membrane module towards high separation efficiency: Process modeling in fouling perspective

Hollow fiber microfiltration (MF) and ultrafiltration (UF) membrane processes have been extensively used in water purification and biotechnology. However, complicated filtration hydrodynamics wield a negative influence on fouling mitigation and stability of hollow fiber MF/UF membrane processes. Thus, establishing a mathematical model to understand the membrane processes is essential to guide the optimization of module configurations and to alleviate membrane fouling. Here, we present a comprehensive overview of the hollow fiber MF/UF membrane filtration models developed from different theories. The existing models primarily focus on membrane fouling but rarely on the interactions between the membrane fouling and local filtration hydrodynamics. Therefore, more simplified conceptual models and integrated reduced models need to be built to represent the real filtration behaviors of hollow fiber membranes. Future analyses considering practical requirements including complicated local hydrodynamics and nonuniform membrane properties are suggested to meet the accurate prediction of membrane filtration performance in practical application. This review will inspire the development of high-efficiency hollow fiber membrane modules.     

A liquid porosimetry technique for correlating intrinsic protein sieving: Applications in ultrafiltration processes

The understanding of variation in sieving properties of membranes is of great importance for the successful development of ultrafiltration applications. A liquid porosimetry technique is presented to quantify the sieving variation among several polyethersulfone ultrafiltration membranes. Observed sieving coefficients were measured with proper precautions taken to control and minimize fouling. These data were translated to intrinsic sieving coefficients using a stagnant film model. The intrinsic membrane sieving coefficient correlated well with the liquid porosimetry data. This liquid porosimetry technique can distinguish between membranes of different molecular weight cut-off and is sensitive enough to capture slight changes in the sieving coefficient of variants of the same cut-off membrane. This technique has several attractive features: it is non-destructive, independent of the module configuration and relatively simple to perform. Two potential applications of this technique are also examined: (1) quantification of the effect of membrane variation on high performance tangential flow filtration (HPTFF) for protein separations and (2) development of a membrane integrity test to ensure batch-to-batch consistency. This technique has the potential for use in membrane quality control, membrane selection, and validation of industrial ultrafiltration processes.     

Macroscopic and microscopic characterizations of a cellulosic ultrafiltration (UF) membrane fouled by a humic acid cake deposit: First step for intensification of reverse osmosis (RO) pre-treatments

One of the critical issues for the application of low-pressure membrane processes (microfiltration, MF or ultrafiltration, UF) as pre-treatment processes for freshwater preparation is membrane fouling due to natural organic matter (NOM). The aim of this preliminary study is to contribute to a better understanding of the fouling phenomena occurring on a regenerated cellulose UF membrane fouled with a humic acid cake deposit. The originality of this work is based on a double approach on surface analysis at both macroscopic and microscopic scales. It is presently reported that humic acid fouling is mainly governed by cake formation, which plays a major role in flux decline via the well-known model of resistances in series. We obtained that the adsorbed resistance is 2% of the total resistance while the cake resistance is 52% of the total resistance, which is higher than that of the virgin membrane. From field emission gun scanning electron microscopy (FESEM) it was found for the first time that the humic acid cake is well organized, and particularly in fractal forms. The fractal dimension (FD) of the cake is determined as 2.52, which is in good agreement with the theoretical fractal dimension of particle–cluster aggregation underlying diffusion-limited aggregation (FD = 2.51). This new microscopic fouling index decreases with the presence of cake and can be correlated with the decrease of the hydraulic permeability. The classical silt density index (SDI) and the new modified fouling index (denoted MFI-UF) were obtained and also proved the presence of the cake. To complete this approach transmembrane streaming potential (denoted SP) measurements were conducted with a new homemade apparatus developed in our lab and presented for the first time in the present article, helped us to observe also a penetration of low molecular fractions of humic acid inside the membrane. Indeed the displacement of the isoelectric point (iep) of the membrane from 2.3 to 1.5 for the virgin and fouled membranes, respectively, permitted to illustrate this penetration. This newly designed SP apparatus is a semi-automatic tool assisted by a software denoted as proFluid 1.2. Furthermore, preliminary experiments with seawater were realized in order to estimate the influence of seawater filtration on the hydraulic permeability and SP parameters for the RC 100-kDa membrane.     

Non-invasive monitoring of fouling in hollow fiber membrane via UTDR

Fouling is the most critical problem associated with membrane separations in liquid media. But it is difficult to control the inevitable membrane fouling because of its invisibility, especially on the inside surface of hollow fiber membranes. This study describes the extension of ultrasonic time-domain reflectometry (UTDR) for the real-time measurement of particle deposition in a single hollow fiber membrane. A transducer with a frequency of 10 MHz and polyethersulfone hollow fiber membranes with 0.8 mm inside diameter (ID) and 1.2 mm outside diameter (OD) were used in this study. The fouling experiments were carried out with 1.8 g/L kaolin suspension at flow rates 16.7 and 10.0 cm/s. The results show that UTDR technique is able to distinguish and recognize the acoustic response signals generated from the interfaces water/upper outside surface of the hollow fiber, lumen upside surface/water, water/lumen underside surface and lower outside surface/water in the single hollow fiber membrane module in pure water phase. The systemic changes of acoustic responses from the inside surfaces of the hollow fiber in the time- and amplitude-domain with operation time during the fouling experiments were detected by UTDR. It is associated with the deposition and formation of the kaolin layer on the inside surfaces. Further, the acoustic measurement indicates that the deposited fouling layer is denser on the lumen underside surface of the hollow fiber than that on the lumen upside surface as a result of weight. Moreover, it is found that the fouling layer grows faster on the inside surface of the hollow fiber at a flow rate of 10.0 cm/s than that at 16.7 cm/s due to the lower shear stress. The fouling layer formed is thicker at a flow rate of 10.0 cm/s than that at 16.7 cm/s. The flux decline data and SEM analysis corroborate the ultrasonic measurement. Overall, this study confirms that UTDR measurement will provide not only a new protocol for the observation of hollow fiber membrane fouling and cleaning, but also a quantitative approach to the optimization of the membrane bioreactor system.     

Humic acid fouling during microfiltration

A major factor limiting the use of microfiltration for surface water treatment is membrane fouling by natural organic matter. The extent and mechanisms of humic acid fouling during microfiltration have been examined using stirred cell filtration experiments and scanning electron microscopy. The extent of fouling was strongly dependent on both the source and preparation of the humic acid solutions. The large flux decline observed during constant pressure microfiltration was caused by the formation of a humic acid deposit located on the upper surface of the membrane. Prefiltration of the humic acid solutions dramatically reduced the rate of fouling through the removal of large humic acid aggregates. The initial fouling in this system was determined almost entirely by the convective deposition of these large particles/aggregates on the membrane surface. This initial deposit accelerated the subsequent rate of humic acid fouling, possibly serving as a nucleation site for deposition of macromolecular humic acids.