Boric acid permeation in forward osmosis membrane processes: modeling, experiments, and implications

Forward osmosis (FO) is attracting increasing interest for its potential applications in desalination. In FO, permeation of contaminants from feed solution into draw solution through the semipermeable membrane can take place simultaneously with water diffusion. Understanding the contaminants transport through and rejection by FO membrane has significant technical implications in the way to separate clean water from the diluted draw solution. In this study, a model was developed to predict boron flux in FO operation. A strong agreement between modeling results and experimental data indicates that the model developed in this study can accurately predict the boron transport through FO membranes. Furthermore, the model can guide the fabrication of improved FO membranes with decreased boron permeability and structural parameter to minimize boron flux. Both theoretical model and experimental results demonstrated that when membrane active layer was facing draw solution, boron flux was substantially greater compared to the other membrane orientation due to more severe internal concentration polarization. In this investigation, for the first time, rejection of contaminants was defined in FO processes. This is critical to compare the membrane performance between different membranes and experimental conditions.     

Experimental study of a 4040 spiral-wound forward-osmosis membrane module

This paper analyzes the structural features of a spiral-wound forward-osmosis (SW FO) membrane module via an experimental approach and presents the relationships between the water flux and operating conditions for design and operation of a large-scale FO process. The SW FO module has four ports: an inlet/outlet for the draw solution and an inlet/outlet for the feed solution. Accordingly, two strongly interacting flow streams existed on either side of the membrane with spatially variable properties. Unlike the operation of a membrane cell device loaded with a small membrane coupon, it was appropriate to operate a housing-type FO unit loaded with a 4040 SW FO module with a lower draw flow rate than feed flow rate. Because of the structural features of the SW FO module, the draw solution flowed inside of the membrane envelope under a considerable pressure in order to overcome the flow resistance. The effect of operating conditions on the water flux in a 4040 SW FO module was investigated. A water flux equation based on a temperature-correction factor (TCF) was proposed to predict the water flux at a given temperature. Our study is a good reference point for designing the FO process and FO membrane module.     

High performance thin-film composite forward osmosis hollow fiber membranes with macrovoid-free and highly porous structure for sustainable water production

The development of high-performance and well-constructed thin-film composite (TFC) hollow fiber membranes for forward osmosis (FO) applications is presented in this study. The newly developed membranes consist of a functional selective polyamide layer formed by highly reproducible interfacial polymerization on a polyethersulfone (PES) hollow fiber support. Using dual-layer coextrusion technology to design and effectively control the phase inversion during membrane formation, the support was designed to possess desirable macrovoid-free and fully sponge-like morphology. Such morphology not only provides excellent membrane strength, but it has been proven to minimize internal concentration polarization in a FO process, thus leading to the water flux enhancement. The fabricated membranes exhibited relatively high water fluxes of 32-34 LMH and up to 57-65 LMH against a pure water feed using 2 M NaCl as the draw solution tested under the FO and pressure retarded osmosis (PRO) modes, respectively, while consistently maintaining relatively low salt leakages below 13 gMH for all cases. With model seawater solution as the feed, the membranes could display a high water flux up to 15-18 LMH, which is comparable to the best value reported for seawater desalination applications.     

正渗透膜污染的影响因素及清洗效果研究

为研究正渗透(FO)浓缩过程中的膜通量衰减规律,本文以牛血清白蛋白(BSA)为特征污染物,研究了正渗透过程中原料液的离子强度及BSA浓度、膜方位等参数不同时FO膜的污染规律,以提高膜通量和截留率为目标,对驱动液的种类、浓度,料液流速进行了优化,并优化了适宜的膜清洗方案.结果表明:原料液中离子强度越大,FO膜的初始通量越...     

Forward osmosis concentration of high viscous polysaccharides of Dendrobium officinale: Process optimisation and membrane fouling analysis

Polysaccharides of Dendrobium officinale (DOP) need to be dehydrated and concentrated after extraction for further application. They are usually concentrated by thermal evaporation which consumes great energy. However, high viscosity of DOP makes the concentration more difficult even using non-thermal membrane technologies such as nanofiltration (NF) or reverse osmosis (RO). In this study, effects of process conditions, such as membrane orientations, draw solutions and their concentrations, and flowrate on forward osmosis (FO) concentration of viscous DOP were studied. Active layer to feed solution mode, cross flowrate at 240 mL min⁻¹, and draw solution of 3 m NaCl have been found as the optimal conditions. Foulants on the membrane surface with loose structure could be easily cleaned and removed by hydraulic flushing. DOP concentrated by FO achieved almost 1.3 times at the same time compared with that in NF and RO. DOP could be further concentrated for 1.5 folds at longtime without significant decrease in water flux. In addition, slight reverse solutes in FO process could reduce the viscosity of high viscous DOP, which was good for concentration. Accordingly, FO is a potential technology for concentration of high viscous polysaccharides such as DOP.     

Synthesis and characterization of novel forward osmosis membranes based on layer-by-layer assembly

Forward osmosis (FO) has received considerable interest for water- and energy-related applications in recent years. FO does not require an applied pressure and is believed to have a low fouling tendency. However, a major challenge in FO is the lack of high performance FO membranes. In the current work, novel nanofiltration (NF)-like FO membranes with good magnesium chloride retention were synthesized using layer-by-layer (LbL) assembly. The membrane substrate was tailored (high porosity, finger-like pores, thin cross-section, and high hydrophilicity) to achieve a small structural parameter of 0.5 mm. Increasing the number of polyelectrolyte layers improved the selectivity of the LbL membranes while reducing their water permeability. The more selective membrane 6#LbL (with 6 polyelectrolyte layers) had much lower reverse solute transport compared to 3#LbL and 1#LbL. Meanwhile, the FO water flux was found to be strongly affected by both membrane water permeability and solute reverse transport. Severe solute reverse transport was observed for the active-layer-facing-draw-solution membrane orientation, likely due to the suppression of Donnan exclusion as a result of the high ionic strength of the draw solution. In contrast, the active-layer-facing-feed-solution orientation showed remarkable FO performance (15, 20, and 28 L/m2.h at 0.1, 0.5, and 1.0 M MgCl?, respectively, for membrane 3#LbL using distilled water as feed solution), superior to other NF-like FO membranes reported in the literature. To the best of the knowledge of the authors, this is the first work on the synthesis and characterization of LbL based FO membranes.     

Adverse impact of feed channel spacers on the performance of pressure retarded osmosis

This article analyzes the influence of feed channel spacers on the performance of pressure retarded osmosis (PRO). Unlike forward osmosis (FO), an important feature of PRO is the application of hydraulic pressure on the high salinity (draw solution) side to retard the permeating flow for energy conversion. We report the first observation of membrane deformation under the action of the high hydraulic pressure on the feed channel spacer and the resulting impact on membrane performance. Because of this observation, reverse osmosis and FO tests that are commonly used for measuring membrane transport properties (water and salt permeability coefficients, A and B, respectively) and the structural parameter (S) can no longer be considered appropriate for use in PRO analysis. To accurately predict the water flux as a function of applied hydraulic pressure difference and the resulting power density in PRO, we introduced a new experimental protocol that accounts for membrane deformation in a spacer-filled channel to determine the membrane properties (A, B, and S). PRO performance model predictions based on these determined A, B, and S values closely matched experimental data over a range of draw solution concentrations (0.5 to 2 M NaCl). We also showed that at high pressures feed spacers block the permeation of water through the membrane area in contact with the spacer, a phenomenon that we term the shadow effect, thereby reducing overall water flux. The implications of the results for power generation by PRO are evaluated and discussed.     

正渗透技术浓缩苹果汁过程中反向溶质扩散的研究

反向渗透扩散（RSF）是正渗透技术中的一大挑战,本实验立足于研究正渗透技术浓缩苹果汁性能以及功能性汲取液（乙酸钠、碳酸氢钠、柠檬酸钠溶液）的溶质扩散规律。首先,利用NaCl溶液为汲取液研究正渗透膜的基础特性,通过改变NaCl溶液浓度、进水流速以及膜操作模式,探究正渗透体系的水通量、反向溶质扩散及截留率,分析对去离子水和苹果汁的浓缩能力及溶质扩散规律;其次,对比不同功能性汲取液对苹果汁浓缩的效果和对RSF的影响,以期达到将RSF化弊为利的目的。结果表明,汲取液浓度和膜操作模式影响浓缩效率和RSF;采用压力延迟渗透（PRO）模式,苹果汁浓缩倍数和RSF均比正渗透（FO）模式高,PRO模式下,5 mol·L?1 NaCl汲取液RSF达87.34±6.32 g·m?2·h?1;不同种类功能性汲取液浓缩苹果汁的能力不同,汲水能力:碳酸氢钠>氯化钠>乙酸钠>柠檬酸钠。RSF:乙酸钠>碳酸氢钠>氯化钠>柠檬酸钠。2 mol·L?1柠檬酸钠汲取液的RSF为29.61±2.19 g·m?2·h?1,仅为同浓度NaCl汲取液的一半,与传统的NaCl汲取液相比,柠檬酸钠汲取液可有效控制RSF。     

Integrating forward osmosis into microbial fuel cells for wastewater treatment, water extraction and bioelectricity generation

A novel osmotic microbial fuel cell (OsMFC) was developed by using a forward osmosis (FO) membrane as a separator. The performance of the OsMFC was examined with either NaCl solution or artificial seawater as a catholyte (draw solution). A conventional MFC with a cation exchange membrane was also operated in parallel for comparison. It was found that the OsMFC produced more electricity than the MFC in both batch operation (NaCl solution) and continuous operation (seawater), likely due to better proton transport with water flux through the FO membrane. Water flux from the anode into the cathode was clearly observed with the OsMFC but not in the MFC. The solute concentration of the catholyte affected both electricity generation and water flux. These results provide a proof of concept that an OsMFC can simultaneously accomplish wastewater treatment, water extraction (from the wastewater), and electricity generation. The potential applications of the OsMFC are proposed for either water reuse (linking to reverse osmosis for reconcentration of draw solution) or seawater desalination (connecting with microbial desalination cells for further wastewater treatment and desalination).     

Comprehensive bench- and pilot-scale investigation of trace organic compounds rejection by forward osmosis

Forward osmosis (FO) is a membrane separation technology that has been studied in recent years for application in water treatment and desalination. It can best be utilized as an advanced pretreatment for desalination processes such as reverse osmosis (RO) and nanofiltration (NF) to protect the membranes from scaling and fouling. In the current study the rejection of trace organic compounds (TOrCs) such as pharmaceuticals, personal care products, plasticizers, and flame-retardants by FO and a hybrid FO-RO system was investigated at both the bench- and pilot-scales. More than 30 compounds were analyzed, of which 23 nonionic and ionic TOrCs were identified and quantified in the studied wastewater effluent. Results revealed that almost all TOrCs were highly rejected by the FO membrane at the pilot scale while rejection at the bench scale was generally lower. Membrane fouling, especially under field conditions when wastewater effluent is the FO feed solution, plays a substantial role in increasing the rejection of TOrCs in FO. The hybrid FO-RO process demonstrated that the dual barrier treatment of impaired water could lead to more than 99% rejection of almost all TOrCs that were identified in reclaimed water.     

Swelling and morphology of the skin layer of polyamide composite membranes: an atomic force microscopy study

The paper introduces a new methodology for studying polyamide composite membranes for reverse osmosis (RO) and nanofiltration (NF) in liquid environments. The methodology is based on atomic force microscopy of the active layer, which had been separated from the support and placed on a solid substrate. The approach was employed to determine the thickness, interfacial morphology, and dimensional changes in solution (swelling) of polyamide films. The face (active) and back (facing the support) surfaces of the RO films appeared morphologically similar, in agreement with the recently proposed model of skin formation. Measured thickness and swelling data in conjunction with the intrinsic permeability of the membranes suggest that the selective barrier in RO membrane constitutes only a fraction of the polyamide skin, whereas NF membranes behave as nearly uniform films. For NF membranes, there was reasonable correlation between the changes in the swelling and in the permeability of the membrane and the salinity and pH of the feed.     

Polyelectrolyte-promoted forward osmosis-membrane distillation (FO-MD) hybrid process for dye wastewater treatment

Polyelectrolytes have proven their advantages as draw solutes in forward osmosis process in terms of high water flux, minimum reverse flux, and ease of recovery. In this work, the concept of a polyelectrolyte-promoted forward osmosis-membrane distillation (FO-MD) hybrid system was demonstrated and applied to recycle the wastewater containing an acid dye. A poly(acrylic acid) sodium (PAA-Na) salt was used as the draw solute of the FO to dehydrate the wastewater, while the MD was employed to reconcentrate the PAA-Na draw solution. With the integration of these two processes, a continuous wastewater treatment process was established. To optimize the FO-MD hybrid process, the effects of PAA-Na concentration, experimental duration, and temperature were investigated. Almost a complete rejection of PAA-Na solute was observed by both FO and MD membranes. Under the conditions of 0.48 g mL(-1) PAA-Na and 66 °C, the wastewater was most efficiently dehydrated yet with a stabilized PAA-Na concentration around 0.48 g mL(-1). The practicality of PAA-Na-promoted FO-MD hybrid technology demonstrates not only its suitability in wastewater reclamation, but also its potential in other membrane-based separations, such as protein or pharmaceutical product enrichment. This study may provide the insights of exploring novel draw solutes and their applications in FO related processes.     

Bidirectional permeation of electrolytes in osmotically driven membrane processes

Osmotically driven membrane processes (ODMP) are emerging water treatment and energy conversion technologies. In this work, we investigated the simultaneous forward and reverse (i.e., bidirectional) solute fluxes that occur in ODMP. Numerous experiments were conducted using ternary systems (i.e., systems containing three distinct ions) and quaternary systems (i.e., systems containing four distinct ions) in conjunction with a membrane in a forward osmosis orientation. Ten different combinations of strong electrolyte salts constitute the ternary systems; common anion systems studied included KCl-NaCl, KBr-NaBr, KNO(3)-NaNO(3), KCl-CaCl(2), and KCl-SrCl(2); and common cation systems explored were KCl-KH(2)PO(4), NaCl-NaClO(4), NaCl-Na(2)SO(4), NaCl-NaNO(3), and CaCl(2)-Ca(NO(3))(2). For each combination, two experiments were conducted with each salt being used once in the draw solution and once in the feed solution. Quaternary systems studied were NaCl-KNO(3), NaCl-MgSO(4), MgSO(4)-KNO(3), and NaCl-K(2)SO(4). Experimental fluxes of the individual ions were quantified and compared to a set of equations developed to predict bidirectional electrolyte permeation for ODMP in a forward osmosis orientation. Results demonstrate that ion fluxes from the draw solution to the feed solution are well predicted; however, ion fluxes from the feed solution to the draw solution show slight deviations from the model that can be rationalized in terms of the electrostatic interactions between charged ions. The model poorly predicts the flux of nitrate containing solutions; however, several unique mass transfer mechanisms are observed with implications for ODMP process design.     

Effect of flux (transmembrane pressure) and membrane properties on fouling and rejection of reverse osmosis and nanofiltration membranes treating perfluorooctane sulfonate containing wastewater

Perfluorooctane sulfonate (PFOS) is an emergent contaminant of substantial environmental concerns. In this study, reverse osmosis (RO) and nanofiltration (NF) membranes were used to remove this toxic and persistent compound from PFOS-containing wastewater. Five RO membranes and three NF membranes were tested at a feed concentration of 10 ppm PFOS over 4 days, and the PFOS rejection and permeate flux performances were systematically investigated. PFOS rejection was well correlated to sodium chloride rejection. The rejection efficiencies for the RO membranes were > 99%, and those for the NF membranes ranged from 90-99%. Improvement in PFOS rejection, together with mild flux reduction (< 16%), was observed at longer filtration time. Such shifts in rejection and flux performance were probably due to the increased PFOS accumulation at longer duration, as shown by X-ray photoelectron spectroscopy and liquid chromatograph and tandem mass spectrometry results. A fraction of PFOS molecules might be entrapped in the polyamide layer of the composite membranes, which hindered the further passage of both water and other PFOS molecules. In a similar fashion, PFOS rejection and fouling were enhanced for greater initial flux and/or applied pressure, where PFOS accumulation was promoted probably due to increased hydrodynamic permeate drag. Flux reduction was also shown to correlate to membrane roughness, with the rougher membranes tend to experience more flux reduction than the smoother ones.     

Coupling reverse osmosis and osmotic distillation for clarified pomegranate juice concentration: Use of plasma modified reverse osmosis membranes for improved performance

In this study, a low pressure nitrogen plasma (LPNP) activation was implemented to modify the surface characteristics of a commercial thin film composite (TFC) polyamide reverse osmosis (RO) membrane. The free energy of interaction (ΔG_iwi) results showed that the hydrophobic nature of untreated TFC RO membrane became considerably hydrophilic with the effect of LPNP treatment. Among various plasma powers and exposure times tested, a general decreasing trend was observed for the water contact angle with increasing plasma duration, reaching a minimum of 13.2 ± 0.8° for 90 W at 15 min. A remarkable increase in water flux of the LPNP modified RO membrane was observed throughout the RO process, which promoted higher soluble solids content (SSC) values in the concentrated juice at the same period of time with the plain one. The higher SSC values achieved by the modified RO membrane enabled 30% time-saving during further osmotic distillation process.     

Removal of natural steroid hormones from wastewater using membrane contactor processes

Growing demands for potable water have strained water resources and increased interest in wastewater reclamation for potable reuse. This interest has brought increased attention to endocrine-disrupting chemicals (EDCs) as emerging water contaminants. The effect of EDCs, and in particular natural steroid hormones, on humans is of heightened interest in the study of wastewater reuse in advanced life support systems (e.g., space missions) because they are excreted in urine and have high endocrine-disrupting potencies. Direct contact membrane distillation (DCMD) and forward osmosis (FO) are being investigated for wastewater treatment in space. Retention of two natural steroid hormones, estrone and 17beta-estradiol, by these two processes was evaluated in the current investigation. DCMD provided greater than 99.5% hormone rejection; DCMD also provided constant flux, greater than 99.9% urea and ammonia rejection, and high water recovery. FO provided from 77 to 99% hormone rejection depending on experiment duration and feed solution chemistry.     

Reverse osmosis desalting of inland brackish water of high gypsum scaling propensity: kinetics and mitigation of membrane mineral scaling

The potential for mineral scaling that may limit the generation of new potable water resources by reverse osmosis (RO), from inland brackish water of high gypsum scaling propensity, was experimentally explored via flux decline measurements and real-time RO membrane surface imaging. Antagonistic gypsum and calcium carbonate scaling kinetics were demonstrated for high-sulfate brackish water desalting. RO scaling studies with brackish water from the California San Joaquin Valley (approximately 10 000 mg/L total dissolved solids) revealed that membrane gypsum scaling was increasingly retarded with rising bicarbonate concentrations. Crystal growth rate, fractional membrane scale coverage, and flux decline decreased by up to about 63, 78, and 73%, respectively, as the bicarbonate concentration increased, at the membrane surface, from < 0.01 to 7.81 mM, for a gypsum saturation index of 2. Inhibition of gypsum crystal growth was attributed to bicarbonate adsorption onto the crystal surfaces, and CaCO3 scaling was undetected even up to a calcite saturation index of approximately 16. Given the suppression of gypsum scaling by bicarbonate, it is essential to considerthis effect in the conventional practice of pH adjustment to suppress CaCO3 scaling. The present results suggest that antagonistic and synergistic mineral crystallization kinetics effects are important for optimizing scale-control strategies (e.g., acid and antiscalants addition to the RO feed).     

Use of reverse osmosis membranes to remove perfluorooctane sulfonate (PFOS) from semiconductor wastewater

Perfluorooctane sulfonate (PFOS) and related substances are persistent, bioaccumulative, and toxic, and thus of substantial environmental concern. PFOS is an essential photolithographic chemical in the semiconductor industry with no substitutes yet identified. The industry seeks effective treatment technologies. The feasibility of using reverse osmosis (RO) membranes for treating semiconductor wastewater containing PFOS has been investigated. Commercial RO membranes were characterized in terms of permeability, salt rejection, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and membrane surface zeta potential (streaming potential measurements). Filtration tests were performed to determine the membrane flux and PFOS rejection. Over a wide range of feed concentrations (0.5 - 1500 ppm), the RO membranes generally rejected 99% or more of the PFOS. Rejection was better for tighter membranes, but was not affected by membrane zeta potential. Flux decreased with increasing PFOS concentration. While the flux reduction was severe for a loose RO membrane probably due to its higher initial flux, very stable flux was maintained for tighter membranes. At a very high feed concentration (about 500 ppm), all the membranes exhibited an identical stable flux. Isopropyl alcohol, present in some semiconductor wastewaters, had a detrimental effect on membrane flux. Where present it needs to be removed from the wastewater prior to using RO membranes.     

Chicory juice clarification by membrane filtration using rotating disk module

Clarification is the first step of inulin production from chicory juice, and membrane filtration as an alternative can greatly simplify this process, increase juice yield, improve product quality, and reduce the cost and waste volume. In this study, a rotating disk module (RDM) was used to investigate the clarification of chicory juice by four micro- and ultrafiltration membranes. Compared with dead end filtration, the RDM had a much higher permeate flux and product quality. High rotating speeds produced high permeate fluxes and reduced flux decline, because of the strong back transport of foulant from fouling layer to feed solution. At high rotating speeds of 1500–2000 rpm, the permeate flux increased with membrane pore size and transmembrane pressure (TMP), while at low rotating speeds (<1000 rpm), permeate flux was independent of membrane type and TMP due to a thick deposited fouling layer as a dominant filtration resistance, while carbohydrate transmission decreased at higher TMP because of denser cake layer as an additional selective membrane. The highest carbohydrate transmission (∼98%) and desirable permeate turbidity (2.4 NTU) was obtained at a TMP of 75 kPa and a rotating speed of 2000 rpm for FSM0.45PP membrane. With the RDM, the Volume Reduction Ratio (VRR) could reach 10 with a high permeate flux (106 L m⁻² h⁻¹) in the concentration test, and permeate was still rich in carbohydrate and well clarified. Chemical cleaning with 0.5% P3-ultrasil 10 detergent solution was able to recover 90% water flux of fouled membrane.     

Nanofiltration membrane fouling by oppositely charged macromolecules: investigation on flux behavior, foulant mass deposition, and solute rejection

Nanofiltration membrane fouling by oppositely charged polysaccharide (alginate) and protein (lysozyme) was systematically studied. It was found that membrane flux decline in the presence of both lysozyme and alginate was much more severe compared to that when there was only lysozyme or alginate in the feed solution. The flux performance for the mixed foulants was only weakly affected by solution pH and calcium concentration. These effects were likely due to the strong electrostatic attraction between the two oppositely charged foulants. Higher initial flux caused increased foulant deposition, more compact foulant layer, and more severe flux decline. The deposited foulant cake layer had a strong tendency to maintain a constant foulant composition that was independent of the membrane initial flux and only weakly dependent on the relative foulant concentration in feed solution. In contrast, solution chemistry (pH and [Ca2?]) had marked effect on the foulant layer composition, likely due to the resulting changes in the foulant-foulant interaction. The mixed alginate-lysozyme fouling could result in an initial enhancement in salt rejection. However, such initial enhancement was not observed when there was 1 mM calcium present in the feedwater, which may be attributed to the charge neutralization of the foulant layer.