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1.
Many studies have been undertaken to understand the fouling of the ultrafiltration membranes in drinking water treatment. Physico-chemical fouling of membranes depends on characteristics of the raw water and membrane surface properties. In the case of Biwa lake, some chemical parameters as Si and Fe concentrations change with temperature (season) causing irreversible fouling. While some exits on the influence of the particle mineralogy on the fouling, little work has been developed to elucidate the relation between the physicochemical complexity of the cake and the fouling. Generally clays or oxides are known to lead to a reversible fouling. In this work, the interactions between a UF organic membrane with minerals leading to a hardly reversible fouling are studied. In the case of the Biwa lake water, fouling of ultrafiltration membranes results from the formation of a Si-rich ferric gel directly deposited on the membrane surface and a secondary allophanic gel layer at a bigger distance. The deposit nature and the membrane/cake interactions were studied using infra-red, X-ray diffraction, Al and Si NMR and EXAFS technics. The effect of mineral particles, especially ferric oxides associated with silica, has been demonstrated. The formation of Fe---Si gel directly on the membrane surface is mainly responsible for the fouling. The change of these particles is less negative than the membrane surface. The structure of such a material is complex. The low permeability of the gel is at the prime origin of the fouling.  相似文献   

2.
In protein ultrafiltration (UF), the limiting flux phenomenon has been generally considered a consequence of the presence of membrane fouling or the perceived formation of a cake/gel layer that develops at high operating pressures. Subsequently, numerous theoretical models on gel/cake physics have been made to address how these factors can result in limiting flux. In a paradigm shift, the present article reestablishes the significance of osmotic pressure by examining its contribution to limiting flux in the framework of the recently developed free solvent osmotic pressure model. The resulting free-solvent-based flux model (FSB) uses the Kedem–Katchalsky model, film theory and the free solvent representation for osmotic pressure in its development. Single protein tangential-flow diafiltration experiments (30 kDa MWCO CRC membranes) were also conducted using ovalbumin (OVA, 45 kDa), bovine serum albumin (BSA, 69 kDa), and immuno-gamma globulin (IgG, 155 kDa) in moderate NaCl buffered solutions at pH 4.5, 5.4, 7 and 7.4. The membrane was preconditioned to minimize membrane fouling development during the experimental procedure. The pressure was randomly selected and flux and sieving were determined. The experimental results clearly demonstrated that the limiting flux phenomenon is not dominated by membrane fouling and the FSB model theoretically illustrates that osmotic pressure is the primary factor in limiting flux during UF. The FSB model provides excellent agreement with the experimental results while producing realistic protein wall concentrations. In addition, the pH dependence of the limiting flux is shown to correlate to the pH dependency of the specific protein diffusion coefficient.  相似文献   

3.
Hydrous manganese dioxide (HMO) nanoparticles incorporated cellulose acetate (CA) composite ultrafiltration (UF) membranes are prepared with the aim of improving the water permeation and BSA contaminant removal. The HMO nanoparticles are synthesized from manganese ion and characterized by FT‐IR, XRD, and FESEM. The effect of variation of HMO on CA membranes is probed using FT‐IR, EDAX, contact angle, SEM, and AFM analysis to demonstrate their chemical functionality, hydrophilicity, and morphology. CA/HMO membranes are showing the enhancement in pure water flux (PWF), water uptake, porosity, hydrophilicity, fouling resistance, BSA rejection, and flux recovery ratio (FRR). CA‐1 membrane displayed higher PWF (143.6 Lm2h?1), BSA rejection (95.9%), irreversible fouling (93.3%), and FRR (93.3%). Overall results confirmed that the CA/HMO nanocomposite UF membranes overcome the bottlenecks and shows potential for water treatment applications.  相似文献   

4.
A method based on a simple linear regression fitting was proposed and used to determine the type, the chronological sequence, and the relative importance of individual fouling mechanisms in experiments on the dead-end filtration of colloidal suspensions with membranes ranging from loose ultrafiltration (UF) to nanofiltration (NF) to non-porous reverse osmosis (RO). For all membranes, flux decline was consistent with one or more pore blocking mechanisms during the earlier stages and with the cake filtration mechanism during the later stages of filtration. For ultrafiltration membranes, pore blocking was identified as the largest contributor to the observed flux decline. The chronological sequence of blocking mechanisms was interpreted to depend on the size distribution and surface density of membrane pores. For salt-rejecting membranes, the flux decline during the earlier stages of filtration was attributed to either intermediate blocking of relatively more permeable areas of the membrane skin, or to the cake filtration in its early transient stages, or a combination of these two mechanisms. The findings emphasize the practical importance of the clear identification of, and differentiation between mechanisms of pore blocking and cake formation as determining the potential for the irreversible fouling of membranes and the efficiency of membrane cleaning.  相似文献   

5.
This study investigates the performance of ultrafiltration (UF) by membranes coated with titanium dioxide (TiO2) photocatalyst under ultraviolet (UV) illumination in removing natural organic matter (NOM) and possibly in reducing membrane fouling. Experiments were carried out using heat-resistant ceramic disc UF membranes and humic acids as model substances representing naturally occurring organic matter. Membrane sizes of 1, 15, and 50 kDa were used to examine the effects of coating under ultraviolet irradiation. A commercial humic solution was subjected to UF fractionation (batch process); gel filtration chromatography was applied to study the effects of molecular weight distribution of NOM on UF membrane fouling. When compared to naked membranes, UV254 (ultraviolet light of lambda=254 nm) illumination of TiO2-coated membranes exhibits more flux decline with similar effluent quality. Although the UF membrane is able to remove a significant amount of humic materials, the incorporated photocatalysis results in poor performance in terms of permeate flux. The TiO2-coated membrane under UV254 irradiation alters the molecular weight (MW) distribution of humic materials, reducing them to <1 kDa, which is smaller than the smallest (1-kDa) membrane in this study. Thus, TiO2-coated membranes under UV254 irradiation do not perform any better in removing natural organic matter and reducing membrane fouling.  相似文献   

6.
A new random copolymer was synthesized by reacting hydrophilic N,N-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl) (DMMSA) with hydrophobic butyl methacrylate (BMA) through a conventional radical polymerization. The as-prepared sulfobetaine copolymer (DMMSA–BMA) was blended with polyethersulfone (PES) to fabricate antifouling ultrafiltration membrane for BSA separation. The X-ray photoelectron spectroscopy analysis of blend membranes revealed concentration of sulfobetaine groups at the membrane surfaces that endowed the membrane with higher hydrophilicity and better antifouling property. For the membrane with 8.0 wt% DMMSA–BMA copolymer concentration (No. 5), irreversible fouling has been considerably reduced and the flux recovery rate of the blend membrane reached as high as 82.8%. Furthermore, the blend membrane could effectively resist BSA fouling in a wide pH range from 4.0 to 8.0.  相似文献   

7.
A rapid characterization method was used to study protein fouling of cellulose acetate membrane during dead-end, in-line, constant flux microfiltration. Based on pressure-permeate volume profiles, two fouling phases could be identified and compared at different permeate fluxes. Using protein staining dyes, the model foulant (bovine serum albumin) was found to deposit on the upstream side of the membrane as a loose cake at its isoelectric point. The effects of solution pH on both the nature and extent of membrane fouling, and membrane cleaning were examined. To further understand and quantitatively analyze the fouling behavior, a combined mathematical model which took into account pore blocking, cake formation and pore constriction was developed based on existing fouling models. The data obtained by modeling was in good agreement with experimental fouling data. Theoretical analysis of data clearly indicated that cake formation was the main fouling mechanism. Using methods such as dynamic light scattering, the significant role of large protein aggregates in membrane fouling was confirmed. The dimer composition of protein did not change significantly during the fouling experiments, clearly indicating that smaller aggregates played less important role in membrane fouling.  相似文献   

8.
Cu(OH)2 nanowires were prepared and incorporated into poly(vinylidene fluoride) (PVDF) to fabricate Cu(OH)2-PVDF ultrafiltration (UF) membrane via immersion precipitation phase inversion process.The effect of Cu(OH)2 nanowires on the morphology of membranes was investigated by X-ray photoelectron spectroscopy (XPS),Fourier transform infrared (FTIR) spectroscopy,atomic force microscopy (AFM),scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements.The results showed that all the Cu(OH)2-PVDF membranes had wider fingerlike pore structure and better hydrophilicity,smoother surface than pristine PVDF membrane due to the incorporation of Cu(OH)2 nanowires.In addition,water flux and bovine serum albumin (BSA) rejection were also measured to investigate the filtration performance of membranes.The results indicated that all the Cu(OH)2-PVDF membranes had high water flux,outstanding BSA rejection and excellent antifouling properties.It is worth mentioning that the optimized performance could be obtained when the Cu(OH)2 nanowires content reached 1.2 wt%.Furthermore,the membrane with 1.2 wt% Cu(OH)2 nanowires showed outstanding oil-water emulsion separation capability.  相似文献   

9.
An analysis of the flux decline encountered during ultrafiltration (UF) in a batch cell is presented by including the combined influence of the osmotic pressure and the gel layer. A predictive model for the flux decline in unstirred and stirred batch cell UF processes is developed by unifying the osmotic pressure and gel layer models. UF experiments were performed in a batch cell with polymeric solutes (PEG, dextran and PVA) and a protein (BSA), ranging widely in molecular weights and physico-chemical properties, under various operating conditions (pressure, solution pH, and stirrer speed). The present unified model predictions match closely with the experimental flux behaviour for all cases, while individual osmotic pressure and gel layer models are found to be inadequate.  相似文献   

10.
Cross-flow ultrafiltration and microfiltration have been used to recover refined soy sauce from soy sauce lees for over 25 years. The precise mechanism which dominated the permeate flux during batch cross-flow filtration has not been clarified. In the present study, we proposed a modified analytical method incorporated with the concept of deadend filtration to determine the initial flux of cross-flow filtration and carried out the permeate recycle and batch cross-flow filtration experiments using soy sauce lees. We used UF and MF flat membrane (0.006 m2 polysulfone) module under different transmembrane pressures (TMP) and cross-flow velocities. The modified analysis provided an accurate prediction of permeate flux during the filtration of soy sauce lees, because this model can consider the change in J0 at initial stage of filtration which was caused by the pore constriction and plugging inside membrane, and these changes may not proceed when the cake was formed on the membrane surface. Mean specific resistance of the cake increased with TMP due to the compaction of the cake and decreased with cross-flow velocity due to the change of deposited particle size, but less depended on the membrane in the present study. These results indicate that the value of J0 determined by modified method was relevant to exclude the effects of the initial membrane fouling by pore constriction due to protein adsorption and plugging with small particles. The modified analytical method for the cake filtration developed in the present study was considered to be capable of selecting an appropriate operating conditions for many cross-flow filtration systems with UF, MF membranes.  相似文献   

11.
Highly fouling-resistant ultrafiltration (UF) membranes were synthesized by heterogeneous photograft copolymerization of two water-soluble monomers, poly(ethylene glycol) methacrylate (PEGMA) and N,N-dimethyl-N-(2-methacryloyloxyethyl-N-(3-sulfopropyl)ammonium betaine (SPE), with and without cross-linker monomer N,N'-methylene bisacrylamide (MBAA), onto a polyethersulfone (PES) UF membrane. The characteristics, the stability, and the UF separation performance of the resulting composite membranes were evaluated in detail. The membranes were characterized with respect to membrane chemistry (by ATR-IR spectroscopy and elemental analysis), surface wettability (by contact angle), surface charge (by zeta potential), surface morphology (by scanning electron microscopy), and pure water permeability and rejection of macromolecular test substances (including the "cutoff" value). The surface chemistry and wettability of the composite membranes did not change after incubating in sodium hypochlorite solution (typically used for cleaning UF membranes) for a period of 8 days. Changes in water permeability after static contact with solutions of a model protein (myoglobin) were used as a measure of fouling resistance, and the results suggest that PEGMA- and SPE-based composite membranes at a sufficient degree of graft modification showed much higher adsorptive fouling resistance than unmodified PES membranes of similar or larger nominal cutoff. This was confirmed in UF experiments with myoglobin solutions. Similar results, namely, a very much improved fouling resistance due to the grafted thin polymer hydrogel layer, were also obtained in the UF evaluation using humic acid as another strong foulant. In some cases, the addition of the cross-linker during modification could improve both permeate flux and solute rejection during UF. Overall, composite membranes prepared with an "old generation" nonfouling material, PEGMA, showed better performance than composite membranes prepared with a "new generation" one, the zwitterionic SPE.  相似文献   

12.
Cu(OH)_2 nanowires were prepared and incorporated into poly(vinylidene fluoride)(PVDF) to fabricate Cu(OH)_2-PVDF ultrafiltration(UF) membrane via immersion precipitation phase inversion process. The effect of Cu(OH)_2 nanowires on the morphology of membranes was investigated by X-ray photoelectron spectroscopy(XPS), Fourier transform infrared(FTIR) spectroscopy, atomic force microscopy(AFM), scanning electron microscopy(SEM) and X-ray diffraction(XRD) measurements. The results showed that all the Cu(OH)_2-PVDF membranes had wider fingerlike pore structure and better hydrophilicity, smoother surface than pristine PVDF membrane due to the incorporation of Cu(OH)_2 nanowires. In addition, water flux and bovine serum albumin(BSA) rejection were also measured to investigate the filtration performance of membranes. The results indicated that all the Cu(OH)_2-PVDF membranes had high water flux, outstanding BSA rejection and excellent antifouling properties. It is worth mentioning that the optimized performance could be obtained when the Cu(OH)_2 nanowires content reached 1.2 wt%. Furthermore, the membrane with 1.2 wt% Cu(OH)_2 nanowires showed outstanding oil-water emulsion separation capability.  相似文献   

13.
《Comptes Rendus Chimie》2007,10(9):803-812
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.  相似文献   

14.
Fouling in the low-pressure membrane filtration of secondary effluent for water reuse can be severe due to the complex nature of the components in the water. Pre-filtration, coagulation and anion exchange resin were investigated as pre-treatments for reducing fouling of microfiltration (MF) and ultrafiltration (UF) membranes in the treatment of activated sludge-lagoon effluent. The key fouling components were determined using several analytical techniques to detect differences in the organic components between the feed and permeate.Pre-filtration (1.5 μm) enhanced the permeate flux for MF by removing particulates, but had little effect for UF. Marked flux improvement was obtained by coagulation pre-treatment at 5 mg L−1 Al3+ with internal membrane fouling being substantially alleviated. Anion exchange resin removed >50% of effluent organic matter but did not improve the flux or reduce irreversible membrane fouling. These results, together with detailed organic compositional analyses, showed that the very high-molecular weight organic materials (40–70 kDa) comprised of hydrophilic components such as soluble microbial products, and protein-like extracellular matter were the major cause of membrane fouling.  相似文献   

15.
The fouling tendency, due to adsorption on the pore walls, of two pairs of modified and unmodified ultrafiltration membranes, with similar observed retentions determined by dextran and gel permeation chromatography, was studied. The membranes investigated were made of modified and unmodified polyaramide (PA) and modified and unmodified polyvinylidene fluoride (PVDF). The PVDF membrane was surface-modified and the PA membrane was made from a modified polymer solution. Membrane modification was used to reduce fouling by adsorption. Octanoic acid was used as the fouling substance, representing a large number of small, hydrophobic compounds. It is demonstrated in this investigation that membrane modification is not always successful. It was determined that at lower concentrations of octanoic acid, the modified PA membrane exhibits a smaller fouling tendency than the unmodified PA membrane, while the result is reversed for concentrations above 60% of the saturation concentration. The fouling tendency of the unmodified PVDF membrane is much lower than that of the modified PVDF membrane at all concentrations. The cross-sections of the membranes were visually examined with scanning electron microscopy, but no difference could be observed between the modified and unmodified membranes. The membranes were also examined with Fourier transform infrared spectroscopy. The spectra of the two PA membranes were different, while no difference was observed for the unmodified and surface-modified PVDF membranes. Remains of octanoic acid were found in the membranes, although they had been thoroughly rinsed with deionized water and the initial pure water flux was recovered.  相似文献   

16.
Ultrafiltration membranes with similar pore sizes were prepared from acrylonitrile homopolymer and copolymers with increasing acrylamide content. The membranes containing acrylamide were more hydrophilic, had a smaller dispersion force component of the surface energy, and a smaller negative zeta potential than those prepared from the homopolymer. The effect of the differing surface chemistry of these membranes with similar pore sizes was examined by studying the ultrafiltration of bovine serum albumin (BSA) as a function of feed pH. The hydrophilic membranes showed higher permeate fluxes and flux recoveries than the hydrophobic membrane, in spite of their reduced repulsive electrostatic interaction. With increasing pH, protein transmission increased markedly for the acrylamide containing membranes whereas the transmission through the hydrophobic membrane remained low. These rejection data are explained by the combined effects of the increased hydrophilicity, decreased dispersive surface energy and reduced electrostatic repulsion of the acrylamide containing membranes.  相似文献   

17.
Surface porosities of Amicon XM100A and XM300 membranes have been measured by electron microscopy and found to be less than 1 per cent. From the measured pore size distributions it is deduced that 50 per cent of the solvent flow is through 20 to 25 per cent of the pores.The conventional model for concentration polarisation in ultrafiltration (UF), which assumes a homogeneously permeable membrane surface, has been modified to account for regions of differing permeability. An effective free area correction factor (≤ 1.0) has been introduced to allow for the effect of membrane surface properties on gel-polarised UF flux.Ultrafiltration experiments with protein solutions and membranes with a range of water fluxes confirm that gel-polarised UF flux is dependent on membrane permeability and surface properties. Effective free area correction factors vary from about 0.4 to 1.0 with values < 1.0 obtained for membranes with water fluxes typically < 150 1/m2 hr at 100 kPaSupport for the effective free area concept in UF is provided by an analogy between a gel-polarised UF membrane and a composite reverse osmosis membrane. In both cases the magnitude of the upper ‘controlling’ resistance may be influenced by the pore size and spacing of the lower supporting structure.  相似文献   

18.
Micellar-enhanced ultrafiltration (MEUF) of phenol and a cationic surfactant, cetylpyridinium chloride (CPC), is studied using two polysulfone membranes of 5- and 50-kDa molecular weight cutoff (MWCO) and two ceramic membranes of 15- and 50-kDa MWCO. Filtrations are run under laminar cross-flow and steady-state conditions. The effect of operation variables (pressure and retentate flux) and membrane properties (nature and MWCO) on permeate flux, surfactant, and phenol rejections is analyzed. The permeate flux depends, among other variables, on the fouling favored by membrane-micelle interactions, which are strongest in the 50-kDa MWCO ceramic membrane. On the other hand, surfactant rejection is mainly determined by the pore size and influenced by the pressure for both 50-kDa MWCO membranes. An equilibrium distribution constant, K(s), of phenol between surfactant micelles and water is calculated. Its value is not significantly affected by operation conditions and membrane type. K(s) is also approximately 20% lower than the value determined in a previous work with batch dead-end ultrafiltration.  相似文献   

19.
Operation at sub-critical fluxes can be used to control membrane fouling. The original definition of the critical flux stated that operation was sub-critical if no or negligible fouling occurred. Over time there has been a relaxing of the criteria and many now consider a low rather than zero rate of fouling to be indicative of sub-critical operation especially when dealing with complex feeds. Here the region of low fouling is termed “nominally sub-critical”. Unwashed yeast, washed yeast and extra polymeric substance (EPS) suspensions were filtered at controlled fluxes to investigate the role of cells and soluble components in nominally sub-critical conditions using ultrafiltration (UF) and microfiltration (MF) membranes. As the UF membrane could not be effectively cleaned it was not used in the later part of the study. Tracking of membrane resistance, of the 0.2 μm membranes was continued through the whole study. After the initial increase, rises very slowly, increasing on average only 0.4% after each experiment and cleaning cycle. For the MF membranes, the rate of fouling increased with increasing feed concentration, increasing membrane pore size and decreasing shear stress. The effect of increasing shear stress was to reduce the amount of reversible fouling but the irreversible component was invariant with shear stress for the range studied. Also the rate and reversibility of fouling were found to be sensitive to changes in pH. The sum of the rates of transmembrane pressure (TMP) rise for washed yeast cells and EPS suspensions were in all cases found to be lower than that for unwashed yeast. The origin of the additional resistance is discussed and other relevant literature reviewed.  相似文献   

20.
The main problem in treating oil/water emulsion from car wash waste-water by ultrafiltration (UF) is fouling caused by oil adsorption on the membrane surface and internal pore walls. This study demonstrates that the addition of bentonite clay can reduce the adsorption layer on cellulose acetate UF membrane, resulting in a reduction of total membrane resistance (Rt). Experiments were conducted to identify and describe three possible mechanisms: (i) bulk oil emulsion concentration reduction; (ii) particle aggregation and (iii) detachment of the adsorbed gel layer by shear force. Adsorption of oil emulsion by bentonite can lead to a significant reduction of bulk oil emulsion concentration, one of the major causes of flux enhancement. Results show that contact of oil emulsion with bentonite forms larger particles resulting in flux increment. An optimum particle size of 37 μm, corresponds with a bentonite concentration of 300 mg/l and provided the highest flux. Beyond this limiting concentration, flux improvement gradually declined, possibly due to the formation of packed cake of particles on the membrane surface. The presence of bentonite in the oil emulsion promotes high shear stress which acts against the gel layer. This high shear stress, caused by bentonite particles and cross-flow velocity, reverses the adsorbed gel layer to the bulk of the liquid phase.  相似文献   

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