Carbon nanotube blended polyethersulfone membranes for fouling control in water treatment

Multi-walled carbon nanotube/polyethersulfone (C/P) blend membranes were synthesized via the phase inversion method. The resultant membranes were then characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and contact angle. The C/P blend membranes appeared to be more hydrophilic, with a higher pure water flux than the polyethersulfone (PES) membranes. It was also found that the amount of multi-walled carbon nanotubes (MWCNTs) in the blend membranes was an important factor affecting the morphology and permeation properties of the membranes. After 24 h of surface water filtration with 7 mgC/L TOC content, the C/P blend membranes displayed a higher flux and slower fouling rate than the PES membranes. Subsequent analyses of the desorbed foulants showed that the amount of foulant on bare PES membranes was 63% higher than the C/P blend membrane for 2% MWCNTs content. Thus, the carbon nanotube content of the C/P membranes was shown to alleviate the membrane fouling caused by natural water.     

A permeability-controlled microfiltration membrane for reduced fouling in drinking water treatment

A novel surface-modified polypropylene microfiltration membrane is investigated for its potential use in drinking water treatment. The flux decline rate of the modified membrane is substantially lower than the original polypropylene membrane for filtration of a soft, high-natural organic matter (NOM) surface water because a progressive adjustment in membrane permeability counteracts the flux decline due to fouling. In general, the prospects for reduced flux decline by membrane modification depend upon the characteristics of raw water such as hardness, particulate and NOM properties and concentration, and pretreatment strategies.     

Interplay of different NOM fouling mechanisms during ultrafiltration for drinking water production

Ultrafiltration is an emerging technology for drinking water production, but a main challenge remains the lack of understanding about fouling. This paper investigates the impact of molecular interactions between different natural organic matter (NOM) compounds on ultrafiltration fouling mechanisms. We performed dead-end filtration experiments with individual and mixed humic acid and alginate (polysaccharide). Alginate showed detrimental, but mostly reversible, flux decline and high solute retention. Our results indicate that this was caused by pore blocking transformed into cake building and weak molecular foulant-membrane and foulant-foulant interactions. In the presence of calcium, aggravated fouling was observed, related to complexation of alginate and its subsequently induced gel formation. With humic acid, more severe irreversible fouling occurred due to humic acid adsorption. Minor adsorption of alginate onto the membrane was also observed, which probably caused the substantial irreversible flux decline. The fouling characteristics in the mixtures reflected a combination of the individual humic acid and alginate experiments and we conclude, that the individual fouling mechanisms mutually influence each other. A model elucidates this interplay of the individual fouling mechanisms via hydrophobic and electrostatic interactions. In our study such an interplay resulted in an alginate cake, or gel in the presence of calcium, which is relatively irreversibly adsorbed onto the membrane by humic acid associations. This study shows the importance of mutual influences between various foulants for improved understanding of fouling phenomena. Furthermore it shows that substances with a minor individual influence might have a large impact in mixed systems such as natural water.     

High-performance thin-layer hydrogel composite membranes for ultrafiltration of natural organic matter

Thin-layer hydrogel composite (TLHC) ultrafiltration (UF) membranes were synthesized by photo-grafting of either poly(ethylene glycol) methacrylate (PEGMA) or N,N-dimethyl-N-(2-methacryloyloxyethyl-N-(3-sulfopropyl) ammonium betaine (SPE) onto commercial polyethersulfone (PES) UF membranes. The performance of TLHC UF membranes was evaluated for natural organic matter (NOM) filtration and compared to commercial PES UF membranes. The fouling evaluation was done by investigation of membrane-solute interactions (adsorptive fouling) and membrane-solute-solute interactions (UF). The results suggest that the TLHC membranes convincingly displayed a higher adsorptive fouling resistance than unmodified PES UF membranes. In long-term stirred dead-end UF, a much lower fouling was observed for TLHC membranes than for commercial membranes with the same flux and rejection. Further, water flux recovery was also much higher. An analysis using an existing blocking model was performed in order to elucidate the effect of a polymer hydrogel layer on fouling mechanism as well as cake layer characteristics. The TLHC membranes synthesized by photo-grafting of PEGMA (40 g/L) and PEGMA with a low concentration of cross-linker monomer in the reaction mixture (ratio: 40/0.4 (g/L)/(g/L)) showed a much better performance than the other composite membranes. Those membranes could reduce the cake resistance on the membrane surface. This work has relevance for the design of high-performance UF membranes for applications in water treatment.     

Membrane coagulation bioreactor (MCBR) for drinking water treatment

In this paper, a novel submerged ultrafiltration (UF) membrane coagulation bioreactor (MCBR) process was evaluated for drinking water treatment at a hydraulic retention time (HRT) as short as 0.5h. The MCBR performed well not only in the elimination of particulates and microorganisms, but also in almost complete nitrification and phosphate removal. As compared to membrane bioreactor (MBR), MCBR achieved much higher removal efficiencies of organic matter in terms of total organic carbon (TOC), permanganate index (COD(Mn)), dissolved organic carbon (DOC) and UV absorbance at 254nm (UV(254)), as well as corresponding trihalomethanes formation potential (THMFP) and haloacetic acids formation potential (HAAFP), due to polyaluminium chloride (PACl) coagulation in the bioreactor. However, the reduction of biodegradable dissolved organic carbon (BDOC) and assimilable organic carbon (AOC) by MCBR was only 8.2% and 10.1% higher than that by MBR, indicating that biodegradable organic matter (BOM) was mainly removed through biodegradation. On the other hand, the trans-membrane pressure (TMP) of MCBR developed much lower than that of MBR, which implies that coagulation in the bioreactor could mitigate membrane fouling. It was also identified that the removal of organic matter was accomplished through the combination of three unit effects: rejection by UF, biodegradation by microorganism and coagulation by PACl. During filtration operation, a fouling layer was formed on the membranes surface of both MCBR and MBR, which functioned as a second membrane for further separating organic matter.     

Modification of low pressure membranes with carbon nanotube layers for fouling control

Carbon nanotubes (CNTs) with different physiochemical properties were layered onto low pressure membranes and tested for antifouling properties using a natural surface water with high fouling potential. Membranes modified with the largest diameter pristine multi-walled CNTs (MWCNTs) were most effective in controlling membrane fouling, tripling the time it took for the membrane to become noticeably fouled at a CNT loading of 22 g/m². The differences in the structure of CNT layers were an important contributing factor for antifouling properties; scanning electron microscopy imaging showed that large diameter MWCNTs formed homogeneous porous layers across the membrane surface, while less effective, small diameter MWCNTs formed heterogeneous layers. Water quality analysis showed that CNT-membranes constructed with larger diameter CNTs were more effective at removing larger organic macromolecules responsible for fouling from feedwater compared to membranes made with smaller diameter CNTs. This reduced the concentration of foulants reaching the PVDF membrane and thus helped reduce membrane fouling. Beneficial for application, increased loadings of CNTs onto the membrane surface increased resistance to fouling while only slightly reducing the clean water permeability of the modified membranes. Overall, CNT layered membranes were shown to highly resist membrane fouling with potential applications in sustainable water treatment.     

TiO2 and polyvinyl alcohol (PVA) coated polyester filter in bioreactor for wastewater treatment

Prepared by coating TiO₂/polyvinyl alcohol (PVA) on a low cost polyester filter cloth (22 μm), a composite membrane (10 μm pore size) was successfully used in an anoxic/oxic membrane bioreactor (A/O-MBR) for treating a simulate wastewater in removing nitrate/ammonium for water reuse in a polyester fiber production plant. Its permeate flux and the anti-fouling properties against extracellular polymeric substances (EPS) were studied. Comparing with a commercial (0.1 μm) PVDF (polyvinylidene fluoride) membrane, similar effluent qualities were achieved, meeting the basic COD requirements for reuse. Anti-EPS accumulation, the TiO₂/PVA Polyester composite membrane had higher sustained permeability and required less frequent cleaning. Its filtration time was 4 times longer when operated at a higher flux than the PVDF membrane. The nano-TiO₂ enhances the interaction between PVA and polyester, forms a more hydrophilic surface, drastically reduces the contact angle with water and reduces EPS fouling. The slow (trans-membrane pressure) TMP rise, loose cake layer, the low filtration resistances, and the EPS, SEM analysis confirmed the advantage of the composite membrane. Potential in lowering the membrane cost, the operation and maintenance cost, and in enhancing MBR waste water treatment efficiency is expected by the use of this new composite membrane.     

Development of antifouling reverse osmosis membranes for water treatment: A review

With the rapidly increasing demands on water resources, fresh water shortage has become an important issue affecting the economic and social development in many countries. As one of the main technologies for producing fresh water from saline water and other wastewater sources, reverse osmosis (RO) has been widely used so far. However, a major challenge facing widespread application of RO technology is membrane fouling, which results in reduced production capacity and increased operation costs. Therefore, many researches have been focused on enhancing the RO membrane resistance to fouling. This paper presents a review of developing antifouling RO membranes in recent years, including the selection of new starting monomers, improvement of interfacial polymerization process, surface modification of conventional RO membrane by physical and chemical methods as well as the hybrid organic/inorganic RO membrane. The review of research progress in this article may provide an insight for the development of antifouling RO membranes and extend the applications of RO technology in water treatment in the future.     

Analysis of filtration characteristics in submerged microfiltration for drinking water treatment

Hollow fiber membranes have been widely employed for water and wastewater treatments. Nevertheless, understanding the filtration characteristics of hollow fiber membranes is complicated by the axial distributions of transmembrane pressure (TMP) and flux, which are key factors for both fouling control and module design. In this study, model equations to account for different fouling mechanisms were derived to analyze the performance of submerged hollow fiber systems with different conditions in terms of feed water characteristics and membrane material. A series of experiments with synthetic feed and raw water were carried out using hydrophilic and hydrophobic membrane modules. The model successfully fits the experimental results for synthetic feed as well as raw water. The major fouling mechanisms for filtration of raw water using hydrophilic and hydrophobic membranes are identified as cake formation and standard blocking, respectively. The model calculations indicate that the distributions of flux and cake (fouling) resistance are sensitive to the fiber length of the membrane.     

Short-term adhesion and long-term biofouling testing of polydopamine and poly(ethylene glycol) surface modifications of membranes and feed spacers for biofouling control

Ultrafiltration, nanofiltration membranes and feed spacers were hydrophilized with polydopamine and polydopamine-g-poly(ethylene glycol) surface coatings. The fouling propensity of modified and unmodified membranes was evaluated by short-term batch protein and bacterial adhesion tests. The fouling propensity of modified and unmodified membranes and spacers was evaluated by continuous biofouling experiments in a membrane fouling simulator. The goals of the study were: 1) to determine the effectiveness of polydopamine and polydopamine-g-poly(ethylene glycol) membrane coatings for biofouling control and 2) to compare techniques commonly used in assessment of membrane biofouling propensity with biofouling experiments under practical conditions. Short-term adhesion tests were carried out under static, no-flow conditions for 1 h using bovine serum albumin, a common model globular protein, and Pseudomonas aeruginosa, a common model Gram-negative bacterium. Biofouling tests were performed in a membrane fouling simulator (MFS) for several days under flow conditions similar to those encountered in industrial modules with the autochthonous drinking water population and acetate dosage as organic substrate. Polydopamine- and polydopamine-g-poly(ethylene glycol)-modified membranes showed significantly reduced adhesion of bovine serum albumin and P. aeruginosa in the short-term adhesion tests, but no reduction of biofouling was observed during longer biofouling experiments with modified membranes and spacers. These results demonstrate that short-term batch adhesion experiments using model proteins or bacteria under static conditions are not indicative of biofouling, while continuous biofouling experiments showed that membrane surface modification by polydopamine and polydopamine-g-poly(ethylene glycol) is not effective for biofouling control.     

Comparison of fouling characteristics of two different poly-vinylidene fluoride microfiltration membranes in a pilot-scale drinking water treatment system using pre-coagulation/sedimentation, sand filtration, and chlorination

Two pilot-scale hybrid water treatment systems using two different poly-vinylidene fluoride (PVDF) microfiltration (MF) membranes (i.e. symmetric and composite) were operated at a constant permeate flux of 104.2l m(-2)h(-1) (=2.5 md(-1)) with a pre-coagulation/sedimentation, sand filtration (SF), and chlorination to produce potable water from surface water. Turbidity was removed completely. And humic substances, Al, and Fe were removed very well by the pilot-scale membrane system. To control microbial growth and mitigate membrane fouling, a NaOCl solution was injected into the effluent from SF before reaching the two membranes (pre-chlorination). However, it adversely affected membrane fouling due to the oxidization and adsorption of inorganic substances such as Al, Fe, and Mn. In the next run, the NaOCl was introduced during backwash (post-chlorination). As compared with the result of pre-chlorination, this change increased the operating period of the symmetric and the composite membranes from about 10 and 50 days to about 60 and 200 days, respectively.     

Reversible and irreversible low-pressure membrane foulants in drinking water treatment: Identification by principal component analysis of fluorescence EEM and mitigation by biofiltration pretreatment

With the increased use of membranes in drinking water treatment, fouling - particularly the hydraulically irreversible type - remains the main operating issue that hinders performance and increases operational costs. The main challenge in assessing fouling potential of feed water is to accurately detect and quantify feed water constituents responsible for membrane fouling. Utilizing fluorescence excitation-emission matrices (EEM), protein-like substances, humic and fulvic acids, and particulate/colloidal matter can be detected with high sensitivity in surface waters. The application of principal component analysis to fluorescence EEMs allowed estimation of the impact of surface water constituents on reversible and irreversible membrane fouling. This technique was applied to experimental data from a two year bench-scale study that included thirteen experiments investigating the fouling potential of Grand River water (Ontario, Canada) and the effect of biofiltration pre-treatment on the level of foulants during ultrafiltration (UF). Results showed that, although the content of protein-like substances in this membrane feed water (= biofiltered natural water) was much lower than commonly found in wastewater applications, the content of protein-like substances was still highly correlated with irreversible fouling of the UF membrane. In addition, there is evidence that protein-like substances and particulate/colloidal matter formed a combined fouling layer, which contributed to both reversible and irreversible fouling. It is suggested that fouling transitions from a reversible to an irreversible regime depending on feed composition and operating time. Direct biofiltration without prior coagulant addition reduced the protein-like content of the membrane feed water which in turn reduced the irreversible fouling potential for UF membranes. Biofilters also decreased reversible fouling, and for both types of fouling higher biofilter contact times were beneficial.     

Surface modified bacterial biosorbent with poly(allylamine hydrochloride): Development using response surface methodology and use for recovery of hexachloroplatinate(IV) from aqueous solution

In this study, poly(allylamine hydrochloride) (PAA/HCl) was cross-linked with fermentation bacterial waste (Escherichia coli) in order to introduce a large amount of amine groups as binding sites for potassium hexachloroplatinate(IV), as a model anionic pollutant. The sorption performance of PAA/HCl-modified E. coli was greatly affected by the dosages of PAA/HCl and crosslinker (epichlorohydrin, ECH), and by the pH of the modification reaction medium. These factors were optimized through the response surface methodology (RSM). A three-level factorial Box-Behnken design was performed, and a second-order polynomial model was successfully used to describe the effects of PAA/HCl, ECH and the pH on the Pt(IV) uptake (R² = 0.988). The optimal conditions that were obtained from the RSM were 0.49 g of PAA/HCl, 0.05 mL of ECH and pH 10.02, with 1.0 g of dried E. coli biomass. The biosorption isotherm and kinetics studies were carried out in order to evaluate the sorption potential of the PAA/HCl-modified E. coli that was prepared under the optimized conditions. The sorption performance of the developed bacterial biosorbent was 4.36 times greater than that of the raw E. coli. Desorption was carried out using 0.05 M acidified thiourea and the biosorbent was successfully regenerated and reused up to four cycles. Therefore, this simple and cost-effective method suggested here is a useful modification tool for the development of high performance biosorbents for the recovery of anionic precious metals.     

Novel poly (vinyl chloride) matrix membrane electrodes for the determination of phenolic pollutants in waste water

The construction and electrochemical response characteristics of poly (vinyl chloride) matrix membrane sensors for seven phenolic compounds (phenol, o-cresol, p-cresol, p-chlorophenol, o-nitrophenol, alpha-naphthol and beta-naphthol) are described.The membranes incorporate ion association complexes of these seven phenolic anions with phenanthroline-iron(II) as electroactive materials.These sensors show linear response for phenol, o-cresol, p-cresol, p-chlorophenol, o-nitrophenol, alpha-naphthol, and beta-naphthol over wide concentration ranges, with an average anionic slope 54.3 mV per concentration decade.The suggested sensors exhibit fast response time (1 min), low determination limits (1 x 10(-5)M), good stability (2-3 weeks), reasonable selectivity to phenolic compounds in the presence of other water pollutants. The average percentage recovery was 99.78+/-0.088 for individual phenolates and 99.61+/-0.198 for phenolates in mixtures.The investigated sensors were successfully used for direct potentiometric determination of traces of these phenolic compounds in wastewater samples. Results with mean accuracy of 99.74+/-0.29%, 99.82+/-0.36%, 99.65+/-0.47%, 99.73+/-0.37%, 99.77+/-0.30%, 99.86+/-0.31% and 99.91+/-0.22% was obtained for the seven sensors, respectively.These results were compared with data obtained using the British pharamacopial method (The British Pharmacopoeia, Her Majesty's Stationary Office, London, 1993) and others (Clarke's Isolation and Identification of Drugs in Pharmaceuticals Body Fluids and Post-mortem Materials, 2nd Edition, The Pharmaceutical Press, London, 1998).     

Impact of temperature on nitrification in biological activated carbon (BAC) filters used for drinking water treatment

The impact of temperature on nitrification in biological granular activated carbon (GAC) filters was evaluated in order to improve the understanding of the nitrification process in drinking water treatment. The study was conducted in a northern climate where very cold water temperatures (below 2 degrees C) prevail for extended periods and rapid shifts of temperature are frequent in the spring and fall. Ammonia removals were monitored and the fixed nitrifying biomass was measured using a method of potential nitrifying activity. The impact of temperature was evaluated on two different filter media: an opened superstructure wood-based activated carbon and a closed superstructure activated carbon-based on bituminous coal. The study was conducted at two levels: pilot scale (first-stage filters) and full-scale (second-stage filters) and the results indicate a strong temperature impact on nitrification activity. Ammonia removal capacities ranged from 40 to 90% in pilot filters, at temperatures above 10 degrees C, while more than 90% ammonia was removed in the full-scale filters for the same temperature range. At moderate temperatures (4-10 degrees C), the first stage pilot filters removed 10-40% of incoming ammonia for both media (opened and closed superstructure). In the full-scale filters, a difference between the two media in nitrification performances was observed at moderate temperatures: the ammonia removal rate in the opened superstructure support (more than 90%) was higher than in the closed superstructure support (45%). At low temperatures (below 4 degrees C) both media performed poorly. Ammonia removal capacities were below 30% in both pilot- and full-scale filters.     

Modelling the removal of p-TSA (para-toluenesulfonamide) during rapid sand filtration used for drinking water treatment

A finite element model was set-up to determine degradation rate constants for p-TSA during rapid sand filtration (RSF). Data used for the model originated from a column experiment carried out in the filter hall of a drinking water treatment plant in Berlin (Germany). Aerated abstracted groundwater was passed through a 1.6 m long column-shaped experimental sand filter applying infiltration rates from 2 to 6 m h⁻¹. Model results were fitted to measured profiles and breakthrough curves of p-TSA for different infiltration rates using both first-order reaction kinetics and Michaelis-Menten kinetics. Both approaches showed that degradation rates varied both in space and time. Higher degradation rates were observed in the upper part of the column, probably related to higher microbial activity in this zone. Measured and simulated breakthrough curves revealed an adaption phase with lower degradation rates after infiltration rates were changed, followed by an adapted phase with more elevated degradation rates. Irrespective of the mathematical approach and the infiltration rate, degradation rates were very high, probably owing to the fact that filter sands have been in operation for decades, receiving high p-TSA concentrations with the raw water.     

Importance of speciation methods in analytical control of water treatment processes with application to fluoride removal from waste waters

Analytical methods of speciation for the control of water treatment processes, particularly for the removal of fluoride by aluminium hydroxide polymers as precipitant, have been discussed. It has been shown that combination of ultrafiltration with spectroscopic methods and fluoride ion-selective electrode offers a powerful means for the control of both the precipitant and pollutant, e.g. fluoride. ²⁷Al n.m.r. has been used for the identification of hydrolytic products of aluminium(III) and the ultrafiltration technique has been applied for the separation of the active polymer. The hydrolytic products were also characterized by timed spectrometric method. The interaction between aluminium hydroxide polymer and fluoride was studied by means of fluoride ion-selective electrode, ultrafiltration and atomic absorption spectrometry. The usefulness of these speciation methods for choosing the best conditions for water treatment process is discussed. By applying them for the removal of fluoride, it was found that the fluoride levels can be brought down to less than 10 mg l^?1, the limit set by Swiss regulatory body for discharge of waste water. The importance of using such speciation methods for evaluating the possible impact of the “products” of the water treatment (dissolved species in treated water, discharged solid) is also emphasized.     

Optimization of a gravity‐driven membrane (GDM) system operated with simple manual cleanings for household drinking water treatment

Manual cleaning protocols were developed for a gravity‐driven membrane (GDM) module. Such a module is a promising solution for household water treatment in low‐ and middle‐income countries. A filtration system equipped with the GDM module was tested in a batchwise manner using three different feed water solutions. Two types of manual cleaning protocols were performed to delay the permeability decrease, namely cleaning between batches and long‐term cleaning (every 15 batches). The optimized protocol for cleaning between batches consisted of 3 twisting and 10 vertical shaking movements; the optimized long‐term cleaning protocol consisted of 70 vertical shaking movements for both the middle region of the module and the module header. These cleaning protocols allowed the filtration system to produce sufficient water to meet the minimum requirements for a five person family using all three kinds of feed water solutions. The module produced water without Escherichia coli, even for the wastewater influent.     

聚合硅酸铝铁混凝处理水中残余铝含量的研究

通过一系列生产实验,探讨了PAFSC的碱化度和Al/Fe/Si摩尔比以及水样pH值,水温对水中残余铝含量的影响,结果表明,用PAFSC处理后的水样具有更低的残余铝含量,残余铝随水温升高呈增加趋势,最佳pH值随水温的增加而降低。     

Advanced water treatment with manganese oxide for the removal of 17alpha-ethynylestradiol (EE2)

Municipal wastewater is supposed to be one of the most important sources of endocrine-disrupting compounds (EDCs) in water. Therefore, advanced treatments and cost-efficient techniques should be developed to prevent the spread of this type of pollution into the environment. In this view, experiments were conducted in which the removal of 17alpha-ethynylestradiol (EE2), a synthetic and persistent estrogen, from water was monitored in three upstream bioreactors (UBRs), filled with, respectively, sand, granulated activated carbon (GAC) and MnO(2) granules. Tap water, spiked with 15,000ngEE2/L was filtered through the reactors with a hydraulic retention time of approximately 1h. The removal of EE2 in the sand, GAC and MnO(2) reactors was, respectively, 17.3%,>99.8% and 81.7%. The removal in the GAC reactor was mainly due to adsorption. The MnO(2) reactor, however, removed significantly more EE2 than could be predicted from its adsorption capacity, probably thanks to its catalytic properties. These catalytic properties could make it a cost-efficient technique for the removal of EE2, but further research at more environmentally relevant concentrations is needed.