Advanced FO membranes from newly synthesized CAP polymer for wastewater reclamation through an integrated FO‐MD hybrid system

A new cellulose acetate propionate (CAP) polymer has been synthesized and used to prepare high‐performance forward osmosis (FO) membranes. With an almost equal degree of substitution of acetyl and propionyl groups, the CAP‐based dense membranes show more balanced physicochemical properties than conventional cellulose acetate (CA)‐based membranes for FO applications. The former have a lower equilibrium water content (6.6 wt. %), a lower salt diffusivity (1.6×10¹⁴ m² s^?1) and a much lower salt partition coefficient (0.013) compared with the latter. The as‐prepared and annealed CAP‐based hollow fibers have a rough surface with an average pore radius of 0.31 nm and a molecular weight cut off of 226 Da. At a transmembrane pressure of 1 bar, the dual‐layer CAP‐CA hollow fibers show a pure water permeability of 0.80 L m^?2 h^?1 bar^?1 (LMH/bar) and a rejection of 75.5% to NaCl. The CAP‐CA hollow fibers were first tested for their FO performance using 2.0 M NaCl draw solution and deionized water feed. An impressive water flux of 17.5 L m^?2 h^?1 (LMH) and a reverse salt flux of 2.5 g m^?2 h^?1 (gMH) were achieved with the draw solution running against the active CAP layer in the FO tests. The very low reverse salt flux is mainly resulting from the low salt diffusivity and salt partition coefficient of the CAP material. In a hybrid system combining FO and membrane distillation for wastewater reclamation, the newly developed hollow fibers show very encouraging results, that is, water production rate being 13–13.7 LMH, with a MgCl₂ draw solution of only 0.5 M and an operating temperature of 343 K due to the incorporation of bulky propionyl groups with balanced physiochemical properties. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1245–1254, 2013     

Synthesis and characterization of PES/PSF/PEG by immersion precipitation for Mediterranean seawater desalination by FO membrane

In the present study, a simple, inexpensive, nontoxic, and environmentally friendly polyethylene glycol (PEG) polymer was used to enhance the hydrophilicity of the forward osmosis (FO) membrane using various PEG concentrations as a pore forming agent in the casting solution of polyethersulfone/polysulfone (PES/PSF) blend membranes. A nonwoven PES/PSF FO blend membrane was fabricated via the immersion precipitation phase inversion technique. The membrane dope solution was cast on polyethylene terephthalate (PET) nonwoven fabric. The results revealed that PEG is a pore forming agent and that adding PEG promotes membrane hydrophilicity. The membrane with 1 wt% PEG (PEG1) had about 27% lower contact angle than the pristine blend membrane. The PEG1 membrane has less tortuosity (which reduces from 3.4–2.73), resulting in a smaller structure parameter (S value) of 277 μm, due to the presence of open pores on the bottom surface structure, which results in diminished ICP. Using 1 M NaCl as the draw solution and distilled water as the feed solution, the PEG1 membrane exhibited higher water flux (136 L m⁻² h⁻¹) and lower reverse salt flux (1.94 g m⁻² h⁻¹). Also, the selectivity of the membrane, specific reverse salt flux, (J_s/J_w) showed lower values (0.014 g/L). Actually, the PEG1 membrane has a 34.6% higher water flux than the commercial nonwoven-cellulose triacetate (NW-CTA) membrane. By means of varied concentrations of NaCl salt solution (0.6, 1, 1.5, and 2 M), the membrane with 1 wt% PEG showed improved FO separation performance with permeate water fluxes of 108, 136, 142, and 163 L m⁻² h⁻¹. In this work, we extend a promising gate for designing fast water flux PES/PSF/PEG FO blend membranes for water desalination.     

Cellulose esters for forward osmosis: Characterization of water and salt transport properties and free volume

The fundamental salt and water transport properties of cellulose ester polymers have been studied and correlated with their hydrated free volume, as probed by positron annihilation lifetime spectroscopy (PALS), to provide scientific insights for material development in seawater desalination. It has been found that the hydrated free volume is strongly dependent on water uptake. The water sorption in polymeric films reduces the fractional free volume (FFV) at low degrees of hydration due to the overwhelming hole-filling effect, but gradually increases FFV when more water sorption takes place as a result of the swelling effect. The diffusivity and permeability of both water and salt vary with changes in wet-state FFV. Diffusion selectivity of H₂O/NaCl increases dramatically as the hydrated FFV decreases, while solubility selectivity of H₂O/NaCl is dependent on both hydrated free volume and chemical structure. Moreover, thin freestanding films with no sub-layer support have been prepared by spin casting these polymers on silicon wafers for the purpose of eliminating internal concentration polarization (ICP) in the forward osmosis (FO) process. Based on the theoretical prediction from the solution-diffusion model, the performance ratio (i.e., the ratio of the experimental to theoretical water flux) of the sub-layer free films can be calculated. It can reach as high as around 50%, which is 2–3 times of the values reported elsewhere when testing traditional asymmetric membranes. Using a model 3.5 wt.% NaCl feed solution and a 2M NaCl draw solution, a water flux of 21.8 LMH has been observed, which is the highest value ever reported. The high water flux in the FO desalination process indicates that the concept of sub-layer-free thin films is promising for the next generation FO membranes.     

Short-term fouling propensity and flux behavior in an osmotic membrane bioreactor for wastewater treatment

The short-term fouling behavior of forward osmosis (FO) membrane in an osmotic membrane bioreactor (OMBR) was investigated, using NaCl or MgCl₂ as the draw solutions. The effect of membrane orientation, mixed liquor suspended solids (MLSS) concentration and draw solution (DS) osmotic pressure on water flux and membrane fouling behaviors was examined, along with the effects of simulated elevated salinity on sludge properties and on membrane fouling. Water flux and membrane fouling were not significantly affected by both MLSS concentration (4.91–12.60 g/L) and osmotic pressure (3.0–15.0 MPa), but were severely affected by elevated salinity, due to changes in activated sludge properties, in particular the increase in extracellular polymeric substances (EPS) and sludge hydrophobicity. MgCl₂ as the DS showed more significant influence on activated sludge properties and membrane fouling than NaCl but gave rise to lower salt accumulation. Analyses of the membrane foulants showed that small sludge floc/particles and EPS (in particular, proteins) were enriched in the fouling layer. UPLC–MS/MS analyses of the proteins showed that hydrophobic proteins were the main cause of membrane fouling.     

Thin-film composite forward osmosis membrane prepared from polyvinyl chloride/cellulose carbamate substrate and its potential application in brackish water desalination

Synthesized by the reaction between α-cellulose and m-tolyl isocyanate (MTI), cellulose carbamate (CC) was blended with polyvinyl chloride (PVC) to fabricate substrates for thin-film composite (TFC) forward osmosis (FO) membranes. The introduction of CC into substrates improved both membrane structure and performance. The substrates exhibited higher porosity and hydrophilicity, and better connective pore structure; while rejection layer exhibited better morphology but limited cross-linked degree decrease after the introduction of CC. According to the results, the CC blend ratio of 10% was the optimal ratio. With this blend ratio, the TFC-10 membrane presented favorable water permeability (1.86 LMH/bar) and structure parameter (337 μm), which resulted in excellent FO performance (water flux with a value of 40.40 LMH and specific salt flux with a value of 0.099 g/L under rejection layer faces draw solution [DS] mode when 1 M NaCl and deionized water were utilized as DS and feed solution). In addition, the TFC-10 membrane showed good water flux and low-sulfate ion leakage in the potential application of brackish water desalination.     

Developing thin‐film‐composite forward osmosis membranes on the PES/SPSf substrate through interfacial polymerization

A new scheme has been developed to fabricate high‐performance forward osmosis (FO) membranes through the interfacial polymerization reaction on porous polymeric supports. p‐Phenylenediamine and 1,3,5‐trimesoylchloride were adopted as the monomers for the in‐situ polycondensation reaction to form a thin aromatic polyamide selective layer of 150 nm in thickness on the substrate surface, a lab‐made polyethersulfone (PES)/sulfonated polysulfone (SPSf)‐alloyed porous membrane with enhanced hydrophilicity. Under FO tests, the FO membrane achieved a higher water flux of 69.8 LMH when against deionized water and 25.2 LMH when against a model 3.5 wt % NaCl solution under 5.0 M NaCl as the draw solution in the pressure‐retarded osmosis mode. The PES/SPSf thin‐film‐composite (TFC)‐FO membrane has a smaller structural parameter S of 238 μm than those reported data. The morphology and topology of substrates and TFC‐FO membranes have been studied by means of atomic force microscopy and scanning electronic microscopy. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

A novel ammonia—carbon dioxide forward (direct) osmosis desalination process

A novel forward (direct) osmosis (FO) desalination process is presented. The process uses an ammonium bicarbonate draw solution to extract water from a saline feed water across a semi-permeable polymeric membrane. Very large osmotic pressures generated by the highly soluble ammonium bicarbonate draw solution yield high water fluxes and can result in very high feed water recoveries. Upon moderate heating, ammonium bicarbonate decomposes into ammonia and carbon dioxide gases that can be separated and recycled as draw solutes, leaving the fresh product water. Experiments with a laboratory-scale FO unit utilizing a flat sheet cellulose tri-acetate membrane demonstrated high product water flux and relatively high salt rejection. The results further revealed that reverse osmosis (RO) membranes are not suitable for the FO process because of relatively low product water fluxes attributed to severe internal concentration polarization in the porous support and fabric layers of the RO membrane.     

Effects of polyethylene glycol on the structure and filtration performance of thin-film PA-Psf composite forward osmosis membranes

In forward osmosis, internal concentration polarization is related to the properties (e.g., hydrophilicity, porosity, structural resistant) of membrane support layer. In this work, polyethylene glycol with a low molecular weight of 400 Da was introduced as a support layer additive during the fabrication of thin-film polyamide-polysulfone composite forward osmosis membranes. The forward osmosis performances including water flux and reverse salt flux of the membranes were tested in the mode of AL-FS where the membrane active layer faced toward feed solution. Results showed that the addition of polyethylene glycol would reduce internal concentration polarization and improve membrane performance in forward osmosis by means of enhancing membrane hydrophilicity and changing pore morphologies of membrane support layer. The membrane prepared with 6 wt.% polyethylene glycol was found to exhibit the highest water flux of 47.4 Lm^?2h^?1 with a reverse salt flux of 7.6 gm^?2h^?1 when using DI water and 2.0 M NaCl as the feed and the draw solution, respectively, indicating an optimal polyethylene glycol dosage of 6 wt.% in this work.     

Thin-film composite forward osmosis membranes with substrate layer composed of polysulfone blended with PEG or polysulfone grafted PEG methyl ether methacrylate

To advance commercial application of forward osmosis (FO), we investigated the effects of two additives on the performance of polysulfone (PSf) based FO membranes: one is poly(ethylene glycol) (PEG), and another is PSf grafted with PEG methyl ether methacrylate (PSf-g-PEGMA). PSf blended with PEG or PSf-g-PEGMA was used to form a substrate layer, and then polyamide was formed on a support layer by interfacial polymerization. In this study, NaCl (1 mol?L⁻¹) and deionized water were used as the draw solution and the feed solution, respectively. With the increase of PEG content from 0 to 15 wt-%, FO water flux declined by 23.4% to 59.3% compared to a PSf TFC FO membrane. With the increase of PSf-g-PEGMA from 0 to 15 wt-%, the membrane flux showed almost no change at first and then declined by about 52.0% and 50.4%. The PSf with 5 wt-% PSf-g-PEGMA FO membrane showed a higher pure water flux of 8.74 L?m⁻²?h⁻¹ than the commercial HTI membranes (6–8 L?m⁻²?h⁻¹) under the FO mode. Our study suggests that hydrophobic interface is very important for the formation of polyamide, and a small amount of PSf-g-PEGMA can maintain a good condition for the formation of polyamide and reduce internal concentration polarization.     

Poly(ethylene glycol) crosslinked sulfonated polysulfone composite membranes for forward osmosis

Forward osmosis (FO) membranes were prepared by a coating method with poly(ethylene glycol) crosslinked sulfonated polysulfone (SPSf) as a selective layer. The poly(ether sulfone)/SPSf substrate was prepared by phase inversion. The composite membranes were characterized with respect to membrane chemistry (by attenuated total reflectance/Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy), hydrophilicity (by static contact angle measurement), and surface morphology (by scanning electron microscopy and atomic force microscopy). The FO performance was also characterized. The effects of the crosslinker concentration on the hydrophilicity and FO performance were investigated. The crosslinked membrane exhibited a high hydrophilicity with a lowest contact angle of 15.5°. Under FO tests, the membranes achieved a higher water flux of 15.2 L m^?2 h^?1 when used against deionized water as the feed solution and a 2 mol/L sodium chloride (NaCl) solution as the the draw solution. The membranes achieved a magnesium sulfate rejection of 96% and an NaCl rejection of 55% when used against a 1 g/L inorganic salt solution as the feed solution and a 2 mol/L glucose solution as the draw solution. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43941.     

High performance forward osmosis cellulose acetate (CA) membrane modified by polyvinyl alcohol and polydopamine

Cellulose acetate (CA) is a low cost and readily available material widely used in forward osmosis (FO) membranes. However, the performance of pure CA membranes is not good enough in salt separation and the traditional modification methods are generally multistep and difficult to control. In this paper, we reported high performance cellulose acetate (CA) composite forward osmosis (FO) membranes modified with polyvinyl alcohol (PVA) and polydopamine (PDA). PVA was first cross-linked onto the surface of CA membranes, and then PDA was coated with a rapid deposition method. The membranes were characterized with respect to membrane chemistry (FTIR and XPS), surface properties comprising wettability (by water contact angle), and osmosis performance. The modified membrane coated by PVA and PDA shown better hydrophilicity and exhibited 16.72 LMH osmotic water flux and 0.14 mMH reverse solute flux with DI water as feed solution and 2.0 M NaCl as draw solution and active layer facing the feed solution. This simple and highly effective modification method makes it as an excellent candidate for further exploration for FO.     

Synthesis and characterization of PVC-TFC hollow fibers for forward osmosis application

Forward osmosis (FO) is considered among the most encouraging water desalination processes as a result of its high performance and low energy demand. Thin-film composite (TFC) hollow fibers (HF) were synthesized and examined in the FO process. Three different concentrations of polyvinyl chloride (PVC) support polymer were fabricated via the phase inversion technique. The polyamide layer was synthesized on the outer surface of the PVC-HF substrate via interfacial polymerization (IP) reaction. To the best of our knowledge, PVC HF was used in this research for the first time as a support for TFC-FO membranes. PVC HFs have high-quality specifications that are expected to have outstanding performance in TFC-FO applications, especially for water desalination. The obtained membranes were characterized using contact angle measurement, scanning electron microscopy, atomic force microscope and Fourier-transform Infrared. The performance of the PVC-TFC HF was examined in the FO under standard conditions. Results showed that the membrane fabricated with a lower concentration of PVC substrate exhibited higher water flux in comparison to the higher concentration PVC membrane. Changing the concentration of PVC from 15% to 18% reduced water flux from 25 to 13 L m⁻² h⁻¹; however, salt flux also decreased from 8 to 3 g m⁻² h⁻¹.     

刮刀厚度对聚酰胺正渗透复合膜性能的影响

为考察正渗透过程基膜厚度对膜水通量的作用,有效地提高膜的综合性能,采用浓度2 mol/L的NaCl作为汲取液、去离子水为原料液作为评价系统,考察了刮刀厚度不同对正渗透复合膜性能的影响。结果表明,以筛孔80μm的筛网作为支撑材料,当采用厚度为45μm的刮刀所制备的超滤膜作为支撑材料时,制备所得的正渗透复合膜性能为佳,结构参数S可低至1.086 mm;并具有最好的稳定性以及最佳的污染冲洗恢复效果。     

正渗透膜分离的研究进展

正渗透是浓度驱动的膜技术,是指水通过选择性渗透膜从高水化学势区域向低水化学势区域的传递过程。本文介绍了正渗透的基本构成（驱动力、汲取液和正渗透膜材料）,指出膜两侧的浓差极化是水通量性能的最大障碍,采用通量模型说明了膜在两种放置方向下存在的内浓差极化和外浓差极化,内浓差极化对驱动力的减小起着重要的作用;论述了膜材料、原料液浓度、汲取液浓度对正渗透和压力延迟渗透水通量的影响;此外,评述了正渗透过程的膜污染和能耗。     

正渗透—纳滤耦合处理苦咸水脱盐工艺

以2 000 mg/L氯化钠模拟苦咸水,采用二价无机盐作为汲取液,研究了正渗透淡化苦咸水时的水通量;通过软件计算和试验研究了不同组成汲取液的纳滤性能,并且设计了二级纳滤系统用于汲取液的回收。结果表明:相同浓度时硫酸镁汲取液正渗透水通量最低,而氯化镁汲取液水通量最高;相反在纳滤过程中,硫酸镁汲取液性能最佳,氯化镁最差;稀释硫酸钠汲取液浓度为30 g/L时,二级纳滤过程可以将汲取液浓缩至初始浓度(60 g/L),并制得浓度低于500 mg/L的产水。     

Thin film composite forward osmosis membranes with poly(2‐hydroxyethyl methacrylate) grafted nano‐TiO2 as additive in substrate

The poly(2‐hydroxyethyl methacrylate) grafted titanium dioxide nanoparticles were synthesized and added to the substrate of flat‐sheet thin film composite forward osmosis (TFC‐FO) membranes. The hydrophilicity of substrate was improved, which was advantageous to enhance the water flux of TFC‐FO membranes. The membranes containing a 3 wt % TiO₂‐PHEMA in the substrate exhibited a finger‐like structure combined with sponge‐like structure, while those with lower or without TiO₂‐PHEMA content showed fully finger‐like structures. As for FO performance, the TFC‐FO membranes with 3 wt % TiO₂‐PHEMA content achieved the highest water flux of 42.8 LMH and 24.2 LMH against the DI water using 2M NaCl as the draw solution tested under the active layer against draw solution (AL‐DS) mode and active layer against feed solution (AL‐FS) mode, respectively. It was proven that the hydrophilic property of membrane substrates was a strong factor influencing the water flux in FO tests. Furthermore, the structural parameter was remarkably decreased with an increase of TiO₂‐PHEMA content in membrane substrate, indicating the reducing of internal concentration polarization. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43719.     

Effect of cellulose triacetate membrane thickness on forward‐osmosis performance and application for spent electroless nickel plating baths

Cellulose triacetate (CTA) forward‐osmosis (FO) membranes were prepared via the phase inversion method. The influence of thickness on the performance and morphology of CTA FO membranes was discussed in detail. When the thickness of the membrane was 50.0 ± 0.5 μm (CTA4), the prototype CTA membranes displayed a water flux of 20.2 L m^?2 h^?1 and a reverse salt transport of 14.6 g m^?2 h^?1 using 1 mol/L NaCl as the draw solution and deionized water as the feed solution during the FO process at 25 °C. In addition, the high‐performance CTA4 FO membranes have been used to process spent electroless nickel plating baths where the water flux could reach 13 L m^?2 h^?1 and NiSO₄·6H₂O crystals occurred in the feed solution of the spent electroless nickel plating baths. The recovery rates of NiSO₄·6H₂O and water from the spent electroless nickel plating baths were 44.54% and 53.53%, respectively. This study focused on improving membrane design for the FO process and finding a new method of waste liquor or wastewater treatment. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45049.     

正渗透过程中汲取质反向渗透研究进展

正渗透(FO)作为一种浓度驱动的膜技术,因其膜污染轻、能耗低和回收率高等优点而逐渐成为膜技术领域的研究热点之一。汲取质的反向渗透是正渗透过程中不可忽视的现象,但其研究相对比较滞后。本文主要介绍了汲取质反渗模型的研究进展,分析了渗透压差、膜表面流速、膜结构与膜材料、温度、汲取质种类、膜取向、离子水力半径等因素对汲取质反向渗透的影响情况,并发现汲取质的反向渗透通量可由其浓度或汲取液渗透压的一元多项式表达。总体而言,FO模式的汲取质反渗模型经过不断发展已相对比较完善,而压力阻尼渗透(PRO)模式的反渗模型则缺陷较大,有待进一步研究;此外,关于汲取质反渗过程影响因素及其影响机制的研究对于汲取质、膜材料的选择与开发,以及正渗透过程的优化均具有重要的指导作用,因此会引起越来越多的关注。     

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.     

正向渗透膜分离技术及其应用综述

正向渗透是一项新型的利用半透膜两侧溶液渗透压差作为驱动力的膜分离技术。文章介绍了正向渗透膜分离技术的原理和影响因素,对其在各个领域(包括海水淡化、废水处理、橙汁浓缩、水袋)的研究进展进行了综述。现有的研究表明,可用于正向渗透工艺的膜不同于常规的反渗透膜,需要从膜结构开发适合的膜组件;采用NH3和CO2制备提取液是目前研究中具有应用前途的方式之一,具有产水率高且易于分离浓缩的优点。