Synthesis and application of ethylenediamine tetrapropionic salt as a novel draw solute for forward osmosis application

The development of suitable draw solutes for forward osmosis (FO) process is a big obstacle on the way of its real industrialization. In this work, a novel draw solute, ethylenediamine tetrapropionic (EDTP) acid (salt) is developed for FO application. The successful synthesis is confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and high resolution mass spectrum. By optimizing the pH of EDTP solution, its composition is varied, and therefore, its water solubility and osmotic pressure are effectively improved. The effects of EDTP concentration on the osmotic pressure and FO performance are also investigated. Its outstanding osmotic pressure and big molecular size result in a high water flux of 22.69 LMH and a low salt flux of 0.32 gMH with 0.8 M EDTP draw solution (water as the feed solution, pressure retarded osmosis mode). The good stability and easy recovery by nanofiltration of EDTP solution also demonstrate its great potential as the draw solute for future FO applications. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1309–1321, 2015     

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.     

Use of Micellar Solutions as Draw Agents in Forward Osmosis

Recent advances in membrane technologies have enhanced the viability of water treatment strategies that employ semipermeable barriers. Forward osmosis (FO), which exploits the natural osmotic pressure gradient between a “draw” solution and a “feed” solution to produce potable water, offers a low‐energy, low‐cost alternative to more conventional treatment methods. Surfactants, because of their tendencies to aggregate into micelles and to adsorb at interfaces, provide intriguing osmotic pressures and offer exploitable properties by which draw solutions can be regenerated. The effectiveness of surfactant‐based FO using cellulose triacetate membranes has been assessed in terms of water flux and reverse surfactant diffusion using cetylpyridinium chloride, sodium dodecylsulfate, and Triton X‐100. The ratios of water flux to surfactant flux exceeded 600 L mol^?1 for all surfactants studied. Surfactant recoveries of over 99 % were achieved by ultrafiltration using regenerated cellulose membranes.     

The application of polyethyleneimine draw solution in a combined forward osmosis/nanofiltration system

The objective of this study is to investigate the effect of solution chemistry of branched polyethyleneimine (PEI) draw solute and to evaluate the PEI draw solute in a combined forward osmosis (FO)/nanofiltration (NF) system. Pure water was extracted from feed solution using the FO process, and the separation of pure water was achieved by the NF process. Lower molecular weight PEI showed higher water flux than higher molecular weight PEI, due to the lower internal concentration polarization caused by a higher diffusion rate and the easy permeation of pure water by lower viscosity of the draw solution (DS). The FO water flux was determined by the osmotic pressure induced by protonation/deprotonation of PEI, and the reverse draw solute flux was determined by the combination of PEI size due to the speciation and electrostatic interaction between the membrane and PEI. This study shows that the J_s/J_w value of PEI at pH 7 was smaller than those of sodium chloride and magnesium sulfate. The recovery of PEI DS using NF has a higher value (99.4%) than of sodium chloride (20.6%) and magnesium sulfate (97.0%); this means that PEI would be a promising draw solute in an FO–NF combined system for the saline water desalination. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42198.     

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.     

The applications of porous FO membranes and polyelectrolyte draw solution in the high-salinity organic wastewater treatment with a hybrid forward osmosis-membrane distillation system

Hybrid forward osmosis-membrane distillation (FO-MD) system have been considered as a promising technology for wastewater treatment. In the current study, initial and modified porous FO membranes are fabricated, and the intrinsic membrane separation properties are also investigated. Polyacrylic acid sodium (PAAS), sodium polystyrene sulfonate (PSS) and polyethylene glycol (PEG) are used to evaluate the effects of draw solution (DS) in FO experiments. Particularly, alkali treated modified porous FO membrane and PAAS are utilized in the subsequent wastewater treatment owing to the high performance of permeation and rejection. Furthermore, the optimal values of operating parameters (flow velocity, DS concentration and DS temperature), which are selected according to the effects of water flux (J_V) in the FO and MD process, are evaluated and utilized to investigate the dynamic changes of J_V in the high-salinity organic wastewater treatment with hybrid FO-MD system. Results show that the hybrid FO-MD system with porous FO membranes and polyelectrolyte DS maintain the operation in a constant flux of 16.61 LMH, and the permeate solution can be effectively recovered with favorable quality. This study provides remarkable implications for the design of porous FO membranes and the application of hybrid FO-MD system in the wastewater treatment.     

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     

Multi-functional forward osmosis draw solutes for seawater desalination

Forward osmosis (FO), as one of the emerging desalination technologies, has the potential to produce freshwater from a variety of water sources by utilizing the osmotic pressure gradient across a semi-permeable membrane. Drawsolution, as an essential component of any FO process, can extract watermolecules fromseawater orwastewater. An ideal draw solution should meet three essential requirements, namely high osmotic pressure, low reverse flux, and facile regeneration mechanism. The selection of proper draw solutes is especially critical for an energy-efficient FO process since the energy consumption mostly arises from the separation or regeneration of the draw solution. Recently, we developed a few multi-functional FO draw solutes, mainly aiming to enhance the FO water flux and to explore facile re-concentration methods. This review summarizes these draw solutes, including Na⁺-functionalized carbon quantum dots, thermoresponsive copolymers, hydrophilic magnetic nanoparticles, and thermoresponsive magnetic nanoparticles.     

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.     

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     

Characteristics and potential applications of a novel forward osmosis hollow fiber membrane

There has been a resurgence of interest in forward osmosis (FO) as a potential means of desalination, dewatering and in pressure retarded osmosis, which Sidney Loeb was advocating over 3 decades ago. This paper describes the characteristics and potential applications of a newly developed FO hollow fiber membrane, which was fabricated by interfacial polymerization on the inner surface of a polyethersulfone (PES) hollow fiber. This FO membrane presents excellent intrinsic separation properties, with a water flux of 42.6 L/m² h using 0.5 M NaCl as the draw solution and DI water as the feed with the active layer facing the draw solution orientation at 23 °C. The corresponding ratio of salt flux to water flux was only 0.094 g/L, which is superior to all other FO membranes reported in the open literature. To evaluate different application scenarios, various NaCl solutions (500 ppm (8.6 mM), 1 wt.% (0.17 M) and 3.5 wt.% (0.59 M)) were used as the feed water to test the performance of the FO membrane. The membrane can achieve a water flux of 12.4 L/m² h with 3.5 wt.% NaCl solution as the feed and 2 M NaCl as the draw solution, suggesting it has good potential for seawater desalination.     

Preparation of novel magnetic nanoparticles as draw solutes in forward osmosis desalination

Novel magnetic nanoparticles (MNPs), Fe₃O₄@SiO₂ and Fe₃O₄@SiO₂@PEG-(COOH)₂, were prepared by loading different amounts of SiO₂ or/and PEG-(COOH)₂ onto Fe₃O₄ nanoparticles, and their feasibility to be used as forward osmosis (FO) draw solutes was investigated. The characterization of the materials showed that, compared to normal Fe₃O₄ nanoparticles, the modified MNPs exhibited enhanced dispersity and high osmotic pressure in aqueous solution. The FO experiment indicated that the synthesized draw solutes could obtain a water flux as high as 10 L·m^-2·h^-1 with an aquaporin FO membrane. The optimal concentration of the added tetraethyl orthosilicate was 30% during the synthesis. The novel MNPs could be easily recovered from draw solutions by magnetic field, and the recovery rate of Fe₃O₄@SiO₂ and Fe₃O₄@SiO₂@PEG-(COOH)₂ was 83.95% and 63.37%, respectively. Moreover, after 5 recycles of reuse, the water flux of Fe₃O₄@SiO₂ and Fe₃O₄@SiO₂@PEG-(COOH)₂ as draw solutes still remained 64.36% and 85.26%, respectively. The experimental results demonstrated that the synthesized core–shell magnetic nanoparticles are promising draw solutes, and the Fe₃O₄@SiO₂@PEG-(COOH)₂ was more suitable to be used as draw solute in FO process.     

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。     

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.     

Fabrication of fullerenol-incorporated thin-film nanocomposite forward osmosis membranes for improved desalination performances

Development and use of novel membranes for forward osmosis (FO) applications have gained popularity throughout the world. To enhance FO membrane performance, a novel thin-film nanocomposite membrane was fabricated by interfacial polymerization incorporating Fullerenol (C₆₀(OH)_n) nanomaterial, having n in the range of 24–28 into the active layer. Different concentrations of fullerenol loading (100, 200, 400, and 800 ppm) were added to the top skin layer. The structural and surface properties of the pure thin-film composite membrane (TFC) and fullerenol-incorporated thin-film nanocomposite (FTFC) membranes, were characterized by ATR-FTIR, SEM, and AFM. FO performance and separation properties were evaluated in terms of water flux, reverse salt flux, antifouling propensity, water permeability and salt permeability for all TFC and FTFC membranes. Osmotic performance tests showed that FTFC membranes achieved higher water flux and reverse salt flux selectivity compared with those of TFC membranes. The FTFC membrane with a fullerenol loading of 400 ppm exhibited a water flux of 26.1 L m^?2 h^?1 (LMH), which is 83.03% higher than that of the TFC membrane with a specific reverse salt flux of 0.18 g/L using 1 M sodium chloride draw solution against deionized water in FO mode. The fullerenol incorporation in FTFC membranes also contributed to a decreased fouling propensity.     

Chitosan- and dehydroascorbic acid-coated Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles: preparation,characterization and their potential as draw solute in forward osmosis process

Forward osmosis (FO) is a natural osmosis process that has attracted a significant attention due to its many advantages. However, the development of FO process depends on the development of proper draw solutions. In this work, chitosan (CS)-coated Fe₃O₄ nanoparticles and dehydroascorbic acid (DHAA)-coated Fe₃O₄ nanoparticles were successfully synthesized by co-precipitation method and their performance as draw solutes was investigated for application in FO systems. CS and DHAA could improve the surface hydrophilicity of the Fe₃O₄ nanoparticles. The synthesized nanoparticles were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometry (VSM) which the results presented a small size, crystalline morphology and high magnetization value for their structure as well as a good dispersion in water. Cellulose triacetate/cellulose acetate (CTA/CA)-based membranes were also prepared by immersion precipitation and used as FO membranes. The synthesized FO membranes were characterized by FESEM. The performance evaluation of synthesized nanoparticles revealed that the water flux of Fe₃O₄ nanoparticles capped with DHAA was higher than that of the chitosan-coated Fe₃O₄ nanoparticles. At the end of the process, the Fe₃O₄ nanoparticles were easily separated from the diluted draw solution by applying the magnetic field.     

Effects of organic acids on the performance of cellulose triacetate forward osmosis membrane

Forward osmosis (FO) membrane performance was improved using different organic acids (formic acid, acetic acid, lactic acid) for the addition of the casting solution. Scanning electron microscope (SEM) images of all the FO CTA membranes exhibited essentially the membranes have a structure of looking like two dense skin layers and a sponge‐like supporting layer. Additionally, based on the surface roughness values analysis of Atomic Force Microscope (AFM), the membranes with lactic acid, with similar roughness to the membranes without any acid, have bigger roughness than the membranes with formic acid or acetic acid. Furthermore, the water flux of membranes with acids has been improved and the reverse salt flux decreased. The membranes with lactic acid, with an outstanding penetration performance, were utilized to test the performance when 1 mol/L sodium chloride (NaCl), magnesium chloride (MgCl₂)_, magnesium sulfate (MgSO₄), and sodium sulfate (Na₂SO₄) were, respectively, as the draw solutions. The results revealed that the membranes have a higher rejection ratio for MgSO₄. Besides, in the process of separating oil–water mixture, the membranes with the organic acids have a better separation efficiency than the membrane without any acid during FO process and the water flux recovery rate could achieve above 90% insuring the membrane anti‐fouling. POLYM. ENG. SCI., 59:E138–E145, 2019. © 2018 Society of Plastics Engineers     

温度对正向渗透的影响机制与数值模拟

正向渗透(FO)是一种以溶液自身渗透压作为推动力的膜分离技术。温度对溶液、膜的性质以及溶液与膜之间的相互作用有很大影响,进而影响FO的水通量。利用数值模拟与试验研究了温度对FO性能的影响。结果表明,当膜两侧等温时,FO水通量随着温度的升高而增大;当膜两侧不等温时,原液(FS)一侧温度的影响比提取液(DS)一侧更大,主要是因为温度升高降低了溶液黏度,强化了过膜扩散过程,而温度对DS渗透压的影响不明显。在不同温度条件下,FO水通量和热通量随流量的增大而增大,主要是由于流速的增大压缩膜表面的流体边界层,强化了传质和传热过程。     

Polyamide/polyacrylonitrile thin film composites as forward osmosis membranes

Thin film composites (TFCs) as forward osmosis (FO) membranes for seawater desalination application were prepared. For this purpose, polyacrylonitrile (PAN) as a moderately hydrophilic polymer was used to fabricate support membranes via nonsolvent‐induced phase inversion. A selective thin polyamide (PA) film was then formed on the top of PAN membranes via interfacial polymerization reaction of m‐phenylenediamine and trimesoyl chloride (TMC). The effects of PAN solution concentration, solvent mixture, and coagulation bath temperature on the morphology, water permeability, and FO performance of the membranes and composites were studied. Support membranes based on low PAN concentrations (7 wt %), NMP as solvent and low coagulation bath temperature (0 °C) demonstrated lower thickness, thinner skin layer, more porosity, and higher water permeability. Meanwhile, decreasing the PAN solution concentration lead to higher water permeance and flux and lower reverse salt flux, structural parameter, and tortuosity for the final TFCs. Composites made in N,N‐dimethylformamide presented lower permeance and flux for water and salt and higher salt rejection, structural parameter, and tortuosity. FO assay of the composites showed lower water permeance values in saline medium comparing to pure water. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44130.