Recent developments in nanofiltration membranes based on nanomaterials

Nanofiltration membranes are the core elements for nanofiltration process. The chemical structures and physical properties of nanofiltration membranes determine water permeability, solute selectivity, mechanical/thermal stability, and antifouling properties, which greatly influence the separation efficiency and operation cost in nanofiltration applications. In recent years, a great progress has been made in the development of high performance nanofiltration membranes based on nanomaterials. Considering the increasing interest in this field, this paper reviews the recent studies on the nanofiltration membranes comprising various nanomaterials, including themetal andmetal oxide nanoparticles, carbon-based nanomaterials,metal–organic frameworks (MOFs),water channel proteins, and organic micro/nanoparticles. Finally, a perspective is given on the further exploitation of advanced nanomaterials and novel strategy for fabricating nano-based nanofiltration membranes. Moreover,the development of precision instruments and simulation techniques is necessary for the characterization of membrane microstructure and investigation of the separation and antifouling mechanism of nanofiltration membranes prepared with nanomaterials.     

Thin-film composite nanofiltration membranes prepared by electropolymerization

A novel approach to preparation of composite asymmetric nanofiltration membranes is reported based on a thin selective layer deposited by electropolymerization (EP) on top of an asymmetrically porous and electronically conductive porous support. Support films with ultrafiltration characteristics were cast from a concentrated dispersion of carbon black particles, a few tens of nanometers large, in a solution of polysulfone followed by precipitation in a non-solvent bath (phase inversion). Composite membranes with poly(phenylene oxide) and polyaniline thin top layers were prepared by EP deposition from solutions of phenol and aniline, respectively, of which polyaniline film demonstrated a dense uniform structure and water flux and rejection to sucrose and magnesium sulfate in the nanofiltration range.     

Color and COD retention by nanofiltration membranes

In the present study the application of the nanofiltration process was investigated mainly in the retention ofcolor and chemical oxygen demand (COD) present in textile industry wastewater. Nanofiltration experiments were carried out in a pilot unit, operating in crossflow. Three different types of spiral wound membranes, DK 1073, NF 45 and MPS 31 were used simultaneously in the same unit. The results of the tests showed that for color retention, the values were around 99% for the DK 1073 and NF 45 membranes and the 87% for COD retention for the DK 1073. The permeate flux for the different wastewaters varied from 30.5 to 70 L/h.m². Fouling was observed in all membranes due to the accumulation of molecular species close to the filtering surface. The process was efficient and promising for the reuse of wastewater from this type of industry.     

Advances in Polymer-based Nanostructured Membranes for Water Treatment

Water pollution has become the most severe dilemma in the entire world. In this review, we have discussed the advancement in preparation and properties, plus background and challenges regarding polymer-based nanocomposite membranes. Nanofiltration thin film composite membranes have been given tremendous attention over last two decades relative to conventional systems in desalination of sea water, waste water from industries and ultra pure water production etc. In recent years, significant research efforts have been devoted towards the development of high-performance membranes through surface modification of polymers and nanoparticles, nanotubes, etc. to achieve appreciable salt rejection, water flux and antifouling properties.     

Chemical modification of polyethersulfone nanofiltration membranes: A review

Polysulfone (PS) and poly(ether)sulfone (PES) are often used for synthesis of nanofiltration membranes, due to their chemical, thermal, and mechanical stability. The disadvantage for applying PS/PES is their high hydrophobicity, which increases membrane fouling. To optimize the performance of PS/PES nanofiltration membranes, membranes can be modified. An increase in membrane hydrophilicity is a good method to improve membrane performance. This article reviews chemical (and physicochemical) modification methods applied to increase the hydrophilicity of PS/PES nanofiltration membranes. Modification of poly(ether)sulfone membranes in view of increasing hydrophilicity can be carried out in several ways. Physical or chemical membrane modification processes after formation of the membrane create more hydrophilic surfaces. Such modification processes are (1) graft polymerization that chemically attaches hydrophilic monomers to the membrane surface; (2) plasma treatment, that introduces different functional groups to the membrane surface; and (3) physical preadsorption of hydrophilic components to the membrane surface. Surfactant modification, self‐assembly of hydrophilic nanoparticles and membrane nitrification are also such membrane modification processes. Another approach is based on modification of polymers before membrane formation. This bulk modification implies the modification of membrane materials before membrane synthesis of the incorporation of hydrophilic additives in the membrane matrix during membrane synthesis. Sulfonation, carboxylation, and nitration are such techniques. To conclude, polymer blending also results in membranes with improved surface characteristics. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel nanofiltration membranes with tunable permselectivity by polymer mediated phase separation in polyamide selective layer

Microstructure in selective layer has played a decisive role in permselectivity of nanofiltration (NF) membranes, and nanomaterials were well-known additives that had been applied to mediate the microstructure and permeability of polyamide NF membranes. However, nanoadditives generally displayed a poor dispersion in membranes or in fabrication process. To solve this problem, we showed an interesting concept that novel NF membranes with hybrid selective layer consisting of flexible polyisobutylene (PIB) and rigid polyamide could be fabricated from wel-defined interfacial polymerization. The hydrophobic polymer mediated phase separation and microdomains formation in polyamide layer were found. The immiscibility between the rigid polyamide and flexible PIB as well as the resultant interface effect was interpreted as the reason for the polymer enhanced permselectivity, which was similar with the well-known thin film nanocomposite (TFN) membranes that nanoparticles incorporated contributed significantly to membrane permeability and rejection performance. Our results have demonstrated that novel NF membranes with enhanced performance can be prepared from im-miscible polymers, which is a new area that has not been extensively studied before.     

A comprehensive review of nanofiltration membranes:Treatment, pretreatment, modelling, and atomic force microscopy

Nanofiltration membranes (NF) have applications in several areas. One of the main applications has been in watertreatment for drinking water production as well as wastewater treatment. NF can either be used to treat all kinds of water including ground, surface, and wastewater or used as a pretreatment for desalination. The introduction of NF as a pretreatment is considered a breakthrough for the desalination process. NF membranes have been shown to be able to remove turbidity, microorganisms and hardness, as well as a fraction of the dissolved salts. This results in a significantly lower operating pressure and thus provides a much more energy-efficient process. Similar to other membrane processes, a major problem in NF membrane applications is fouling. Several studies have investigated the mechanisms of fouling in NF membranes and suggested methods to minimize and control the fouling of NF membranes. For NF membrane characterizations and process prediction, modeling of NF processes and the use of atomic force microscopy (AFM) are very important. The ability to predict the performance of NF processes will lead to a lower number of experiments, saving of time and money, and help to understand the separation mechanisms during NF. A comprehensive review of NF in water treatments is presented including a review of the applications of NF in treating water as well as in the pretreatment process for desalination; the mechanism as well as minimization of NF membrane fouling problems; and theories for modelling and transport of salt, charged and noncharged organic compounds in NF membranes. The review will also address the application of AFM in studying the morphology of membrane surfaces as part of the NF membrane characterization.     

From ultra to nanofiltration: A review on the fabrication of ZrO2 membranes

Zirconia (ZrO₂) membranes experienced rapid progress in applications demanding high-stability membranes own to their higher chemical resistance and hydrophilicity compared to silica and alumina. Moreover, ZrO₂ membranes have increased fouling resistance, high permeability, and a long lifetime making them broadly applied in drinking water production, wastewater treatment, petrochemical, food, and beverages industries. However, fabricating ZrO₂ membranes for Nanofiltration and Gas Separation is still challenging. This paper reviews the progress in fabricating ZrO₂ membranes, focusing on strategies for achieving smaller pores without losing their high permeability and selectivity. The current state of the art in commercial ZrO₂ membranes and the recent innovations in academia are critically reviewed. A comprehensive revision of sol-gel technique's critical synthesis and process parameters is presented along with the most recent molecular layer deposition method. This work aims to provide a guide for both starting and established researchers, thus filling a gap in the present literature.     

Thin-film composite membranes for organophilic nanofiltration based on photo-cross-linkable polyimide

This work demonstrates that it is possible to prepare new, competitive thin-film composite (TFC) membranes with a polyolefin ultrafiltration membrane as support and with a non-porous photo-cross-linked polyimide as separation layer for organic solvent nanofiltration. The commercial polyimide Lenzing P84® was modified by a polymer-analogous reaction to introduce side groups with carbon–carbon double bonds to increase its photo-reactivity with respect to cross-linking. Polymer characterization revealed that this was successfully achieved at acceptable level of main chain scission. The higher reactivity of the photo-cross-linkable polyimide had been confirmed by comparison with the original polymer; i.e., shorter gelation times upon UV irradiation, higher suppression of swelling by solvents and complete stability in strong solvents for not cross-linked polyimide such as dimethylformamide (DMF) had been obtained. For films from unmodified and modified polyimide, the degree of swelling in various solvents could be adjusted by UV irradiation time. Photo-cross-linking of the original polyimide did not lead to stability in DMF. TFC membranes had been prepared by polymer solution casting on a polyethylene ultrafiltration membrane, UV irradiation of the liquid film and subsequent solvent evaporation. Polyimide barrier film thicknesses between 10 and 1 μm were obtained by variation of cast film thickness. Performance in organic solvent nanofiltration was analyzed by using hexane, toluene, isopropanol and DMF as well as two dyes with molar masses of ∼300 and ∼1000 g/mol. Permeances of TFC membranes from unmodified polyimide were low (<0.1 L/hm² bar) while rejections of up to 100% for the dye with ∼1000 g/mol could be achieved. TFC membranes from modified and photo-cross-linked polyimide had adjustable separation performance in DMF with a trade-off between permeance and selectivity, in the same range (e.g.: 0.3 L/hm² bar and 97% rejection for the dye with ∼1000 g/mol) as a commercial conventional polyimide membrane tested in parallel. The established membrane preparation method is promising because by tuning the degree of cross-linking of the polymeric barrier layer, the membrane separation performance could be tailored within the same manufacturing process.     

Selectivity of polyamide nanofiltration membranes for cations and phosphoric acid

The results shown in this paper are part of a study to investigate the use of nanofiltration membranes for the recycling of phosphorus from sewage sludge. It especially contains the results of an experimental study about the influencing factors pressure, pH and feed composition on the selectivity of nanofiltration membranes for phosphoric acid and multivalent cations. For the use of pretreated sewage sludge an effective pressure of 11 bar could be identified as an effective operational point. The selectivity turned out to increase with decreasing pH which was studied in a pH-interval of pH 1-4. An increasing concentration of multivalent cations in the feed solution had a negative effect on the permeability of phosphoric acid. Accordingly it could be observed that the nanofiltration worked significantly more effective with sewage sludge ash eluates of the concentration 10 g/l than eluates of the concentration 100 g/l.     

Dual layer composite nanofiltration hollow fiber membranes for low-pressure water softening

Nanofiltration (NF) membrane process has become increasingly attractive due to their unique characteristics to selectively remove specific compounds or ions. The most commonly NF membranes are negatively charged which is unsuitable for hardness removal. Therefore, the development of novel NF membranes with a positively charged skin has become a key issue for low pressure water softening.     

Negatively charged organic–inorganic hybrid silica nanofiltration membranes for lithium extraction

Effective extraction of lithium from high Mg~(2+)/Li+ratio brine lakes is of great challenge. In this work, organic–inorganic hybrid silica nanofiltration(NF) membranes were prepared by dip-coating a 1,2-bis(triethoxysilyl)ethane(BTESE)-derived separation layer on tubular TiO_2 support, for efficient separation of LiC l and MgCl_2 salt solutions. We found that the membrane calcinated at 400 °C(M1–400) could exhibit a narrow pore size distribution(0.63–1.66 nm) owing to the dehydroxylation and the thermal degradation of the organic bridge groups. All as-prepared membranes exhibited higher rejections to LiCl than to MgCl_2, which was attributed to the negative charge of the membrane surfaces. The rejection for LiCl and MgCl_2 followed the order: LiCl N MgCl_2, revealing that Donnan exclusion effect dominated the salt rejection mechanism. In addition, the triplecoated membrane calcined at 400 °C(M3–400) exhibited a permeability of about 9.5 L·m~(-2)·h~(-1)·bar~(-1) for LiCl or MgCl_2 solutions, with rejections of 74.7% and 20.3% to LiCl and MgCl_2,respectively, under the transmembrane pressure at 6 bar. Compared with the previously reported performance of NF membranes for Mg~(2+)/Li+separation, the overall performance of M3–400 is highly competitive. Therefore, this work may provide new insight into designing robust silica-based ceramic NF membranes with negative charge for efficient lithium extraction from salt lakes.     

Potential use of nanofiltration like-forward osmosis membranes for copper ion removal

The discharge of industrial effluent containing heavy metal ions would cause water pollution if such effluent is not properly treated. In this work, the performance of emerging nanofiltration(NF) like-forward osmosis(FO)membrane was evaluated for its efficiency to remove copper ion from water. Conventionally, copper ion is removed from aqueous solution via adsorption and/or ion-exchange method. The engineered osmosis method as proposed in this work considered four commercial NF membranes(i.e., NF90, DK, NDX and PFO) where their separation performances were accessed using synthetic water sample containing 100 mg·L~(-1) copper ion under FO and pressure retarded osmosis(PRO) orientation. The findings indicated that all membranes could achieve almost complete removal of copper regardless of membrane orientation without applying external driving force.The high removal rates were in good agreement with the outcomes of the membranes tested under pressuredriven mode at 1 MPa. The use of appropriate salts as draw solutes enabled the NF membranes to be employed in engineered osmosis process, achieving a relatively low reverse solute flux. The findings showed that the best performing membrane is PFO membrane in which it achieved N 99.4% copper rejection with very minimum reverse solute flux of 1 g·m~(-2)·h~(-1).     

Fouling of nanofiltration and ultrafiltration membranes applied for wastewater regeneration in the textile industry

Textile effluents usually contain high concentrations of inorganics as well as organics, and the therefore difficult to treat. Membrane processes can be used for many of these wastewaters in the textile industry. Two typical examples are discussed: (1) the use of nanofiltration for the treatment of exhausted dye baths, in view of water recycling, and (2) the use of ultrafiltration for the removal of spin finish from waste water resulting from rinsing of textile fibres. Both applications are in principle feasible, but in practice the process is negatively influenced by membrane fouling. In the first application, fouling is assumed to be caused by (ad)sorption of organic compounds, which has a large influence because of the high concentrations used in textile dyeing. Furthermore, the high salt concentrations result in a decrease of the effective driving force because of the high osmotic pressures obtained for typical dye baths. Experimental results are discussed, and the applicability of nanofiltration is related to the characteristics of the dye baths for different dyeing methods. In the second application, the concentration of organic compounds is relatively low, but because of the hydrophobic nature of the spin finish compounds, a significant effect of membrane fouling is expected. An improvement is suggested by using nanofiltration membranes instead of ultrafiltration membranes.     

A review of nanoparticle-enhanced membrane distillation membranes: membrane synthesis and applications in water treatment

Membrane distillation (MD) is a thermally driven process that uses low-grade energy to operate and has been extensively explored as an alternative cost-effective and efficient water treatment process compared to conventional membrane processes. MD membranes are synthesized from hydrophobic polymers, e.g. polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) or polypropylene (PP), using various methods including phase inversion and electrospinning techniques. Recent literature on MD membranes clearly shows their important role in surface water/wastewater treatment and seawater desalination. Modification of MD membranes with nanoscale materials significantly improves their performance, preventing wetting and fouling. This review presents a critical assessment of the progress on the use of nanomaterials for the modification of MD membranes. The techniques commonly used to synthesize MD membranes, the modifications that have been adopted for the incorporation of nanomaterials onto membranes, and the unique properties these nanomaterials impart on the membranes are discussed. The use of modified membranes in different MD configurations and their application in groundwater, surface water, wastewater, brackish water and seawater treatment is reviewed. Finally, cost implications, commercial viability, environmental sustainability, and future prospects of MD are also discussed to elucidate promising approaches for a future and successful implementation of MD at an industrial scale. © 2019 Society of Chemical Industry     

Highly selective polymeric membranes for gas separation

Polymeric membranes have gained an important place in chemical technology and are used in a broad range of applications. The key property that is exploited is the ability of a membrane to control the permeation rate of a chemical species through the membrane. The goal is to allow one component of a mixture to permeate the membrane freely, while hindering permeation of other component. To accomplish this, we proposed a novel concept of a (universal) ‘organic molecular sieve’ and experimentally proved its possibility by showing that organic polymer molecules at the interface between the permeable phase and the impermeable phase play the role of molecular sieves. This resulted in a significantly improved selectivity in gas separation, in fact going over the so-called ‘upper-bound’ sought for the past 30 years by many researchers but without much success. Since, this is not size selective like an inorganic molecular sieve but diffusion selective (the compatibilizer works like a molecular sieve to separate one gas molecules from the other), it can be used for the preparation of polymeric membranes for separation of any gas molecules pair. Because of polymer processability, this method is quite promising for the continuous mass production of polymeric membranes for real applications, especially when the polymers are insoluble to common solvents so that solution based techniques are hard to apply. This strategy can be applicable to various separation processes of many chemicals and gases.     

Vapor-phase polymerization of high-performance thin-film composite membranes for nanofiltration

Thin-film composite (TFC) membranes are commendable semipermeable barriers for water treatment. Although conventionally immiscible interfaces between aqueous and organic solutions are widely utilized for obtaining TFC membranes, interfacial polymerization still suffers from the issues of harmful solvents, complex diffusion/reaction of the reactants, and thermodynamic and kinetic instability of interfaces. In this study, vapor-phase polymerization with no requirements for organic solvent and immiscible interface is utilized for processing TFC nanofiltration membranes. Through cross-linking of β-cyclodextrin and piperazine layers by trimesoyl chloride vapor, polyester and polyamide TFC membranes with high cross-linking degree are simply prepared in a scalable and reproducible manner. The prepared TFC membranes exhibit stable nanofiltration and desalination performance for all water, organic solvent, and water–organic mixture systems, with permeance up to an order of magnitude higher than that of commercial membranes.     

Reduction of disinfection by-products in natural waters using nanofiltration membranes

Three commercial nanofiltration (NF) membranes, models NF 270, NF 90 (Dow Chemical Inc.) and Desal-HL-51 (GE Water), have been used to investigate trihalomethane and haloacetic acid formation potential (THMFP and HAAFP); the influence of conductivity on permeate flow-rate was also studied. Natural waters from two different sources in Alicante province (SE Spain) were analyzed.At the end of the NF experiments on water from the Amadorio reservoir, the Desal-HL-51, NF 270 and NF 90 membranes exhibited a 20, 25 and 45% drop in permeate flow-rate, respectively. The drop in flow-rate increased with conductivity for all of the membranes, as it becomes evident when comparing the experiments at conductivities of 700 and 6000 µS/cm.Over 90% of the formation potential of bromodichloro methane and dibromochloro methane was eliminated using the NF 90 membrane. The NF 270 and Desal-HL-51 membranes produced smaller decreases in THMFP. Among the haloacetic acids, dichloroacetic acid was least reduced, by 60% and 30% for waters from the Amadorio and Pedrera reservoirs, respectively. The analytes differed considerably.     

Reinforced thin-film composite nanofiltration membranes: Fabrication,characterization, and performance testing

Hollow-fiber (HF) membranes have the advantage of a higher packing density compared to flat-sheet and spiral-wound configurations. However, the low pressure tolerance of HF membranes limits their applications in nanofiltration (NF). In this study, reinforced thin-film composite (r-TFC) HF NF membranes were fabricated and evaluated in tests with water containing different salts and organic matter. Reinforced polysulfone ultrafiltration membranes were used as a support for a polyamide layer prepared from piperazine and trimesoyl chloride monomers. The interfacial polymerization conditions were optimized via selection of the trimesoyl chloride reaction time that gave the highest membrane performance. A specific permeate flux of 5.1 L m^–2 h^–1 bar^–1, an MgSO₄ rejection of 69%, and an NaCl rejection of 26% at a transmembrane pressure of 6 bars were obtained with the optimized r-TFC membranes. Performance studies with water characterized by synthetic solution demonstrated removals of the total organic carbon, ultraviolet absorbance at 254 nm, and turbidity in excess of 65, 80, and 90%, respectively. The results of this study illustrate the feasibility of manufacturing r-TFC HFs and using them in water-treatment applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48001.