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     

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.     

Novel carboxyethyl amine sodium salts as draw solutes with superior forward osmosis performance

A series of carboxyethyl amine sodium salts (CASSs) with different carboxyl group numbers are synthesized as draw solutes for forward osmosis (FO) application. Their chemical structures are examined by ¹HNMR and HRMS. FO performances are investigated and compared in terms of different physicochemical properties. The effects of the CASS concentration on the osmotic pressure and viscosity of the draw solutions, as well as the resulted FO performance are also systematically investigated. A high water flux of 23.07 LMH and an acceptable reverse salt flux of 0.75 gMH can be achieved with 0.5 g mL^?1 triethylenetetramine hexapropionic acid sodium (TTHP‐Na) draw solution under PRO mode, which is superior to most other draw solutes reported in previous literatures. TTHP‐Na draw solution is further evaluated to recycle the Congo red solution via FO process to examine its applicability for waste water treatment. © 2015 American Institute of Chemical Engineers AIChE J, 62: 1226–1235, 2016     

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     

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.     

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.     

A trimethylamine–carbon dioxide draw solution for osmotic engines

This study evaluates the pressure retarded osmosis performance of TMA–CO₂ for potential use in osmotic heat engines. Power densities up to 18.6 W m^?2 were achievable at relatively low pressure (10 bar) using 5 M TMA–CO₂ draw solutions. Compared to NaCl control tests, the TMA–CO₂ exhibited 20% lower water flux due in large part to its larger molecular size and associated higher solution viscosity and lower diffusion coefficient. Compared to the ammonia‐carbon dioxide draw solution, water flux was comparable but reverse solute flux of TMA–CO₂ was nearly one order of magnitude lower. Larger solute size was found to create a performance tradeoff as reduced reverse solute flux improved water flux while higher viscosity and lower diffusion coefficient worsened water flux. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3369–3375, 2018     

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.     

Preparation and characterization of a novel positively charged nanofiltration membrane based on polysulfone

The goal of this study was to prepare positively charged nanofiltration (NF) membranes to remove cations from aqueous solutions. A composite NF membrane was fabricated by the modification of a polysulfone ultrafiltration support. The active top layer was formed by the interfacial crosslinking polymerization of poly(ethylene imine) (PEI) with p‐xylene dichloride (XDC). Then, it was quaternized by methyl iodide (MI) to form a perpetually positively charged layer. The chemical and morphological changes of the membrane surfaces were studied by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy. To optimize the membrane operation, the PEI solution concentration, PEI coating time, XDC concentration, crosslinking time, and MI concentration were optimized. Consequently, high water flux (5.4 L m^?2 h^?1 bar^?1) and CaCl₂ rejection (94%) values were obtained for the composite membranes at 4 bars and 30°C. The rejections of the NF membrane for different salt solutions, obtained from pH testing, followed the order Na₂SO₄ < MgSO₄ < NaCl < CaCl₂. The molecular weight cutoff was calculated by the retention of poly(ethylene glycol) solutions with different molecular weights, and finally, the stoke radius was calculated as 1.47 nm. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41988.     

Impact of osmotic agent on the transport of components using forward osmosis to separate ethanol from aqueous solutions

The separation of low molecular weight organic compounds such as the ethanol from aqueous solutions represents an important area to be investigated and increment the range of applications of forward osmosis. This investigation assesses the effects of using different draw solutes for ethanol separation from dilute aqueous solutions. The influence of glucose, sucrose, sodium chloride, and magnesium chloride was evaluated in terms of total permeate, reverse solute and ethanol fluxes. Inorganic solutes promoted higher total permeate and ethanol fluxes than the organic solutes (2.5 and 1.5 times higher in average, respectively) for the same molar concentration, while presenting only 1.1 times higher reverse solute fluxes. Despite the lower ethanol flux promoted by the organic draw solutes, these osmotic agents promoted higher concentration of ethanol in the total permeate flux, suggesting that they can also be alternatives for specific processes. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4499–4507, 2017     

Evaluation of a modified spray-applied interfacial polymerization method for preparation of nanofiltration membranes

Nanofiltration (NF) membranes were fabricated by using piperazine (PIP) and trimesoyl chloride (TMC) by conventional and spray-applied interfacial polymerization methods, studying the effect of the application method for both phases, the number of applied layers, and the displacement speed for the spray application. A polysulfone ultrafiltration membrane was used as support. NF membranes were characterized by different spectroscopic, microscopic, and physicochemical techniques. Rejection capacity was evaluated for sodium chloride (NaCl), sodium sulfate (Na₂SO₄), and magnesium sulfate (MgSO₄) salts; the decreasing rejection order was Na₂SO₄ > MgSO₄ > NaCl for each NF membrane. NF membrane prepared with one layer of the sprayed out TMC solution and conventional application of PIP solution exhibited the highest salt rejection (99% for 1000 ppm Na₂SO₄) and a permeated flux of 10.28 L m⁻² h⁻¹ at 0.55 MPa. The modified method is a facile-reproducible preparation methodology that reduces the consumption of time, effort, and reagents leading to a scalable manufacturing process for separation technology. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48129.     

操作条件对正渗透分离性能的影响

正渗透是以渗透压差为驱动力的新型膜分离过程。采用水流分布较佳的膜池结构,研究了膜朝向、流动方式对正渗透水通量性能的影响,结果表明PRO模式（当膜的活性层朝向驱动液时）的水通量明显高于FO模式（当膜的活性层朝向原料液时）,但其衰减程度较大;在溶液浓度差相同的条件下,逆流操作更利于水通量的提高。针对FO模式和逆流条件,探讨了溶液温度对水通量和反向盐通量的影响,结果表明：膜两侧溶液温度同步升高时,正渗透过程的水通量和反向盐通量均增加,且水通量的增加幅度大于反向盐通量;单侧增加溶液的温度时,驱动液侧温度升高对水通量性能的提升效果优于原料液侧。综合考虑过程能耗和系统性能,认为单独升高驱动液温度更具实用价值。     

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。     

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。     

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.     

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

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

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.     

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.     

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.     

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.