Enhanced forward osmosis from chemically modified polybenzimidazole (PBI) nanofiltration hollow fiber membranes with a thin wall

To develop high-flux and high-rejection forward osmosis (FO) membranes for water reuses and seawater desalination, we have fabricated polybenzimidazole (PBI) nanofiltration (NF) hollow fiber membranes with a thin wall and a desired pore size via non-solvent induced phase inversion and chemically cross-linking modification. The cross-linking by p-xylylene dichloride can finely tune the mean pore size and enhance the salt selectivity. High water permeation flux and improved salt selectivity for water reuses were achieved by using the 2-h modified PBI NF membrane which has a narrow pore size distribution. Cross-linking at a longer time produces even a lower salt permeation flux potentially suitable for desalination but at the expense of permeation flux due to tightened pore sizes. It is found that draw solution concentration and membrane orientations are main factors determining the water permeation flux. In addition, effects of membrane morphology and operation conditions on water and salt transport through membrane have been investigated.     

Investigation on removing recalcitrant toxic organic polluters in coking wastewater by forward osmosis

Investigation was made on the efficiency of two commercial membranes in removing via forward osmosis (FO) the low molecular weight organic compounds typical of coking wastewater. The membranes were supplied by Poten and HTI companies. The organics in the simulated coking water were indole and pyrridine. Under FO mode, the rejection to the organics by Poten membrane was around 50%, whereas that for HTI membrane was obviously higher, ranging from 65% to 74%. The response of the two membranes in terms of Water flux and reverse salt flux (RSF) towards changing feed/draw solution (DS) flow rates in FO mode showed similar tendency, but different degree. Generally, the flux in FO using HTI membranes was lower. For HTI membrane, FO operated with pressure retarded osmosis (PRO) mode was also performed and the overall rejection of the organics was slightly lower than that in FO mode. In the long term FO test within 15 days, both Poten and HTI membranes displayed flux reduction and rejection enhancement. But the variation with Poten membrane was much more obvious. Discussion was carried out about the reasons and the mechanisms behind the FO performance difference between two membranes and the variation in flux and rejection with operation conditions. Characterizations by SEM, FTIR, AFM, XRD and XPS were tried to support the proposed explanations.     

Recent advances in nanofiltration,reverse osmosis membranes and their applications in biomedical separation field

In the face of human society’s great requirements for health industry, and the much stricter safety and quality standards in the biomedical industry, the demand for advanced membrane separation technologies continues to rapidly grow in the world. Nanofiltration(NF) and reverse osmosis(RO) as the highefficient, low energy consumption, and environmental friendly membrane separation techniques, show great promise in the application of biomedical separation field. The chemical compositions, microstr...     

Enhanced hollow fiber membrane performance via semi-dynamic layer-by-layer polyelectrolyte inner surface deposition for nanofiltration and forward osmosis applications

The layer-by-layer (LBL) polyelectrolyte deposited membranes have drawn increasing attention in various applications due to the ease of selective layer formation and their stability and versatility. In this study, the LBL deposition was performed at the inner surface of the polyethersulfone (PES) hollow fiber substrate to form composite nanofiltration (NF) membrane. The semi-dynamic deposition procedure was adopted with the aid of syringes. The newly developed inner deposited (id-LBL) membranes were then tested in NF and forward osmosis (FO) applications and the performance were compared with outer surface deposition as well as some literature data. The id-LBL membranes could not only withstand higher operating pressure but also possess superior hardness rejection especially in high concentration mixed salt solutions (more than 95% rejection to Mg²⁺ and Ca²⁺ in a 5000 ppm total dissolved salt (TDS) mixture under 4.8 bar). As for the FO process, with only two layer deposition, the id-LBL membranes also demonstrated significant performance improvement with increased water flux (up to 70 L/m² h using 0.5 M MgCl₂ as draw solution in active layer facing draw solution configuration) and reduced salt leakage (around 0.5 g/m² h using 1 M MgCl₂ draw solution in active layer facing feed water configuration). This study suggests that for hollow fiber substrate, the inner surface is more suitable for the formation of the selective layer via LBL deposition than the outer surface.     

Influence of filtration conditions on the performance of nanofiltration and reverse osmosis membranes in dairy wastewater treatment

Filtration performance and fouling of nanofiltration (NF) and reverse osmosis (RO) membranes in the treatment of dairy industry wastewater were investigated. Two series of experiments were performed. The first one involved a NF membrane (TFC-S) for treating the chemical-biological treatment plant effluents. The second one used a RO membrane (TFC-HR) for treating the original effluents from the dairy industry. The permeate flux was higher at higher transmembrane pressures and higher feed flowrates. The curves of permeate flux exhibited a slower increase while the feed flowrate decreased and the pressure increased. Membrane fouling resulted in permeate flux decline with increasing the feed COD concentration. Furthermore, the flux decline due to the COD increase was found higher at higher pressures for both NF and RO membranes.     

Treatment of tanning effluent using nanofiltration followed by reverse osmosis

An investigation on the recovery of chromium from the effluent of a chrome-tanning bath has been performed using nanofiltration (NF) followed by reverse osmosis (RO). The experiments are conducted using a rectangular cross flow cell under laminar and turbulent regimes. Significant flux enhancement is achieved using thin wires as turbulent promoters. The performance criteria are evaluated in terms of the concentration of chromium, COD, BOD, TDS, TS, pH, and conductivity of the permeate. The effects of different operating parameters on permeate flux and observed retention of chromium are evaluated experimentally. The retention of chromium is found to be 91–98% for NF and 98.8–99.7% for RO for the experimental conditions of this study. Concentrations of chromium and COD of the final permeate are well within the permissible limits.     

Comparison of polyamide nanofiltration and low-pressure reverse osmosis membranes on As(III) rejection under various operational conditions

A nanofiltration (NF) membrane and a low-pressure reverse osmosis (LPRO) membrane both with aromatic polyamide selective layer from the same manufacturer were employed for the comparison of their performances in terms of As(III) rejection and filtration flux under a variety of operational conditions. In addition to the smaller membrane pore size, the LPRO membrane possesses much more dissociable functional groups than the NF membrane. When the feed pH was below the pKa₁ value (9.22) of H₃AsO₃, for which the steric hindrance is the only rejection mechanism, the removal efficiencies by NF and LPRO were about 10% and 65%, respectively. When the feed pH was higher, for which electrostatic effect began to take effect, the removal efficiencies could reach 40% and 90% for NF and LPRO, respectively. The rejection performance of LPRO was marginally affected by the feed As(III) concentration or ionic strength, although ionic strength had a strong effect on the filtration flux. In contrast, feed As(III) concentration and ionic strength had little effect on the filtration flux but great influence on the As(III) rejection performance of NF. The filtration flux was enhanced with the increase of transmembrane pressure for either NF or LPRO. The NF model could predict the general trend of the effects of the filtration flux, the feed water chemistry and its own concentration on As(III) rejection ratio by the NF membrane, but the rejection ratios were over-predicted.     

纳滤/反渗透膜处理重金属废水的性能

The performance of different nanofiltration （NF） and reverse osmosis （RO） membranes was studied in treating the toxic metal effluent from metallurgical industry. The characteristics and filtration behavior of the processes including the wastewater flux, salt rejection and ion rejection versus operating pressure were evaluated. Then the wastewater flux of RO membrane was compared with theoretical calculation using mass transfer models, and good consistency was observed. It was found that a high rejection rate more than 95% of metal ions and a low Chemical Oxygen Demand （COD） value of 10 mg·L^-1 in permeate could be achieved using the RO composite membrane, while the NF rejection of the salt could be up to 78.9% and the COD value in the permeate was 35 mg·L^-1. The results showed that the product water by both NF and RO desalination satisfied the State Reutilization Qualification, but NF would be more suitable for large-scale industrial practice, which offered significantly higher permeate flux at low operating pressure.     

Pilot plant studies on the removal of trihalomethanes by composite reverse osmosis membranes

The effect of single trihalomethane (THM) (CHCl₃) content in various types of water on the performance of two types of reverse osmosis composite membranes (the AFC99 membrane in tubular module B1, PCI, and the FT30 membrane in a spiral-wound element BW3040, FilmTec) have been investigated. The performance of these membranes in RO tests carried out using distilled water, tap water and brackish water (1000–5000 ppm NaCl) with the addition of THM have been evaluated in terms of permeate flux and the rejection of dissolved solids and THM. The FT30 membrane provided THM rejection better than 99.5% during the reverse osmosis treatment of tap water and brackish water. The AFC99 membrane exhibited only 80% retention of THM, obtained for the transmembrane pressures in the range of 10 to 30 bars. It was found that the presence of CHCl₃ slightly affects the transport and separation properties of the composite membranes used.     

A novel dual-layer forward osmosis membrane for protein enrichment and concentration

We have demonstrated the prospect of dual-layer polybenzimidazole-polyethersulfone/polyvinylpyrrolidone (PBI–PES/PVP) hollow fiber nanofiltration (NF) membranes in the forward osmosis (FO) process for the enrichment and concentration of pharmaceutical products without denaturing the component of interests. The dual-layer hollow fiber membrane via coextrusion technology has an ultra-thin selective skin around 10 μm, fully open-cell water channels underneath and a microporous sponge-like support structure. The self-charged PBI selective skin has an average pore radius at 0.4 nm with a sharp pore size distribution. Experimental results show that the newly developed dual-layer hollow fiber nanofiltration membrane can achieve a high throughput for lysozyme enrichment and less protein fouling when using it as a FO membrane. In addition, the high divalent salt rejection towards Mg²⁺ at around 90% of this dual-layer membrane ensures the enriched lysozyme product with high purity and without change and denaturing.     

Recent advances in polymer and polymer composite membranes for reverse and forward osmosis processes

Semipermeable membranes are the core elements for membrane water desalination technologies such as commercial reverse osmosis (RO) process and emerging forward osmosis (FO) process. Structural and chemical properties of the semipermeable membranes determine water flux, salt rejection, fouling resistance, and chemical stability, which greatly impact energy consumption and costs in osmosis separation processes. In recent years, significant progress has been made in the development of high-performance polymer and polymer composite membranes for desalination applications. This paper reviews recent advances in different polymer-based RO and FO desalination membranes in terms of materials and strategies developed for improving properties and performances.     

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.     

Molecular design of the cellulose ester-based forward osmosis membranes for desalination

This work has investigated the fundamental science of phase inversion and formation mechanism of cellulose ester membranes at the interface between polymer and casting substrate. It also explores the desired membrane preparation conditions for forward osmosis (FO) applications. With the aid of positron annihilation lifetime spectroscopy (PALS), the similarity in physicochemical properties between the polymer and the substrate was found to play a significant role in determining the porosity of the bottom interfacial layer. The structure of the dense interfacial layer was also strongly dependent on membrane thickness and solvent composition. Experimental results surprisingly reveal that the original pore size of the as-cast membrane plays a critical role determining the final performance of the subsequent annealed membrane independently of annealing temperature and time. In addition, since a threshold pore size exists during annealing above which pores become difficult to downsize, we have found that a thin dense selective layer integrated in an asymmetric membrane may not always be the best option for FO. A balanced membrane structure consisting of a thin porous support and a thin dense selective layer has been developed for FO, which shows a low internal concentration polarization (ICP) and a relatively high water flux when seawater was employed as the feed.     

Nanofiltration and reverse osmosis thin film composite membrane module for the removal of dye and salts from the simulated mixtures

Nanofiltration (NF) and reverse osmosis (RO) thin film composite polyamide membrane modules were used to remove the color from the contaminated solution mixture. The feasibility of membrane processes for treating simulated mixture by varying the feed pressures (100-400 psi) and feed concentrations was studied to assess the separation performance of both NF and RO membranes. It was found that the efficiency of NF and RO membranes used in the treatment of colored water effluents was greatly affected by the presence of salts and dyes in the mixture. Color removal by NF with a high rejection of 99.80% and total dissolved solids (TDS) of 99.99% was achieved from RO by retaining significant flux rate compared to pure water flux, which suggested that membranes were not affected by fouling during the simulated wastewater process operation. The effect of varying concentrations of Na₂SO₄ salt and methyl orange (MO) dye on the performance of spiral wound membranes was determined. Increasing the dye concentration from 500 to 1000 mg/L resulted in a decrease of salt rejection at all operating pressures and for both concentrations of 5000 and 10,000 mg/L as the feed TDS. Increasing the salt concentration from 5000 to 10,000 mg/L resulted in a slight decrease in dye removal.     

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.     

Poly(vinyl) alcohol coating of the support layer of reverse osmosis membranes to enhance performance in forward osmosis

Membrane hydrophilicity influences the transport of water through the membrane in osmotically driven separations such as forward osmosis. In this paper, we coated the polysulfone support layer of two types of commercially available reverse osmosis membranes (brackish water and seawater) with hydrophilic polyvinyl alcohol (PVA). The aim of this was to increase the support layer hydrophilicity and, correspondingly, the rate of water transport through the membrane. Previous work with polydopamine coatings of the polysulfone support of reverse osmosis membranes has yielded promising results. In this work, we explore more readily available materials. Specifically, we studied the effects of two different PVA crosslinking agents – maleic acid and glutaraldehyde – on the resultant membrane properties and osmotic performance. For seawater membranes we found that PVA crosslinked to a limited degree with maleic acid creates a significant improvement in water flux in RO and FO systems, as compared to membranes with PVA crosslinked by glutaraldehyde. However, brackish water membranes did not have comparably significant changes in membrane performance. We conclude that the smaller pores of the brackish water membrane become clogged, and this effect is magnified by the lack of fractional free volume available within PVA that is highly crosslinked with glutaraldehyde.     

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.     

Powering reversible actuators using forward osmosis membranes: feasibility study and modeling

The aim was to determine the impact of membrane properties and operating conditions upon predicted performance of osmotically driven actuators. An actuator fitted with a forward osmosis membrane was studied, and significantly we examined the reversibility of the actuation process. It was discovered that the actuation-retraction cycle could be repeated for over 60 cycles before salt concentration became similar on both sides of the membrane. The cycle length and number of operative cycles were shown to be a dependent on membrane properties. It was demonstrated that issue of long actuation time can be addressed using membranes with high water permeability.     

An agent-based simulation with NetLogo platform to evaluate forward osmosis process (PRO Mode)

Forward osmosis (FO), as an emerging technology, is influenced by different factors such as operating conditions, module characteristics, and membrane properties. The general aim of this study was to develop a suitable (flexible, comprehensive, and convenient to use) computational tool which is able to simulate osmosis through an asymmetric membrane oriented in pressure retarded osmosis (PRO) mode in a wide variety of scenarios. For this purpose, an agent-based model was created in NetLogo platform, which is an easy-to-use application environment with graphical visualization abilities and well suited for modeling a complex system evolving over time. The simulation results were validated with empirical data obtained from literature and a great agreement was observed. The effect of various parameters on process performance was investigated in terms of temperature, cross-flow velocity, length of the module, pure water permeability coefficient, and structural parameter of the membrane. Results demonstrated that the increase in all parameters, except structural parameter of the membrane and the length of module led to the increase of average water flux. Moreover, nine different draw solutes were selected in order to assess the influence of net bulk osmotic pressure difference between the draw solution (DS) and feed solution (FS) (known as the driving force of FO process) on water flux. Based on the findings of this paper, the performance of FO process (PRO mode) can be efficiently evaluated using the NetLogo platform.