Influence of Physicochemical Parameters of Organic Solutes on the Retention and Flux in a Nanofiltration Process

A comparative study of several organic compounds (atrazine, aniline and phenol, and their derivatives, 4‐chlorophenol, 4‐nitrophenol and 4‐nitroaniline) and their removal from aqueous solutions by nanofiltration using an NF‐97 polyamide membrane is presented. The aim was to ascertain any correlation between the physicochemical parameters of the different compounds and the characteristic parameters of the nanofiltration system (permeate flux and rejection coefficient), in order to understand the behavior of the nanofiltration membrane separation processes and any relevant variables. In a previous work, the rejection coefficients and permeate flux values for phenol, 4‐chlorophenol, aniline, and atrazine were obtained. These values were used together with the new ones presented for 4‐nitroaniline and 4‐nitrophenol.     

氯化聚氯乙烯复合纳滤膜的制备及其在模拟RB5染料废水处理中的应用

以氯化聚氯乙烯（CPVC）超滤膜为基膜,采用单宁酸（TA）和哌嗪（PIP）在CPVC膜表面共沉积后与交联剂均苯三甲酰氯（TMC）进行界面聚合得到PA/TA/CPVC复合纳滤膜,采用扫描电镜（SEM）、原子力显微镜（AFM）、红外光谱及接触角对PA/TA/CPVC复合纳滤膜进行了表征,并探讨了干燥时间、TA/PIP浓度比、TA+PIP总浓度、TMC浓度对PA/TA/CPVC复合纳滤膜微观结构与性能的影响。结果表明,TA/PIP浓度比最佳为7/3,TA/PIP层的最佳干燥时间为20min,PA/TA/CPVC复合纳滤膜的纯水通量随着TA+PIP总浓度的增加和TMC浓度的增加而减少,对PEG1000的截留率均在90%以上。PA/TA/CPVC复合纳滤膜纯水通量最大值为4.5L/(m² · h · bar),此时PEG1000的截留率达到95.8%。对模拟RB5染料废水的最大通量为4.3L/(m² · h · bar),此时RB5的截留率为95.4%,对模拟RB5染料废水的稳定性较好。     

Comparative impact of SiO2 and TiO2 nanofillers on the performance of thin-film nanocomposite membranes

Nanoparticle (NP) additions can substantially improve the performance of reverse osmosis and nanofiltration polyamide (PA) membranes. However, the relative impacts of leading additives are poorly understood. In this study, we compare the effects of TiO₂ and SiO₂ NPs as nanofillers in PA membranes with respect to permeate flux and the rejection of organic matter (OM) and salts. Thin-film nanocomposite (TFN) PA membranes were fabricated using similarly sized TiO₂ 15 nm and SiO₂ (10 – 20 nm) NPs, introduced at four different NP concentrations (0.01, 0.05, 0.2, and 0.5% w/v). Compared with PA membranes fabricated without NPs, membranes fabricated with nanofillers improved membranes hydrophilicity, membrane porosity, and consequently the permeability. Permeability was increased by 24 and 58% with the addition of TiO₂ and SiO₂ , respectively. Rejection performance and fouling behavior of the membranes were examined with salt (MgSO₄ and NaCl ) and OM (humic acid [HA] and tannic acid [TA]). The addition of TiO₂ and SiO₂ nanofillers to the PA membranes improved the permeability of these membranes and also increased the rejection of MgSO₄ , especially for TiO₂ membranes. The addition of TiO₂ and SiO₂ to the membranes exhibited a higher flux and lower flux decline ratio than the control membrane in OM solution filtration. TFN membranes' HA and TA rejections were at least 77 and 71%, respectively. The surface change properties of NPs appear to play a dominant role in determining their effects as nanofillers in the composite membrane matrix through a balance of changes produced in membrane pore size and membrane hydrophilicity.     

Effect of the drying temperature on sulfonated polyether sulfone nanofiltration membranes prepared by a coating method

This study reports on the preparation of a novel sulfonated polyether sulfone nanofiltration membrane via a manual coating method. The as-prepared membrane was modified by changing the drying temperature and utilizing additives. As the drying temperature was increased, the rejection performance of the as-prepared nanofiltration membrane increased, while flux decreased. The nanofiltration membrane dried at 40°C had relatively high permeation flux and good rejection performance for divalent ions and dyes; therefore, it is suitable for dye wastewater treatment. The nanofiltration membrane dried at 50°C had relatively low permeation flux and relatively good rejection performance for inorganic salts. The pore size of the skin layer was reduced as the drying temperature was increased. The average diameters of the as-prepared nanofiltration membranes dried at 40 and 50°C were 5.08 and 1.51 nm, respectively. Due to excellent hydrophilicity and relatively low roughness, the as-prepared nanofiltration membranes dried at 40 and 50°C had superior antipollution characteristics.     

Second modification of a polyamide membrane surface

The aim of this study was to develop the water flux and antifouling properties of a polyamide (PA) nanofiltration membrane. A nascent PA membrane was prepared with an interfacial polymerization technique and modified with 2,5‐diaminobenzene sulfonic acid (2,5‐DABSA) as a second modification. The effects of the 2,5‐DABSA monomer concentration and the modification time on the membrane performance were investigated. The chemical structure, morphology, roughness, hydrophilicity, molecular weight cutoff, and antifouling properties of the membranes were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force spectroscopy, contact angle measurement, poly(ethylene glycol) tracers, and cetyl trimethyl ammonium bromide filtration, respectively. The PA membrane with optimized performance was shown to have a greater than 44% higher water permeate flux with a change in the salt rejection in the order RNa₂SO₄ > RCaCl₂ > RNaCl to RNa₂SO₄ > RNaCl > RCaCl₂. The improvement of the hydrophilicity led to excellent antifouling properties in the new PA membranes and illustrated a promising and simple method for the fabrication of high‐performance PA membranes. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43583.     

添加剂对聚砜膜结构和性能的影响

通过浸没沉淀相转化法制备聚砜超滤膜,分别以高分子聚乙烯基吡咯烷酮（PVP-K30,PVP-K90）、聚乙二醇（PEG-6000,PEG-20000）和小分子氯化锌（ZnCl2）、丙酸（AS）6种物质作为制备聚砜超滤膜的添加剂,含量均为10%。并对聚砜超滤膜的断面结构、纯水通量、牛血清蛋白（BSA）截留率、孔隙率及平衡水含量等5项性能进行了测试及表征。由断面结构可以看出,PVP-K90作为添加剂时,制得膜的断面完全为海绵状结构,其它添加剂制得膜断面中均有指状孔结构;PVP-K30作为添加剂时制得膜的纯水通量最大;丙酸作为添加剂制得膜的BSA截留率最高;聚乙烯基吡咯烷酮（PVP）和聚乙二醇（PEG）制得膜的平衡水含量及总孔隙率均较高,但闭孔也较多。     

纳滤膜材料研究进展

简单阐述了纳滤膜的特点与应用,综述了乙酸纤维类、芳香族聚酰胺类等常用有机高分子纳滤膜材料,天然高分子、聚电解质等新型有机高分子纳滤膜材料,无机纳滤膜材料以及无机-有机杂化复合纳滤膜材料的研究进展。分别列举了相应膜材料的典型膜,并从高通量、抗污染、耐有机溶剂与耐氯性等多角度对相应膜材料的结构特性、化学特性、膜制备技术与应用特点进行了对比分析与总结,最后对纳滤膜材料的发展趋势与应用前景作了预测与展望,指出特种高性能纳滤膜材料的开发与微观结构的调控和基于不同纳滤膜材料的结构与功能设计将成为今后一段时间内的研究热点。     

Molecularly imprinted organic solvent nanofiltration membranes – Revealing molecular recognition and solute rejection behaviour

A new class of organic solvent nanofiltration (OSN) membranes featuring molecular recognition sites has been fabricated by a phase inversion molecular imprinting technique. Polybenzimidazole (PBI) was employed as a functional polymer for molecular imprinting for the first time. Apart from acting as a functional polymer, PBI exhibits excellent chemical and solvent stability and can be used as a nanofiltration membrane, acting both as shape-specific adsorbent and size-exclusion membrane. The molecularly imprinted organic solvent nanofiltration (MI-OSN) membranes fabricated in this study showed both nanofiltration membrane performance, and excellent molecular recognition ability. The model system comprised roxithromycin pharmaceutical, 2-aminopyrimidine building block and N,N-dimethylaminopyridine catalyst, which are retained, adsorbed and permeated through the MI-OSN membrane, respectively. The effect of both dope solution concentration and applied pressure on the molecular recognition behaviour of MI-OSN membranes has been investigated by employing Sips and Freundlich adsorption isotherms, as well as examining the physical morphology of the membranes. The rate of adsorption was investigated, revealing that the adsorption follows second-order kinetics and is not limited by diffusion. The imprinted membrane exhibited fourfold higher flux whilst maintaining the same rejection performance in comparison to the control membrane. It is shown that increasing the transmembrane pressure across the MI-OSN membrane irreversibly suppresses the molecular recognition whilst maintaining the rejection and flux performance.     

Preparation and characterization of polyzwitterionic hydrogel coated polyamide-based mixed matrix membrane for heavy metal ions removal

A novel polyzwitterionic hydrogel coated mixed matrix membrane (MMM) was successfully prepared, characterized and used for Cu²⁺, Mn²⁺, and Pb²⁺ heavy metal ions removal from water. Hydrophilic and porous covalent organic framework (COF) nanoparticles (NP) as filler were synthesized from melamine and terephthalaldehyde, and then incorporated into polyamide (PA) thin film composite (TFC) membrane. The hydrogel coating was applied by using a tailored cross-linkable polymer system in combination with concentration polarization enabled cross-linking. The effects of COF NP loading into PA layer and polyzwitterionic hydrogel coating on the membrane morphology and separation performance were studied using different analyses. The MMM prepared with a COF NP loading of 0.02 wt/wt% in the hexane dispersion used for NP deposition during PA layer formation (leading to 0.42 g/m²) exhibited an increased pure water permeability of around 200% compared with the neat PA TFC membrane while the Mn²⁺ ion rejection maintained above 98%. Scanning electron microscopy surface images and zeta potential profiles showed that the hydrogel was successfully deposited on the membrane surface. Furthermore, the hydrogel coating could decrease net surface charge of membranes but did not significantly influence the heavy metal ions rejections under nanofiltration conditions. The results of filtration experiment with protein solution indicated that the hydrogel coated membranes exhibited superior antifouling property, as shown by higher flux recovery ratio after washing with water, compared with neat PA TFC membrane and not coated MMM, respectively.     

Membrane Concentration and Separation of L-Aspartic Acid and L-Phenylalanine Derivatives in Organic Solvents

Abstract

The concentration and separation of the amino acids N-benzyloxycarbonyl L-aspartic acid and L-phenylalanine methyl ester hydrochloride in organic solvents have been investigated using reverse osmosis membranes of two types of cellulose acetate, a nanofiltration membrane of polyamide-polyphenylene sulfone (PA-PPSO) composite and a gas separation membrane of polyimide composite in a stirred batch cell. The organic solvents used included primary, secondary, and tertiary alcohols, an ester, and a ketone. There were significant variations in permeate flux, solute rejection, and membrane stability. Usually the rejection of both amino acids was similar; however, certain membrane-solvent combinations gave significantly different levels of rejection. The highest rejection of amino acids (～0.94) at the lowest pressure of 0.5 MPa was obtained with the PA-PPSO membrane using methanol as a solvent. The cellulose acetate membranes gave reasonable rejection and fluxes but the membrane stability was very poor. The performance of the polyimide composite membrane was good with ethanol but poor with other solvents. The PA-PPSO membrane with methanol as solvent appeared the most promising combination, and the separation performance according to concentration polarization was discussed.

     

耐溶剂复合纳滤膜的研究进展

耐溶剂纳滤是一种新型的膜分离技术,用于有机混合物的分离。商品耐溶剂纳滤膜大多是采用相转化法制备的整体皮层非对称膜,膜皮层较厚,通量较低。耐溶剂复合纳滤膜由基膜和分离层组成,具有薄皮层、高溶剂通量和高溶质截留率的优点。耐溶剂复合纳滤膜的制备与改性也因此成为近年来的研究热点。本文从界面聚合、表面涂覆、层层自组装、原位生长、有机-无机杂化和表面改性六个方面介绍耐溶剂复合纳滤膜的研究进展,最后对其发展前景进行展望。     

有机溶剂纳滤膜的润湿性对渗透和分离性能的影响

有机溶剂纳滤是一种绿色、高效、节能的新型膜分离技术,在回收和处理有机溶剂中具有广泛的应用前景。本文采用浸渍法分别将聚合物聚二甲基硅氧烷（PDMS）、嵌段聚醚酰胺（PEBAX2533）和聚乙烯醇（PVA）与聚砜（PS）超滤基膜复合,制备了3种不同润湿性的聚合物耐溶剂纳滤膜,研究了PDMS/PS、PEBAX/PS和PVA/PS复合膜对甲醇、乙醇、异丙醇、正己烷、正庚烷的渗透性能,考察了3种聚合物膜对伊文思蓝/甲醇溶液的有机溶剂纳滤性能。结果表明,有机溶剂在不同润湿性复合膜的渗透和传递性能与溶剂本身的溶度参数、分子量、黏度和极性等有很密切的相关性,溶剂的分子量、黏度、分子动力学直径越小,在同一极性复合膜中渗透通量越大;对伊文思蓝/甲醇溶液的有机溶剂纳滤分离表明,PDMS/PS和PEBAX/PS复合膜的截留率均可达90%以上,通量分别为 58.0L/(m²·h·MPa)和72.2L/(m²·h·MPa);PVA/PS复合膜的截留率为85.1%左右,通量为57.5L/(m²·h·MPa)。     

Nanofiltration of Hormone Mimicking Trace Organic Contaminants

Abstract

The removal mechanisms of three hormone mimicking organic compounds by nanofiltration (NF) membranes have been examined. Two NF membranes having different pore sizes were used in laboratory‐scale nanofiltration experiments with feed solutions spiked with a hormone mimicking compound—nonylphenol, tert‐butylphenol, or bisphenol A. Retention of the compounds was determined at various solution chemistries, namely aqueous solution pH, ionic strength, and presence of natural organic matter. The nanofiltration behavior of the selected hormone mimicking compounds appears similar to that of natural hormones as reported in our previous work. While the solution pH can dramatically influence the retention of hormone mimicking compounds by a loose NF membrane, ionic strength does not affect the nanofiltration of such contaminants. However, in the presence of natural organic matter in the feed solution, ionic strength appears to play a significant role in solute‐solute and solute‐membrane interactions, resulting in increased retention due to partitioning of the hormone mimicking compounds onto organic matter at a higher ionic strength.     

腐殖酸共存条件下NF90纳滤膜去除水中邻苯二甲酸二丁酯

水中共存有机物会对纳滤产生影响,以邻苯二甲酸二丁酯(DBP)为对象,研究了NF90膜对纯水、模拟水和河水中DBP的去除效果。DBP的初始质量浓度为100μg/L。结果表明,NF90膜能实现对微量DBP的有效去除,截留率高达90%以上;在模拟水中,腐殖酸共存时,会引起膜通量的下降和截留率的上升,pH为7时,截留率最高,其他无机离子(K+、Ca2+)的加入,会减小膜通量增大截留率,其中,Ca2+的影响尤为明显;河水中的无机物和有机物成分复杂,膜通量会进一步减小,截留率进一步提高;纳滤初期,吸附会影响截留率,6 h后吸附达到饱和,稳定运行96 h后,膜污染会引起膜通量和截留率的下降。     

Preparation and characterization of polyamide nanofiltration composite membranes with TiO2 layers chemically connected to the membrane surface

A polyamide (PA) nanofiltration (NF) composite membrane with TiO₂ layers was designed and prepared, in which the TiO₂ layers were chemically linked to the crosslinked polyamide layers of the membrane. In this study, TiO₂, one of the well known photo‐catalysts effectively degrading organics with UV light, was introduced to the PA NF membrane by using 3‐aminopropyltrimethoxysilane (APTMOS), titanium (IV) isopropoxide (TIP) to improve its antifouling property. In particular, for this membrane, SiO₂ layers were formed between the TiO₂ layer and the crosslinked polyamide layer of the membrane to protect the organic parts of the membrane from the TiO₂ catalyzed UV degradation. The prepared membrane with TiO₂ layers was then characterized using several analytical methods: scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS), x‐ray diffraction (XRD) and permeation tests. It was found that the prepared membrane was stable; especially the TiO₂ layer of the membrane was found to be stable after several times of use for permeation test. The membrane showed a typical NF property, despite of the presence of the TiO₂ layer. From long time tests with or without UV light, it was found that there was good antifouling effect on the membrane by the TiO₂ layer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

抗污染膜在电镀废水回用中的应用

用抗污染超滤膜聚偏氟乙烯(PVDF)合金膜、高压纳滤膜(聚芳香酰胺膜)处理含Cr6+,Ni2+,Cu2+重金属离子的电镀废水.抗污染PVDF合金超滤膜在经过三次电镀废水处理后,膜通量由4.2 L/h降为3.6 L/h,透过液的透光率大于96.3%,可去除大部分有机物.超滤透过液经过纳滤处理后,纳滤透过量由1.8 L/h降低为1.7 L/h,并且在1.5 h后基本保持不变,对Cr6+,Ni2+,Cu2+的去除率达97%以上.电镀废水经抗污染超滤膜-高压纳滤组合工艺处理,可达电镀清洗水标准,回用率达到85%.     

Solvent and pH resistance of surface crosslinked chitosan/poly(acrylonitrile) composite nanofiltration membranes

The resistance of novel surface crosslinked Chitosan/poly(acrylonitrile) (PAN) composite nanofiltration (NF) membranes to pH and organic solvents was studied with respect to the effects of crosslinking parameters, namely, glutaraldehyde concentration and crosslinking time. The pH resistance was determined by permeation of aqueous acidic (pH 2.5) and basic (pH 11) solutions as well as swelling studies in the pH range of 2.5–11. The solvent resistance was determined by swelling, immersion, and permeation studies with several industrially important organic solvents, namely methanol, ethanol, iso‐propanol, methyl ethyl ketone, ethyl acetate and hexane. It was observed that the crosslinked composite membranes maintain the permeate fluxes for test solvents for 2 h of continuous operation without any significant change in flux. SEM studies on membrane samples after immersion as well as permeation with the above‐mentioned solvents indicated that the membrane morphology was maintained. The results are explained in terms of solvent–membrane polar and hydrophobic interactions, using solubility parameters of membrane and solvents and dielectric constants of solvents. Pure water flux and polyethylene glycol transmission data indicated that at pH 2.5 and 11, the membrane stability increased with increasing glutaraldehyde concentration and was much better at pH 11 than at pH 2.5. All surface crosslinked membranes showed reduced swelling between pH 4–10. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1782–1793, 2000     

Preparation and properties of hollow fibre nanofiltration membrane with continuous coffee-ring structure

Polyamide(PA)hollow fibre composite nanofiltration(NF)membranes with a coffee-ring structure and beneficial properties were prepared by adding graphene oxide(GO)into the interfacial polymerization process.The presentation of the coffee-ring structure was attributed to the heterogeneous,finely dispersed multiphase reaction system and the“coffee-stain”effect of the GO solution.When the piperazine concentration was 0.4 wt-%,the trimesoyl chloride concentration was 0.3 wt-%,and the GO concentration was 0.025 wt-%,the prepared NF membranes showed the best separation properties.The permeate flux was 76 L·m^?2·h^?1,and the rejection rate for MgSO4 was 98.6%at 0.4 MPa.Scanning electron microscopy,atomic force microscopy,and attenuated total reflectance-Fourier transform infrared spectroscopy were used to characterize the chemical structure and morphology of the PA/GO NF membrane.The results showed that GO was successfully entrapped into the PA functional layer.Under neutral operating conditions,the PA/GO membrane showed typical negatively charged NF membrane separation characteristics,and the rejection rate decreased in the order of Na2SO₄>MgSO₄>MgCl₂>NaCl.The PA/GO NF membrane showed better antifouling performance than the PA membrane.     

Surface modification of polyamide nanofiltration membrane by grafting zwitterionic polymers to improve the antifouling property

A simple two‐step surface modification method of polyamide nanofiltration membrane, involving the activation of amide groups by formaldehyde and the subsequent cerium [Ce (IV)]‐induced graft polymerization of zwitterionic 3‐(methacryloylamino) propyl‐dimethyl‐(3‐sulfopropyl) ammonium hydroxide) (MPDSAH) monomers, was employed to improve membrane antifouling property. The membranes before and after modification were characterized by attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR), scanning electron microscopy, and atomic force microscopy. The changes in both surface chemical composition and morphology of membranes confirmed the successful graft polymerizations of MPDSAH onto polyamide nanofiltration membrane. The static water contact angle measurements showed that surface hydrophilicity of the modified membranes was significantly enhanced. As the MPDSAH concentration increased, the water flux of grafted membrane decreased gradually, while salt rejection increased slightly. The fouling experiments with bovine serum albumin solution demonstrated that modified membranes exhibited better resistance to protein fouling. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41144.     

Investigation on the enhancement of solvent-resistant nanofiltration membrane performance utilizing PDA-UiO-66@CNT as an interlayer

With the growing complexity of separation systems, the application of thin film composite nanofiltration (TFN) membranes in organic solvent separation faces numerous challenges. To augment its solvent stability, an in-situ constructed dopamine hydrogel doped with UiO-66@CNT was developed as an intermediate layer on a polyetherimide (PEI) ultrafiltration membrane. Subsequent interfacial polymerization on this interlayer led to the formation of a solvent-resistant nanofiltration membrane with a vast covalent bond structure, large specific surface area, and enhanced hydrophilicity. Our findings revealed that when the CNT loading in the UiO-66@CNT composite nanoparticles was 2 wt%, the TFN-U₂C₂ membrane exhibited a maximum pure water flux of 126.32 L/(m²·h) and a methanol flux of 45.45 L/(m²·h). The rejection rates for Congo red aqueous and methanol solutions were 96.88% and 92.14%, respectively. The membrane also demonstrated commendable anti-fouling properties. Remarkably, even after 48 h of immersion in various organic solvents, the membrane retained its morphology and separation efficiency. Compared to the TFN-U₂ membrane without CNT addition, the enhancement in separation performance was considerably significant. Hence, this membrane has significant potential for application in treatment of wastewater containing organic solvents and is promising in related fields.