Efficiency of various chemical cleanings for nanofiltration membrane fouled by conventionally-treated surface water

Nanofiltration systems are generally cleaned chemically. The optimal choice of the cleaning agent is a function of membrane material and foulant in a complex manner. This study evaluated the cleaning efficiency and effects of several cleaning agents on NF255 nanofiltration membrane. The nanofiltration pilot plant was fed with conventionally-treated surface water from a water treatment plant in southern Finland. Fouled membranes were cleaned weekly with different chemicals and procedures, and the cleaning efficiencies were compared in terms of flux recoveries and foulant removals. On the basis of the cleaning chemical analysis, the fouling material consisted of biofouling, organic deposits and metal complexes. In these circumstances, alkaline cleaners with chelatants resulted in the most efficient cleaning both in terms of flux recovery and foulant removal. Alkaline cleaning modified the membrane and improved the flux substantially in comparison to the virgin state. The results demonstrate that the choice of chemical cleaning agent is critical to cleaning efficiency, both technically and economically. The same flux recovery could be reached either by a single cleaning phase or by three sequential cleaning phases.     

Chemical Cleaning of Microfiltration Membranes Fouled by Whey

Millipore hydrophobic polyvinylidene fluoride (PVDF) microfiltration membranes were used for whey processing. Fouled membranes were cleaned with acid (HCl), alkaline (NaOH) and surfactant (Triton‐X100). The latter resulted in maximum flux recovery and resistance removal. Hydrochloric acid had a moderate effect and sodium hydroxide was the weakest cleaning agent. This is due to the cleaning strength of emulsifiers compared to acid or alkali. However acids are more efficient than alkaline solutions for removal of mineral compounds which remain on the membrane surface. Cleaning efficiency depends on the concentration of cleaning agent being higher for higher surfactant concentration. For acids and alkali, the efficiency increases with increasing the concentration of the reagent reaches a maximum (optimum concentration) and then decreases. This can be explained by changes in permeability of the deposit layer with the concentration of the cleaning agent. Another explanation is the breakage of proteins by acid or alkali which produces more fouling materials and causes less cleaning efficiency. Operating conditions affect the cleaning process. At higher stirring speeds (turbulent flow) or longer cleaning time better removal of deposits and higher cleaning efficiency were observed. The sequential cleaning process may or may not improve the cleaning efficiency. When acidic cleaning was followed by washing with a surfactant an improvement was achieved. This can be attributed to the incomplete removal of deposits by acid. However further cleaning with acid can not improve the cleaning efficiency. During whey processing fouling occurs by deposition of foulants of mostly proteins and macromolecules on the membrane surface or in the membrane matrix. Large substances (compared to the membrane pores) settle on the membrane surface and the small species penetrate and are adsorbed in the membrane pores. Cleaning dissolves and removes the adsorbed foulants from the membrane.     

Application of heat-activated peroxydisulfate process for the chemical cleaning of fouled ultrafiltration membranes

Na Cl O has been widely used to restore membrane flux in practical membrane cleaning processes, which would induce the formation of toxic halogenated byproducts. In this study, we proposed a novel heatactivated peroxydisulfate(heat/PDS) process to clean the membrane fouling derived from humic acid(HA). The results show that the combination of heat and PDS can achieve almost 100% recovery of permeate flux after soaking the HA-fouled membrane in 1 mmol/L PDS solution at 50 °C for 2 h, which is att...     

Direct visual observation of yeast deposition and removal during microfiltration

Periodic reverse flow through membranes is an effective technique to remove foulants from microfiltration (MF) membrane surfaces. This work explored direct visual observation (DVO) of yeast deposition and subsequent removal via backwashing and single backpulses using microvideo photography with cellulose-acetate (CA) and Anopore anodised-alumina (AN) MF membranes. Foulant deposited less uniformly on the surfaces of the CA membranes than on the AN membrane surfaces during forward filtration. Foulant cake layers of approximately 30 μm thickness formed on both membranes after forward filtration for 1–2 h, leading to fouled-membrane fluxes of only 15–25% of the clean-membrane fluxes.Foulant was removed by reverse flow from the CA membrane surfaces in clumps. The time constant for foulant removal was determined from photomicrographs to be approximately 0.2 s, and 95% of the membrane surface was cleaned within 1 s of backpulsing, resulting in 95% recovery of the initial flux. The foulant cake was also removed from the AN membranes in clumps, though much of the membrane remained covered in a monolayer of yeast. The flux through the membrane covered with a full monolayer was determined during forward filtration to be about 70% of the clean membrane flux.A model for flux recovery is proposed which takes into account the fraction of the membrane surface which is completely cleaned as well as the fraction which remains covered in a foulant monolayer. The predicted and experimentally-determined recovered fluxes as a function of backpulse duration are in very good agreement.     

Fouling and cleaning of membranes in the ultrafiltration of the aqueous extract of soy flour

The aqueous extract of soy flour is an emulsion/suspension of proteins, lipids and carbohydrates. The foulant deposit formed on the surface of polysulfone membranes in the ultrafiltration of this complex extract was investigated from several aspects including thickness, physical structure, chemical analysis and rheological behaviour. SEM studies showed the thickness of the foulant deposit was approximately 0.2 μm for 50000 MWCO membrane and 0.4 μm for 100000 MWCO membrane. The structure of the foulant deposit consisted of lipids in a globular form of 0.2 to 1 μm diameter adhered to, and supported by, a protein-polysaccharide matrix. Rheological measurements were conducted on a sample of the foulant deposit collected from the 100000 MWCO membrane. This foulant deposit exhibited pseudoplastic and viscoelastic properties which totally resisted the surface shear stresses in the flat-plate module. Recovery of the water flux of the fouled membranes was achieved by a four-stage cleaning procedure comprising successive stages of washing with sodium hydroxide, protease detergent, sodium hypochlorite and flushing with water.     

Surface modification of polypropylene membranes by γ-ray induced graft copolymerization and their solute permeation characteristics

Porous hydrophobic polypropylene (PP) membranes were subjected to the surface modification by the γ-ray induced graft copolymerization with hydrophilic 2-hydroxyethyl methacrylate (HEMA). The structural changes and surface morphologies of the modified PP membranes were characterized by a Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA) and field emission scanning electron microscopy (FE-SEM). Peroxides produced from γ-ray irradiation were determined by a 1,1-diphenyl-2-picryl hydrazyl (DPPH) method and the surface hydrophilicities of membranes were measured by a static contact angle measurement. The contact angle of the modified membranes reduced with the degree of grafting (DG) of HEMA onto the membrane surface, and it decreased up to about half of that before modification. The permeation behaviors of all membranes were investigated by a bovine serum albumin (BSA) filtration experiment. As a result, the DG of the modified membrane increased with the reaction time. However, in the case of irradiation dosage it showed the maximum value at 20 kGy. Also, the modified membrane showed a higher solution flux, lower BSA adsorption, and the better flux recovery after cleaning than that of the unmodified membrane. Particularly, 40.6% grafted membrane showed a two-fold increase in a BSA solution flux, 62% reduction in total fouling and three-fold increase in flux recovery after chemical cleaning.     

Versatility of hydrophilic and antifouling PVDF ultrafiltration membranes tailored with polyhexanide coated copper oxide nanoparticles

Hydrophilic poly(vinylidene fluoride) (PVDF) nanocomposite ultrafiltration (UF) membranes with excellent antifouling and antibiofouling characteristics are fabricated by employing polyhexanide coated copper oxide nanoparticles (P–CuO NPs). The presence of P–CuO NPs is played a significant role in altering the PVDF membrane matrix and probed by XRD, FTIR, FESEM and contact angle analysis. The PVDF/P–CuO nanocomposite membranes exhibited an outstanding antifouling performance indicated by the superior pure water flux, effective foulant separation and maximum flux recovery ratio during UF experiments as a result of the formation of the hydrophilic and more porous membrane due to the uniform distribution of P–CuO NPs. Particularly, the PVDF/P–CuO-3 membrane showed higher PWF of 152.5 ± 2.4 lm⁻²h⁻¹ and porosity of 64.5% whereas the lower contact angle of 52.5°. Further, it showed the higher rejection of 99.5 and 98.4% and the flux recovery ratio of 99.5 and 98.5% respectively for BSA and HA foulants, demonstrated its increased water permeation, foulant separation and antifouling behavior. Further, the decent antibacterial activity is showed by the PVDF/P–CuO nanocomposite membranes with the formation of halo-zone around the membrane when exposed to the bacterial medium demonstrated that, by this process an antibacterial water treatment membrane can be developed by simple phase inversion technique with good membrane stability.     

Study on hypochlorite degradation of aromatic polyamide reverse osmosis membrane

A serious limitation of most commercial polyamide reverse osmosis (RO) membranes is their sensitivity to chlorine attack. By studying the hypochlorite degradation of aromatic polyamide RO membrane, this work was to get some understandings in the prevention of membrane depreciation and develop membranes with improved chlorine resistance. Membrane performances, including water flux and salt rejection, were evaluated before and after hypochlorite exposure under different pH and concentration conditions. The results showed that chlorination destroyed hydrogen bonds in polyamide chains, causing a notable decline of membrane flux especially in acid environment; however, membrane performance was slightly improved after the treatment of alkaline hypochlorite solution for a certain time, which was probably due to the effect of amine groups in barrier layer. Based on the attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) characterizations and performance measurements, the results indicated that N-chlorination reaction of aromatic polyamide was also reversible, in other words, the N-chlorinated intermediate could be regenerated to initial amide with the alkaline treatment before ring-chlorination reaction. This conclusion provided several relative suggestions for membrane cleaning procedures. Finally, a method adopting surface coating was proposed to develop membranes with good chlorine resistance, and the preliminary results showed its potential for applications.     

四甲基氢氧化铵改性聚偏氟乙烯一步接枝聚苯乙烯磺酸油水分离膜的制备及性能

利用四甲基氢氧化铵(TMAH)聚偏氟乙烯(PVDF)进行改性,以过氧化苯甲酰(BPO)为引发剂,将苯乙烯磺酸(SSA)接枝到改性的PVDF骨架上,制得聚偏氟乙烯接枝聚苯乙烯磺酸(PSSA-g-PVDF)油水分离膜。 研究了TMAH质量分数对PSSA的接枝率和油水分离膜性能的影响,同时采用傅立叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)和视频光学接触角测量仪测试了膜的结构和表面接触角。 结果表明,TMAH使PVDF脱去部分氟化氢(HF)产生碳碳双键,硫元素均匀地分布在分离膜中。 PSSA的接枝率随着TMAH的质量分数增加而升高,分离膜的水通量随接枝率的升高先增加后降低。 当TMAH质量分数为20%,分离膜的接触角在30 s内降低到37.2°,接枝率和水通量分别为22.1%、643.3 L/(m·h),截留率和水通量恢复率分别达到90.6%和93.7%,衰减率为7.1%。 循环测试显示膜的水通量恢复率和油水通量恢复率均在90%以上。     

UF of pulp and paper effluent: membrane fouling-prevention and cleaning

Effluent arriving from the Mondi Kraft paper mill at Piet Retief, South Africa, was filtered through tubular poly(ether sulphone) (PES) ultrafiltration membranes under constant pressure cross-flow conditions. The effluent that was fed into the membranes and permeate produced during filtration were characterised by UV–VIS light-spectroscopy. Substances that absorbed onto membranes during filtration caused changes to the permeability characteristics of the membranes. Changes in membrane performance were monitored by pure-water and product flux (pf) measurements.A colourimetric staining technique was developed to determine the nature of foulants adsorbed onto the membranes. Membrane cleaning solutions were subsequently selected using information obtained from the characterisation studies. In addition, the anti-fouling potential of non-covalently attached coating materials was investigated as a possible membrane pretreatment technique. Results showed that foulants present in the effluent are of phenolic and hydrophobic nature. Increasing the hydrophilic characteristics of membranes prior to filtration could reduce the amount of organic foulants that adsorbed onto the membranes. Membrane pretreatment not only reduced fouling, but also improved the effectiveness of cleaning methods. Membranes were effectively cleaned by a combination of mechanical and chemical cleaning techniques.     

Improving surface structure of photocatalytic self‐cleaning membrane by WO3/PANI nanoparticles

To create a self‐cleaning feature and improve antifouling property, polysulfone (PSf) membranes were modified with WO₃ and polyaniline (PANI) nanoparticles (0–2 wt%) via phase inversion method for ultrafiltration of landfill leachate. The mass ratio of WO₃ nanoparticles was varied between 0, 40 and 60 wt% in different loadings. All synthesized membranes were tested with and without UV irradiation to evaluate the self‐cleaning feature. The synthesized PANI was analyzed with scanning electron morphology (SEM), atomic force microscopy (AFM) and Fourier transform infrared spectroscopy (FTIR). The surface hydrophilicity of the modified membranes increases with increasing the nanoparticle loadings (0–2 wt%). The membrane morphology indicated higher porosity and more finger like pores for the modified membranes. The porosity of 86.8% was achieved for the membrane containing 2 wt% PANI. The flux recovery ratio (FR) of membranes without UV radiation was increased by increasing the ratio of PANI to WO₃ nanoparticles, while the antifouling ability of membranes including WO₃ nanoparticles improved and reached to 98.87% after UV radiation. The highest COD removal before (76.65 %) and after (78.42%) UV radiation was obtained for the membrane containing 2 wt% nanoparticle loading. Copyright © 2016 John Wiley & Sons, Ltd.     

Enzymatic cleaning of ultrafiltration membranes fouled by protein mixture solutions

Compared to other typical cleaning agents, application of enzyme in cleaning of membranes fouled with protein solution promised the high cleaning efficiencies with lower environmental impact. This paper is focused on the mechanisms of protein removal by enzyme cleaning agent from the membrane surface by analysis hydraulic resistance, total protein removal using Lowry method, and membrane surface analysis using MALDI-MS and gel electrophoresis to estimate the foulant composition. Using single and binary protein solutions of bovine serum albumin and beta-lactoglobulin as the feed solution for filtration process, the experimental results indicate that optimum cleaning time and cleaning agent concentration is due to the competition between foulant removal and deposition of enzymes on the membrane during the cleaning process. The removal rate of different protein species in the fouling layer is varied, indicating that cleaning strategies can be tailor-made for fouling layer with different protein compositions.     

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.     

The role of foulant–foulant electrostatic interaction on limiting flux for RO and NF membranes during humic acid fouling—Theoretical basis,experimental evidence,and AFM interaction force measurement

A limiting flux model has been recently developed for predicting the fouling behavior of reverse osmosis and nanofiltration membranes by organic macromolecules [C.Y. Tang, J.O. Leckie, Membrane independent limiting flux for RO and NF membranes fouled by humic acid, Environmental Science and Technology 41 (2007) 4767–4773]. Several interesting results have been observed: (a) there was a maximum pseudo-stable flux (the limiting flux) beyond which further increase in applied pressure did not translate to a greater stable flux; (b) all membrane samples attained the limiting flux under constant pressure conditions as long as their initial flux was greater than the limiting flux; (c) the limiting flux did not depend on the properties of membranes; (d) the limiting flux had strong dependence on the feedwater composition, such as pH, ionic strength, and divalent ion concentration. The current study investigates the dependence of limiting flux on intermolecular interaction between foulant molecules. It was observed that the limiting flux was directly proportional to the intermolecular electrostatic repulsive force and that conditions enhancing foulant-deposited-foulant repulsion resulted in greater limiting flux values. Such observations agree well with a theoretical model capturing both hydrodynamic and DLVO interactions. Interaction force measurements by atomic force microscopy (AFM) were also performed. The limiting flux correlated reasonably well with AFM interaction force between the model foulant and the fouled membrane surface.     

A systematic insight into fouling propensity of soluble microbial products in membrane bioreactors based on hydrophobic interaction and size exclusion

Soluble microbial products (SMPs) contained in membrane bioreactor (MBR) supernatant have been proved to be main foulants. To obtain a comprehensive understanding of the fouling potential of SMPs on the basis of both hydrophilic/hydrophobic properties and molecular size, MBR supernatant of a pilot-scaled system treating municipal wastewater was partitioned into different hydrophilic/hydrophobic fractions by DAX-8 resins, with joint size partition of hydrophilic fraction also undertaken. A series of stirred dead-end filtration tests were conducted to investigate the flux decline. Hydrophilic fraction was found the dominant foulant responsible for flux deterioration, which was mainly attributed to the subclass of molecular weight above 100 kDa. The molecular weight distribution and atomic force microscopy images indicated that large molecules in hydrophilic fraction plugged the membrane pores. The backwash tests showed the flux decline caused by hydrophilic fraction was much less recoverable by hydraulic cleaning. It can be inferred that steric factor, i.e. size exclusion was the primary cause in the initial stage of fouling, while the role of hydrophobic interaction was of less significance. Additional modeling work indicates that the main fouling mechanism was complete blocking, further confirming the predominance of size exclusion contributing to membrane fouling by SMPs in MBR supernatant.     

Study on preparation and performances of cellulose acetate forward osmosis membrane

Cellulose acetate (CA) forward osmosis (FO) membranes were prepared via a phase inversion process. CA was used as membrane material for FO. Acetone and 1,4-dioxane were employed as solvent. Polyvinylpyrrolidone (PVP), maleic acid, and methanol were applied as additives. An orthogonal experiment was performed to optimize the ratio of every component in the casting solution. The membrane with best performance was selected to concentrate an anthocyanin solution. Saturated sucrose solution (about 60°Brix) was fit for using as draw solution in the concentration experiment. Water flux, porosity, and rejection rate were measured to evaluate the membrane properties. Reverse water rinsing was used in cleaning membrane that was fouled by anthocyanin solution. Results showed that under membrane thickness of 100 μm, coagulation temperature at room temperature, and evaporation time of 30 s, the optimum components in casting solution were 13% CA, 45% 1,4-dioxane, 31% acetone, 2% maleic acid, 3% PVP, and 6% methanol. In the concentration experiment, the prepared FO membrane showed water flux of 2.04 L m^?2 h^?1 and rejection rate of 98.61%. In the membrane cleaning experiment, the water flux of the FO membrane recovered 87.51% after rinsing for 1 h. The prepared membranes and previously published membranes were compared which showed the prepared membrane could significantly improve the rejection rate for anthocyanin solution.     

Fouling of reverse osmosis membranes by biopolymers in wastewater secondary effluent: Role of membrane surface properties and initial permeate flux

Reverse osmosis (RO) is being increasingly used in treatment of domestic wastewater secondary effluent for potable and non-potable reuse. Among other solutes, dissolved biopolymers, i.e., proteins and polysaccharides, can lead to severe fouling of RO membranes. In this study, the roles of RO membrane surface properties in membrane fouling by two model biopolymers, bovine serum albumin (BSA) and sodium alginate, were investigated. Three commercial RO membranes with different surface properties were tested in a laboratory-scale cross-flow RO system. Membrane surface properties considered include surface roughness, zeta potential, and hydrophobicity. Experimental results revealed that membrane surface roughness had the greatest effect on fouling by the biopolymers tested. Accordingly, modified membranes with smoother surfaces showed significantly lower fouling rates. When Ca²⁺ was present, alginate fouled RO membranes much faster than BSA. Considerable synergistic effect was observed when both BSA and alginate were present. The larger foulant particle sizes measured in the co-existence of BSA and alginate indicate formation of BSA-alginate aggregates, which resulted in greater fouling rates. Faster initial flux decline was observed at higher initial permeate flux even when the flux was measured against accumulative permeate volume, indicating a negative impact of higher operating pressure.     

ANTIFOULING PROPERTIES OF POLYVINYL CHLORIDE) MEMBRANES MODIFIED BY AMPHIPHILIC COPOLYMERS P(MMA-A-MAA)

Three well-defined diblock copolymers of poly(methyl methacrylate-b-methacrylic acid)(P(MMA-b-MAA))were synthesized using atom transfer radical polymerization method and varying poly(methacrylic acid)(PMAA)chain lengths. These copolymers were blended with PVC to fabricate porous membranes via phase inversion process.Membrane morphologies were observed by scanning electron microscopy(SEM),and chemical composition changes of the membrane surfaces were measured by X-ray photoelectron spectroscopy(XPS).Static and dynamic protein adsorption experiments were used to evaluate antifouling properties of the blend membranes.It was found that,the blend membranes containing longer PMAA arm length showed lower static protein adsorption,higher water permeation flux and better protein solution flux recovery.     

Blood compatibility and permeability of heparin-modified polysulfone as potential membrane for simultaneous hemodialysis and LDL removal

Heparin was covalently immobilized on PSf membranes to obtain a dialysis membrane with high affinity for LDL. WCA and streaming potential measurements were performed to investigate wettability and surface charge of the membranes. The morphology of the membranes was investigated by SEM. An ELISA was used to measure the adsorption and desorption of LDL on plain and modified PSf. Blood compatibility was studied by measurement of thrombin time, partial thromboplastin time, kallikrein activity and platelet adhesion. It was found that the blood compatibility of the membrane was improved by covalent immobilization of heparin at its surface. However, PSf-Hep membrane showed higher flux recovery after BSA solution filtration, which revealed antifouling property of PSf-Hep membranes.     

木质素磺酸钠改性聚砜膜的制备及其在正渗透膜中的应用

采用木质素磺酸钠作为亲水添加剂,通过浸没沉淀相转化法制备了木质素磺酸钠共混改性聚砜膜,以改善聚砜膜的亲水性,并用作正渗透膜的支撑层,以降低内浓差极化效应.利用扫描电子显微镜、衰减全反射傅里叶变换红外光谱仪、水接触角仪等研究了不同木质素磺酸钠添加量对聚砜膜的结构和表面性质的影响.结果表明,添加木质素磺酸钠后,聚砜膜的指状孔变得规整且狭长.水接触角实验证实添加木质素磺酸钠能改善聚砜膜的亲水性,当木质素磺酸钠含量为0.4 wt%时,聚砜膜的表面水接触角可降低至65°.正/反渗透测试装置分别用于表征正渗透膜的传质性质和结构参数.结果表明,以0.4 wt%木质素磺酸钠改性聚砜膜为支撑层的正渗透膜的水渗透性能(A=3.12×10~(-5) LMH×Pa~(-1))优于纯聚砜基底正渗透膜(0.76×10~(-5)LMH×Pa~(-1)),而且前者的结构参数(S=2010mm)远小于后者(3450mm),说明木质素磺酸钠改性聚砜膜有效弱化了正渗透膜的内浓差极化效应.