Interfacially synthesized thin film composite RO membranes for seawater desalination

A composite RO membrane with high salt rejection and high flux for the desalination of seawater was prepared by treating a porous polysulfone (PS) support sequentially with a di-amine and then with a polyfunctional acid chloride, thereby forming a thin film of polyamide (PA) on the PS support. In order to establish conditions for the development of suitable thin film composite (TFC) membranes on a coating machine, various parametric studies were carried out which included varying the concentration of reactants, reaction time, curing temperature and curing time for thin film formation by the interfacial polymerization technique. By suitable combination of these factors,a desired thin film of polyamide with improved performance for seawater desalination could be obtained. Moreover, the product water fluxes were considerably enhanced by post-treatment of the TFC membrane. Continuous sheets of TFCs were developed on the mechanical coating unit and tested for RO performance in a plate-and-frame configuration with synthetic seawater. The performance of these composite membranes was also determined for the separation of organics and compared with cellulose acetate (CA) membranes.     

Effect of silane coupling agents on the performance of RO membranes

This study investigates the effect of silane coupling agents on the performance of reverse osmosis (RO) membranes on the basis of sol–gel coating method. The surfaces of the RO membranes were chemically modified with four different alkoxysilanes in order to reduce their hydrophilicity. The objective of this study is to superpose hydrophobic polysiloxane layer on the surface of a polyamide TFC RO membrane and to increase the extent of salt rejection by the modified membranes. A commercial composite RO membrane (SWC1) was treated with silane coupling agents in ethanol at three different concentrations: 1.0, 1.5, and 2.0% (w/v). The silane coupling agents contain one alkyl or phenyl and three alkoxy groups (e.g., methyltriethoxysilane, octyltriethoxysilane, octadecyltrimethoxysilane and phenyltriethoxysilane). In addition, the effect of alkyl or phenyl group hydrophobicity on the permeability and salt rejection of the modified membrane was examined. The surfaces of the modified membranes were characterized by SEM, AFM, contact angle analyzer, and XPS in order to confirm successful sol–gel methods. The modified membranes showed significantly enhanced salt rejection without a decrease in flux. From the surface analysis results, we can observe the changes in the surface roughness, elemental composition, electron energy, and hydrophilicity.     

Simple fabrication of Cu~(2+) doped calcium alginate hydrogel filtration membrane with excellent anti-fouling and antibacterial properties

Herein,copper ion doped calcium alginate(Cu~(2+)/CaAlg) composite hydrogel filtration membranes were prepared by using natural polymer sodium alginate(NaAlg) as raw material.The thermal stability and structure of the composite membranes were characterized by thermogravimetric analysis and infrared spectroscopy.The mechanical strength,anti-fouling performance,hydrophilicity and filtration performance of the membrane were studied.The results show that Cu~(2+)/CaAlg hydrogel membrane has excelle nt mechanical properties and thermal stability.The anti-swelling ability of the membrane was greatly enhanced by doping Cu~(2+).After three alternate filtration cycles,the flux recovery rate of Cu~(2+)/CaAlg hydrogel membrane can still reach 85%,indicating that the membrane has good antipollution performance.When the operation pressure was 0.1 MPa,the rejection of coomassie brilliant blue G250 reached 99.8% with a flux of 46.3 L m ~2 h ~1,while the Na_2 SO_4 rejection was less than 10.0%.The Cu~(2+)/CaAlg membrane was recycled after 24 h in the filtration process,and its flux and rejection rate did not decrease significantly,indicating that the hydrogel membrane has long-term application potential.The Cu~(2+)/CaAlg membrane has a wide range of applications prospect in dye desalination,fine separation and biopharmaceutical technology fields.     

反渗透过程中双壁碳纳米管通水阻盐性能的分子动力学模拟

采用分子动力学模拟方法, 探究了非常规双壁碳纳米管(DWCNT)在反渗透过程中, 不同内外管间距对管道内水分子与盐离子运动行为的影响. 本文采用0.5 mol·L^-1氯化钠水溶液模拟海水, 内管始终采用CNT(8,8)型, 并对盐水层施加恒力模拟反渗透压. 重点考察盐离子数量分布与通水情况, 计算水分子平均力势, 并分析水分子氢键寿命与偶极矩分布. 结果表明, 管间距不仅影响上述各项性质, 还会改变盐离子与水分子在碳管中的渗透特性. 模拟结果显示, 小尺寸DWCNT可以有效实现盐水分离但水通量较小, 大尺寸DWCNT的水容量较大但阻盐效率不高, 而中尺寸DWCNT (即: 管间距为0.815 nm)则具有最佳的通水阻盐性能. 本文试图从分子层面揭示了DWCNT通水阻盐机理, 并为人们设计新型海水淡化渗透膜提供理论指导.     

Preparation of thin-film-composite polyamide membranes for desalination using novel hydrophilic surface modifying macromolecules

A new concept for the preparation of thin-film-composite (TFC) reverse osmosis (RO) membrane by interfacial polymerization on porous polysulfone (PS) support using novel additives is reported. Hydrophilic surface modifying macromolecules (LSMM) were synthesized both ex situ by conventional method (cLSMM), and in situ within the organic solvent of the TFC system (iLSMM). The effects of these LSMMs on the fouling of the TFC RO membranes used in the desalination processes were studied. FTIR results indicated that both cLSMM and iLSMM were present in the active layer of the TFC membranes. SEM micrographs depicted that heterogeneity of the surface increases for TFC membranes compared to the control PS membrane, and that higher concentrations of LSMM provided smoother surface. AFM characteristic data presented that the surface roughness of the skin surface increases for TFC membranes compared to the control. The RO performance results showed that the addition of the cLSMM significantly decreased the salt rejection of the membrane and slightly reduced the flux, while in the case of the iLSMM, salt rejection was improved but the flux declined at different rates for different iLSMM concentrations. The membrane prepared by the iLSMM exhibited less flux decay over an extended operational period.     

Experimental study of desalination using direct contact membrane distillation: a new approach to flux enhancement

New membrane distillation configurations and a new membrane module were investigated to improve water desalination. The performances of three hydrophobic microporous membranes were evaluated under vacuum enhanced direct contact membrane distillation (DCMD) with a turbulent flow regime and with a feed water temperature of only 40 °C. The new configurations provide reduced temperature polarization effects due to better mixing and increased mass transport of water due to higher permeability through the membrane and due to a total pressure gradient across the membrane. Comparison with previously reported results in the literature reveals that mass transport of water vapors is substantially improved with the new approach. The performance of the new configuration was investigated with both NaCl and synthetic sea salt feed solutions. Salt rejection was greater than 99.9% in almost all cases. Salt concentrations in the feed stream had only a minor effect on water flux. The economic aspects of the enhanced DCMD process are briefly discussed and comparisons are made with the reverse osmosis (RO) process for desalination.     

Novel stand-alone PVA mixed matrix membranes conjugated with graphene oxide for highly improved reverse osmosis performance

In this research, an innovative Poly (vinyl alcohol) (PVA) reverse osmosis (RO) membrane with exceptional attributes was fabricated. Graphene Oxide (GO) nanosheets and Pluronic F-127 were infused within crosslinked PVA to fabricate thin film mixed matrix membranes. The newly synthesized membranes were evaluated in terms of several parameters like surface roughness, hydrophilicity, salt rejection, water permeability, Chlorine tolerance and anti-biofouling property, utilizing a dead-end RO filtration unit. Typical characterization techniques were used to assess the characteristics of the membranes. These include SEM, AFM, contact angle measurements and mechanical strength analysis. The conjugation of Pluronic F-127 and GO enhanced the overall performance of the membranes. The modified membranes surfaces had less roughness and higher hydrophilicity in comparison with the unmodified ones. This research showed that membranes that contained 0.08 wt% and 0.1 wt% GO exhibited superior selectivity, mechanical strength, Chlorine tolerance and anti-biofouling property. The truly significant outcome to evolve from this investigation is that improvements have been accomplished while PVA was used as a stand-alone RO layer without the use of any substrate. This study showed that crosslinking of PVA and modifying it with proper fillers overcame the common PVA downsides, primarily swelling and rupture under exceptionally high pressure.     

Effects of bisphenol monomer structure on the surface morphology and reverse osmosis (RO) performance of thin-film-composite membranes composed of polyphenyl esters

Four reverse osmosis (RO) composite membranes, in which thin-film active layers were polyphenyl esters, were prepared by interfacial polymerization of a series of bisphenol monomers and trimesoyl chloride (TMC). An atomic force microscope (AFM) was used to investigate the surface morphology and RO experiments were carried out to measure the rejection and flux characteristics of the membranes. Correlations between the inherent chemical nature of bisphenols possessing structural variations in the middle of phenyl rings and the surface morphology/RO performance of the membranes were studied. Polarity of the connectors between two phenyl rings of bisphenols played an important role in determining the surface morphology and RO performance. Nonpolar bisphenol gave a morphology of uniform, distinct nodular corrugation and a superior RO rejection but a relatively low flux, while the polar one resulted in an irregular, ambiguous nodule structure and a high flux. The size of the bisphenol connectors was also found to be important; the smaller one was more favorable for the formation of membrane with better salt rejection, while the larger one contributed to higher flux. © 1996 John Wiley & Sons, Inc.     

PEG-coated reverse osmosis membranes: Desalination properties and fouling resistance

This study focuses on the use of surface-coated reverse osmosis (RO) membranes to reduce membrane fouling in produced water purification. A series of crosslinked PEG-based hydrogels were synthesized using poly(ethylene glycol) diacrylate as the crosslinker and poly(ethylene glycol) acrylate, 2-hydroxyethyl acrylate, or acrylic acid as comonomers. The hydrogels were highly water permeable, with water permeabilities ranging from 10.0 to 17.8 (L μm)/(m² h bar). The hydrogels were applied to a commercial RO membrane (AG brackish water RO membrane from GE Water and Process Technologies). The water flux of coated membranes and a series-resistance model were used to estimate coating thickness; the coatings were approximately 2 μm thick. NaCl rejection for both uncoated and coated membranes was 99.0% or greater, and coating the membranes appeared to increase salt rejection, in contrast to predictions from the series-resistance model. Zeta potential measurements showed a small reduction in the negative charge of coated membranes relative to uncoated RO membranes. Model oil/water emulsions were used to probe membrane fouling. Emulsions were prepared with either a cationic or an anionic surfactant. Surfactant charge played a significant role in membrane fouling even in the absence of oil. A cationic surfactant, dodecyltrimethyl ammonium bromide (DTAB), caused a strong decline in water flux while an anionic surfactant, sodium dodecyl sulfate (SDS), resulted in little or no flux decline. In the presence of DTAB, the AG RO membrane water flux immediately dropped to 30% of its initial value, but in the presence of SDS, its water flux gradually decreased to 74% of its initial value after 24 h. DTAB-fouled membranes had lower salt rejection than membranes not exposed to DTAB. In contrast, SDS-fouled membranes had higher salt rejection than membranes not exposed to SDS, with rejection values increasing, in some cases, from 99.0 to 99.8% or higher. In both surfactant tests, coated membranes exhibited less flux decline than uncoated AG RO membranes. Additionally, coated membranes experienced little fouling in the presence of an oil/water emulsion prepared from DTAB and n-decane. For example, after 24 h the water flux of the AG RO membrane fell to 26% of its initial value, while the water flux of a PEGDA-coated AG RO membrane was 73% of its initial value.     

添加共试剂改善聚酰胺复合反渗透膜的性能

将N,N′-二甲基乙酰胺(DMAc)作为共试剂添加在间苯二胺水溶液中参与界面聚合反应, 以改善聚酰胺复合反渗透膜(PA-RO-x, x代表添加DMAc的质量分数)的性能. X射线光电子能谱(XPS)和衰减全反射傅里叶红外光谱(ATR-FTIR)分析表明, 随着DMAc含量的增加, 复合膜结构中交联聚酰胺含量相对于线性羧基部分有所增加; 场发射扫描电子显微镜(FE-SEM)和原子力显微镜(AFM)表征结果显示, 随着DMAc含量的增加, 膜表面的粗糙程度逐渐增大; 静态水接触角测试结果表明, 添加DMAc后, 膜的亲水性增强. 结合上述测试结果发现, 添加DMAc可以有效降低水油两相的不相溶性, 提高水相中间苯二胺向正己烷中扩散的速率, 这有助于加快间苯二胺与均苯三甲酰氯反应; 同时, 聚酰胺结构中交联酰胺含量的增加可以提供更多的氢键位点, 有助于水分子快速渗透通过复合膜而不损失截盐率; 膜表面的粗糙程度变大, 有助于提高水通量. 在2 g/L的氯化钠溶液和1.6 MPa测试压力条件下, PA-RO-5.2(DMAc添加质量分数为5.2%)的渗透通量和截盐率分别为66.1 L/(m²·h)和98.7%, 与未添加DMAc的聚酰胺复合反渗透膜相比, 通量增加115%, 截盐率仅下降0.9%.     

Exploring the characteristics,performance, and modification of Matrimid for development of thin‐film composite and thin‐film nanocomposite reverse osmosis membranes

Reverse osmosis (RO) membrane technology is widely employed to address the demands for freshwater. In this study, fabrication and performance evaluation of customized RO membranes comprised of Matrimid and polyacrylonitrile (PAN) is carried out. While exploring adoption of slip coating procedure, the effects of various modification techniques including incorporation of TiO₂ nanoparticles and polyethylene glycol (PEG) into the skin layer as well as cross‐linking were investigated. The individual and combined effects of parameters on membrane morphology, surface characteristics and performance were also examined. Despite the distinctive characteristics of involved materials, delamination‐free composite membranes were successfully formed with an intimate contact at the interface of two layers. The results also indicated that increasing concentration of Matrimid in dope solution led to increase in membrane thickness and consequently decline in water flux. In the best case, membrane prepared using 1 wt.% Matrimid in dope exhibited water flux of 0.98 LMH and NaCl rejection of 95.7%. Also, incorporation of 3 wt.% TiO₂ nanoparticles offered membranes with improved water flux of 1.37 LMH and salt rejection of 95.8%. On the other hand, water flux and salt rejection in membranes containing 5 wt.% PEG were 1.18 LMH and 96.2%, respectively. The co‐presence of both nanoparticles and PEG provided more insights about the contributing factors in tuned membranes. Modification of skin layer by cross‐linking significantly improved salt rejection at the expense of water flux. The results are scientifically interpreted and compared to the values reported in literature.     

Zeolitic imidazolate framework-8 as a reverse osmosis membrane for water desalination: insight from molecular simulation

A molecular simulation study is reported for water desalination in zeolitic imidazolate framework-8 (ZIF-8) membrane. The simulation demonstrates that water desalination occurs under external pressure, and Na(+) and Cl(-) ions cannot transport across the membrane due to the sieving effect of small apertures in ZIF-8. The flux of water permeating the membrane scales linearly with the external pressure, and exhibits an Arrhenius-type relation with temperature (activation energy of 24.4 kJ∕mol). Compared with bulk phase, water molecules in ZIF-8 membrane are less hydrogen-bonded and the lifetime of hydrogen-bonding is considerably longer, as attributed to the surface interactions and geometrical confinement. This simulation study suggests that ZIF-8 might be potentially used as a reverse osmosis membrane for water purification.     

Fabrication,characterization, and performance evaluation of polyethersulfone/TiO2 nanocomposite ultrafiltration membranes for produced water treatment

In the present work, development of neat and nanocomposite polyethersulfone membranes composed of TiO₂ nanoparticles is presented. Membranes are fabricated using nonsolvent phase inversion process with the objective of improving antifouling, hydrophilicity, and mechanical properties for real and synthetic produced water treatment. Membranes are characterized using scanning electron microscopy, Fourier‐transform infrared, contact angle, porosity measurement, compaction factor, nanoparticles stability, and mechanical strength. The performance of prepared membranes was also characterized using flux measurement and oil rejection. Fourier‐transform infrared spectra indicated that noncovalence bond formed between Ti and polyethersulfone chains. The contact angle results confirmed the improved hydrophilicity of nanocomposite membranes upon addition of TiO₂ nanoparticles owing to the strong interactions between fillers and water molecules. The increased water flux for nanocomposite membranes in comparison with neat ones can be due to coupling effects of improved surface hydrophilicity, higher porosity, and formation of macrovoids in the membrane structure. The membrane containing 7 wt% of TiO₂ nanoparticles was the best nanocomposite membrane because of its high oil rejection, water flux, antifouling properties, and mechanical stability. The pure water flux for this membrane was twice greater than that of neat membrane without any loss in oil rejection. The hydrophilicity and antifouling resistance against oil nominates developed nanocomposite membranes for real and synthetic produced water treatment applications with high performance and extended life span.     

ZIF-8吸附剂上CH4/N2的吸附分离性能与热力学性质

将沸石咪唑酯骨架结构材料应用于抽放煤层甲烷的浓缩净化研究。以三乙胺(TEA)为导向剂,ZnSO₄为金属离子源,水为溶剂,采用水热合成法进行了ZIF-8吸附剂的制备。采用XRD、物理吸附、动态吸附分离和反相气相色谱(IGC)等方法对ZIF-8的物理结构、化学稳定性、吸附分离性能和热力学性质进行了研究。结果表明,ZIF-8具有良好的化学稳定性,能够在强酸、强碱和强极性的溶剂中保持结构的稳定性;在298 K时,ZIF-8对CH₄/N₂的分离因子达到3.4,与活性炭相当,但CH₄、N₂在ZIF-8上的吸附热比在活性炭上低20%左右。     

Boron reduction performance of reverse osmosis seawater desalination process

In recent years, seawater desalination systems using reverse osmosis (RO) membranes have been constructed to settle the lack of drinking water. RO desalination membranes have high rejection for most of solutes in seawater. Japanese drinking water standards for the water quality of the permeate can be achieved except for boron. Therefore, the boron rejection needs to be considered in the design of the RO process and during the operation of the plant. Luckily, there is a simple and easy method to estimate boron concentration.In this paper, we report measured boron permeabilities and their relation to salt permeabilities using cross-linked polyamide membranes. Chemical degradation of the membranes affected these permeabilities to different degrees. Boron concentrations in the permeate were then calculated using a computer program that was based on the boron permeabilities calculated from the measured salt permeabilities. Results obtained were compared with actual data taken at a RO plant of Toray Industries, Inc., Ehime. The model data fitted the experimental result, well. It was also found that a relationship existed in the permeate between salt and boron concentrations and that the boron concentration can be obtained from measurement of the salt concentration.     

Preparation and characterization of ZIF-8 and ZIF-67 incorporated poly(vinylidene fluoride) membranes for pervaporative separation of methanol/water mixtures

Metal–organic frameworks (MOFs) are made up of metal centers and organic binders with larger surface area and distinct pore structures. Particularly significant advancement in MOF membranes has been achieved in three different directions: preparation of MOF membranes with larger surface area, improving the membrane performance by surface modification, and its usage with added features. However, its significance has not been completely known and concluded yet. MOF membranes are used in a variety of membrane-based separation like gas permeation, nanofiltration, pervaporation, membrane distillation, etc. This research aims to synthesize MOFs (ZIF-8 and ZIF-67) and MOF membranes (ZIF-8/PVDF and ZIF-67/PVDF) and used them in the pervaporative separation of the methanol/water mixture. MOFs and MOF membranes were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and thermogravimetry analysis. Methanol/water mixtures were be used to study the performance of the prepared membranes. A study on the process parameters such as temperature (40, 45, 50, and 55°C), feed pressure (4, 8, 12, and 16 psi), and feed composition (10%, 20%, 30%, and 40% of water) was carried out to examine the effect of each process parameters for pure membrane. In contrast, Taguchi screening design was used to screen the most influential process variable. The optimized conditions based on Taguchi screening method were 55°C, 12 psi, and 40 %vol of water in feed. The obtained total flux of 425 L/m²h was observed for M3 membrane. As feed temperature increased, the total flux of all three membranes was increased.     

Relationship between structure and transport in cellulose acetate desalination membranes

Several experimental techniques, including measurements of salt rejection, water flux, birefringence, and membrane opaqueness, were used to characterize the structure and performance of typical cellulose acetate desalination membranes. The results indicate that optimum salt rejection and water flux characteristics are related to the presence of molecular orientation effectively perpendicular to the membrane surface. An alignment-type flow mechanism involving water contained within the oriented structure is consistent with the observed structural and transport phenomena. The various membrane fabrication procedures apparently have significant effects on the development of molecular orientation in the thin surface layers of the membrane.     

Removal of aromatic compounds in the aqueous solution via micellar enhanced ultrafiltration: Part 1. Behavior of nonionic surfactants

The effects of nonionic surfactants having different hydrophilicity and membranes having different hydrophobicity and molecular weight cut-off on the performance of micellar-enhanced ultrafiltration (MEUF) process were examined. A homologous series of polyethyleneglycol (PEG) alkylether having different numbers of methylene groups and ethylene oxide groups was used for nonionic surfactants. Polysulfone membranes and cellulose acetate membranes having different molecular cut-off were used for hydrophobic membranes and hydrophilic membranes, respectively. The concentration of surfactant added to pure water was fixed at the value of 100 times of critical micelle concentration (CMC). The flux through polysulfone membranes decreased remarkably due to adsorption mainly caused by hydrophobic interactions between surfactant and membrane material. The decline of solution flux for cellulose acetate membranes was not as serious as that for polysulfone membranes because of hydrophilic properties of cellulose acetate membranes. The surfactant rejections for the cellulose acetate membranes increased with decreasing membrane pore size and with increasing the hydrophobicity of surfactant. On the other hand the surfactant rejections for polysulfone membranes showed totally different rejection trends with those for cellulose acetate membranes. The surfactant rejections for the polysulfone membranes depend on the strength of hydrophobic interactions between surfactant and membrane material and molecular weight of surfactants.     

Modification of polyethersulfone ultrafiltration membranes with phosphorylcholine copolymer can remarkably improve the antifouling and permeation properties

The synthesized phosphorylcholine copolymer composed of 2-methacryloyloxyethylphosphorylcholine (MPC) and n-butyl methacrylate (BMA), blended with polyethersulfone (PES), was used to fabricate antifouling ultrafiltration membranes. Water contact angle measurements confirmed that the hydrophilicity of the MPC-modified PES membranes was enhanced to certain extent. X-ray photoelectron spectroscopy (XPS) analysis verified the substantial enrichment of MPC at the surface of the MPC-modified PES membranes. The adsorption experiments indicated that the adsorption amounts of bovine serum albumin (BSA) on the MPC-modified PES membranes were dramatically decreased in comparison with the control PES membrane. Ultrafiltration experiments were carried out to investigate the effect of MPC modification on the antifouling and permeation properties of the PES membranes, it was found that the rejection ratio of BSA was decreased, the flux recovery ratio was remarkably increased, and the degree of irreversible fouling decreased from 0.46 to 0.09. In addition, the MPC-modified PES membranes could run several cycles without substantial flux loss.     

羟丙基醋酸纤维素反渗透膜

研究了羟丙基醋酸纤维素反渗透膜的制膜工艺和膜性能。实验表明,以甘油—正丙醇或磷酸为添加剂,蒸发时间30—60s,预热处理温度70℃,时间3—5min,可得到在2MPa操作压力下,氯化钠脱除率95—98％,水通量1.0～2.1ml/cm~2·h的反渗透膜。羟丙基醋酸纤维素膜具有一定的耐热性,其使用温度上限比醋酸纤维素膜至少提高了10℃以上。羟丙基醋酸纤维素的溶解性能与醋酸纤维素相似。X射线衍射和热重分析显示羟丙基醋酸纤维素具有与醋酸纤维素相似的聚集态结构。