Study of humic acid adsorption on nanofiltration membranes by contact angle measurements

Membrane fouling is a major problem, which extent depends on the respective natures of the solute and membrane material. Membrane surface characterization under different fouling conditions may help in understanding the fouling mechanism. Such characterization was performed for the case of humic substances filtered on two nanofiltration membranes, using special contact angles measurements. The measured contact angles allowed the calculation of polar and non-polar contributions to the surface energy of dry, hydrated and fouled membranes. The results reveal significant differences in the two membrane behaviours and information about the way that fouling material may be adsorbed on membrane surface.     

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     

界面聚合聚酰胺纳滤膜渗透选择性能优化的研究进展

纳滤因其分离效率高、操作压力低、环境友好等优点,在废水处理、海水淡化和工业分离纯化等众多领域有着重要的应用。界面聚合法制备的聚酰胺（PA）纳滤膜是最为常用的纳滤膜种类之一。然而界面聚合反应速度快,如何通过调控界面聚合过程,优化纳滤膜选择分离层的结构从而提高渗透选择性,以满足不同领域对纳滤膜需求仍是亟需解决的问题。本文从影响界面聚合单体扩散因素的角度出发,综述了近年来PA纳滤膜渗透选择性能优化的研究进展,包括新型PA纳滤膜、纳米材料/PA混合基质膜及超薄PA纳滤膜3个方面,探讨了选择分离层结构调控与纳滤膜渗透选择性能优化的关系,最后指出目前界面聚合制备高渗透选择性PA纳滤膜在规模化、稳定性及可控性存在的问题,并对未来界面聚合纳滤膜在微观结构和聚合过程调控方面的研究进行了展望。     

Preparation and characterization of nanofiltration composite membranes using polyacrylonitrile (PAN). II. Preparation and characterization of polyamide composite membranes

Polyamide (PA) composite membranes in which PA active layers were interconnected with support layers via the formation of ionic bonds were prepared by the interfacial polymerization of piperazine (PIP) with trimesoyl chloride (TMC) on the surfaces of microporous polyacrylonitrile (PAN) supports containing carboxylic acid groups. Formation of the ionic bonds through an acid‐base reaction between ? NH group of PIP and ? COOH of the support was studied using FTIR‐ATR spectroscopy. Variation of the surface morphologies of the composite membranes that was induced by the presence of the ionic bonds was observed with a FESEM and an AFM. Permeation tests with various feed solutions such as PEG 600, Na₂SO₄, MgSO₄, MgCl₂, and NaCl solutions were carried out to see how the characteristics of the PAN supports affected on the flux and rejection of the corresponding PA composite membranes. Chemical stabilities of the composite membranes with the ionic bonds were studied and compared with that of a conventional PA composite membrane, using alcohol solutions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2729–2736, 2001     

耐氧化芳香聚酰胺纳滤膜的研究进展

芳香聚酰胺纳滤膜不耐氧化,易被活性氯氧化降解,导致膜性能急剧下降,缩短膜的使用寿命,目前已成为制约芳香聚酰胺纳滤膜应用和发展的关键问题之一。本文综述了芳香聚酰胺纳滤膜的材料和结构,重点概述了芳香聚酰胺氯化和膜性能下降的机制,并进一步介绍了近年来耐氧化芳香聚酰胺纳滤膜的研究进展。     

Preparation and separation properties of polyamide nanofiltration membrane

Utilizing an interfacial polymerization technique for the preparation of a polymeric composite nanofiltration membrane, both high permeation flux of water and high salt rejection can be achieved. Synthesis conditions, such as concentration of monomer, reaction time, and swelling agent, significantly affected the separation performance of composite membranes. The composite polyamide membrane had a permeation rate of ～2–5 gallon/ft²/day (gfd) and a salt rejection rate of ～94–99% when 2000 ppm aqueous salt solution was fed at 200 psi and 25°C. Also, a higher performance nanofiltration membrane could be prepared by suitably swelling the support matrix in the period of polymerization. The results of various feed concentrations showed that permeate flux decreased with increasing salt concentration in the feed solution. This result may be due to concentration polarization on the surface of polyamide membranes. The separation performance of polyamide membranes showed an almost independent relationship with operation pressure until it was up to 200 psi. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1112–1118, 2002     

丙烯酸接枝聚酰胺/聚醚酰亚胺复合纳滤膜的制备

为了提高复合纳滤膜的抗污染性能,采用紫外光照接枝法将丙烯酸接枝到聚酰胺/聚醚酰亚胺(PA/PEI)复合纳滤膜的皮层上,通过引入羧基基团来增加膜表面的亲水性。考察了丙烯酸单体质量分数、辐照时间对表面接枝率和膜分离性能的影响,并对优选的膜进行了抗污染性能测试。结果表明:丙烯酸质量分数与紫外辐照时间对膜分离性能的影响规律相同,膜通量随质量分数的增加与辐照时间的延长呈现先增加后减小的趋势,而截留率则保持基本不变,当丙烯酸质量分数2%,辐照时间2 min时,膜的通量达到13.12 L/(m2·h),较接枝前的11.94 L/(m2·h)略高;在含有1 g/L牛血清蛋白(BSA)的溶液中,接枝后的膜通量下降明显低于接枝前的膜。研究表明丙烯酸接枝可以有效改善膜表面亲水性,从而有利于提高膜的抗污染性能。     

双组分无机电解质溶液的纳滤膜分离性能

纳滤膜是20世纪90年代问世的新型分离膜,具有两个显著特点：一是其截留分子量介于反渗透膜和超滤膜之间,约为2002000;另一是纳滤膜的表面分离层由聚电解质构成,一般带有负电荷,因此对无机电解质有一定的截留率．     

氨基化氧化石墨烯界面聚合制备超薄复合纳滤膜

采用氨基化氧化石墨烯（NGO）为界面聚合水相单体,制备了超薄复合纳滤膜。研究采用傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）、透射电子显微镜（TEM）、扫描电子显微镜（SEM）、原子力显微镜（AFM）表征了NGO以及复合纳滤膜的化学组成和形貌。系统考察了水相单体浓度、有机相单体浓度对于制备的超薄复合纳滤膜性能的影响。该超薄复合膜在低压（0.2 MPa）下纯水通量可达27.8 L·m^-2·h^-1,对小分子染料有较高的截留率（甲基橙截留率74.8%,橙黄钠截留率96.0%,刚果红截留率98.5%,甲基蓝截留率99%）,对于无机盐的截留率较低（Na₂SO₄截留率21.4%,MgSO₄截留率10.7%,NaCl截留率5.3%,MgCl₂截留率1.5%）,展现出优异的染料/盐分离性能。同时制备的复合纳滤膜展现了较好的长周期稳定性以及抗污染特性。     

Adsorption of perfluorinated compounds on thin‐film composite polyamide membranes

The adsorption behavior of perfluorinated compounds (PFCs), of various chain lengths and two different functional groups, on widely used thin‐film composite polyamide membranes has been investigated. Three commercially available polyamide membranes and two classes of PFCs were evaluated: Dow‐Filmtech BW30, NF90, and NF270 membranes; perfluorosulfonic and perfluoroalkanoic acid with 5, 7, 9, and 11 carbon atoms. The adsorption of PFCs on the membranes strongly depended on the active skin‐top layer material of the membranes, solution chemistry, and structure of PFCs. The piperazine based NF270 membrane showed higher adsorption of PFCs compared to BW30 and NF90 membranes (FT‐30 type membranes). The BW30 membrane, which has a coating layer of aliphatic carbons and hydroxyl groups on the surface of the polyamide substrate, had less interaction with PFCs than the NF90 polyamide membrane had. The adsorption of PFCs increased with increasing ionic strength, decreasing pH, and in divalent ion solutions. PFCs with longer chain lengths and more hydrophobic functional groups showed more attractive interactions with thin‐film composite membranes and, thus, greater adsorption on the membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Characteristics of the nanofiltration composite membranes based on PVA and sodium alginate

Chemically stable nanofiltration (NF) composite membranes based on poly(vinyl alcohol) (PVA) and sodium alginate (SA) (hereafter, these membranes are called PVA/SA composite membranes) were prepared by coating microporous polysulfone (PSF) supports with dilute PVA/SA blend solutions. The PSF supports were pretreated with small monomeric compounds to reduce their pore size and to improve their hydrophilicity before coating with the PVA/SA blend solutions. The concentration of the PVA/SA blend solutions ranged from 0.1 to 0.3 wt %. The membranes prepared in this study were characterized with various methods such as SEM, FTIR, permeation tests, and z‐potential measurements. Especially, chemical stabilities of the membranes were tested, using three aqueous solutions with different pHs such as a HCl solution (pH 1), a K₂CO₃ solution (pH 12.5), and a NaOH solution (pH 13). Their chemical stabilities were compared with that of a polyamide (PA) composite membrane prepared from piperazine (PIP) and trimesoyl chloride (TMC). In this study, it was found that the PVA/SA composite membranes prepared showed not only good chemical stabilities but also good permeation performances in the range from pH 1 to 13. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2471–2479, 2001     

Preparation,characterization, and application of thin film composite nanofiltration membranes

The active aromatic polyamide layers of thin film composite nanofiltration (NF‐TFC) membranes were prepared via interfacial polymerization (IP) from three different types of polyamine: p‐phenylenediamine (PPD), m‐phenylenediamine (MPD), or piperazine (PRP), and trimesoyl chloride (TMC) on polysulfone/sulfonated polysulfone (PSf/SPSf) alloy substrates. Chemical components, cross section structures, and thermal properties of the polyamide active layers and the bulk membranes, characterized by Fourier transfer IR spectroscopy and attenuated total reflection IR spectroscopy, scanning electron microscopy, and differential scanning calorimetry and thermogravimetry, respectively, revealed an interpenetrating layer between the polyamide active layer and the substrate. A ridge–valley structural active layer was formed on the PSf/SPSf substrate for the NF‐TFC membrane with a thick polyacrylamide (PA) layer. Compared with the NF‐TFC membranes on PSf substrates, those on PSf/SPSf alloy substrates had a higher permeability without losing the selectivity by introducing the hydrophilic SPSf into the hydrophobic PSf substrates. The binding between the modified substrate and the active PA layer was also improved. Good separation performances using these NF‐TFC membranes were obtained in the polyvalent ion separation, the ground water softening, and the treatment of wastewater from adipic acid plants in a wide pH range. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1251–1261, 2005     

Simultaneous removal of humic acid and heavy metal from aqueous solutions using charged ultrafiltration membranes

Lab-made negatively charged ultrafiltration (UF) membranes were used for simultaneous removal of humic acid (HA) and heavy metals from water. Effects of the HA/metal ratio, solution pH and ionic strength on rejection coefficients of HA and metals were investigated. The results showed that the rejection coefficients of both HA and metals increase with the increase of pH and the HA/metal ratio, and the decrease of ionic strength. This study indicated that charged UF could be an effective method for the simultaneous removal of HA and heavy metal harnessing the principle of complexation UF and electrostatic repulsion between the membrane and the HA–M complex of the same charges.     

AEPPS对超支化聚酰胺纳滤膜性能的影响

通过与均苯三甲酰氯(TMC)的界面聚合反应,将N-氨乙基哌嗪丙基磺酸盐(AEPPS)两性离子化合物引入超支化聚酰胺纳滤膜中以改善膜性能。着重考察AEPPS的质量分数对膜性能的影响。结果表明,与以往报道该物质与哌嗪或间苯二胺等小分子混合使用效果不同,当AEPPS与端氨基超支化聚酰胺混合作为水相反应物时,随着AEPPS质量分数的增加,膜的脱盐顺序发生变化,由Na₂SO₄>Mg SO₄>Mg Cl₂>Na Cl逐渐变为Mg SO₄>Mg Cl₂≈Na₂SO₄>Na Cl,最后是Mg SO₄>Na₂SO₄>Mg Cl₂>Na Cl。脱盐率先增大后降低,膜通量呈现相反趋势。AEPPS的引入增强了膜的亲水性及抗蛋白质吸附能力。当水溶液中AEPPS质量分数为0.6%时,制备的纳滤膜NF06在牛...     

Factors affecting the interfacial polymerization of polyamide active layers for the formation of polyamide composite membranes

Polyamide (PA) composite membranes were prepared by interfacial polymerization with piperazine, m‐phenylene diamine, and trimesoyl chloride as monomers and polysulfone ultrafiltration membranes as supports. Factors affecting the performances of the composite membranes by changing the characteristics of the PA active layers were studied. First, the monomer compositions were varied, and organic solvents (benzene and 1,2‐dichloroethane) with better solubility for PA than hexane were used for the interfacial polymerization. As chemical additives capable of changing the property of the interface formed between water and organic phases, n‐propanol and i‐propanol were used, and phase‐transfer catalysts such as triethyl benzyl ammonium bromide were used to improve the polymerization efficiency of the PA active layers. The characteristics of the PA composite membranes prepared, including their permeation properties and morphology, were carefully studied with various analytical methods, such as field emission scanning microscopy, atomic force microscopy, differential scanning calorimetry, and permeation testing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2781–2787, 2002     

Cross-linked PAN-based thin-film composite membranes for non-aqueous nanofiltration

A new approach on the development of cross-linked PAN based thin film composite (TFC) membranes for non-aqueous application is presented in this work. Polypropylene backed neat PAN membranes fabricated by phase inversion process were cross-linked with hydrazine to get excellent solvent stability toward dimethylformamide (DMF). By interfacial polymerization a selective polyamide active layer was coated over the cross-linked PAN using N,N′-diamino piperazine (DAP) and trimesoyl chloride (TMC) as monomers. Permeation and molecular weight cut off (MWCO) experiments using various dyes were done to evaluate the performance of the membranes. Membranes developed by such method show excellent solvent stability toward DMF with a permeance of 1.7 L/m² h bar and a molecular weight cut-off of less than 600 Da.     

Novel thin-film composite nanofiltration membranes fabricated via the incorporation of ssDNA for highly efficient desalination

In this work, the biomacromolecule, single-stranded deoxyribonucleic acid (ssDNA) was innovatively incorporated into the polyamide layer to tailor the permeate flux and antifouling performance of the nanofiltration (NF) membranes. With active amines groups, the ssDNA was as the aqueous phase monomers along with piperazine (PIP), and reacted with trimesoyl chloride on polyethersulfone substrate to fabricate thin-film composite (TFC) NF membranes. The NF membrane prepared under optimal ratio of ssDNA/PIP had a pure water permeability of 75.8 L m⁻² h⁻¹ (improved 58% compared to PIP NF membrane) and Na₂SO₄ rejection of 98.0% at 6.0 bar. The rejections for different inorganic salts were the order: Na₂SO₄ (98.0%) > MgSO₄ (89.2%) > MgCl₂ (72.8%) > NaCl (23.0%). Furthermore, the TFC NF membranes showed good antifouling performance in long-term running with 300 ppm bovine serum albumin and humic acid solution. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 47102.     

氧化石墨烯/碱式硫酸铝掺杂聚醚砜/聚酰胺复合纳滤膜的制备及其性能

先由氧化石墨烯（GO）、硫酸铝和尿素通过水热法制得氧化石墨烯/碱式硫酸铝（GO-BAS）复合物,继与哌嗪（PIP）溶液共混作为水相;均苯三甲酰氯（TMC）溶于正己烷作为有机相;采用界面聚合法使两相单体在聚醚砜（PES）基膜表面形成聚酰胺（PA）功能层,制得氧化石墨烯/碱式硫酸铝复合物掺杂的聚醚砜/聚酰胺（PES-PA-GO-BAS）复合纳滤平板膜,并在较低的工作压力（0.3 MPa）下对其进行性能研究。其对无机盐溶液的截留率依次为：Na₂SO₄（91.08%） > MgSO₄（83.42%） > MgCl₂（68.97%） > NaCl（17.62%）;纯水通量可达24.19 L·m^-2·h^-1,较之聚酰胺纳滤膜提高了近60%,且具备良好的稳定性和耐碱性。     

新型复合纳滤膜研究进展

纳滤膜因操作压力低、通量高、具有分离选择性以及运行成本较低等优势引起越来越多的关注,目前已在苦咸水脱盐、污水治理和海水淡化等领域发挥着重要作用。界面聚合作为常见的制备聚酰胺纳滤膜的方法,其聚合反应进程的调控可以有效地调节纳滤膜的微观结构,进而对其分离性能产生重要影响。本文从复合纳滤膜的结构入手,总结了当前常用的提升纳滤膜性能的改性方法,包括优化分离选择层、构建中间层、调整底膜结构三个方面,讨论了界面聚合过程反应单体、添加剂种类、制备条件等对分离层结构和分离性能的影响,并分析了底膜的孔径、孔隙率、亲疏水性等理化性质对复合膜性能的影响以及不同类型中间层的优缺点。在此基础上,总结了当前业界内亟待解决的问题,并对纳滤膜的未来发展趋势进行了展望。     

陶瓷纳滤膜制备与应用研究进展

陶瓷纳滤膜以其优良的热稳定性、化学稳定性和机械强度等特性,在涉及高温、酸碱、有机溶剂等苛刻环境的过程工业领域具有广阔的应用前景。因此,陶瓷纳滤膜材料的制备研究已引起众多科研工作者的关注。本文综述了陶瓷纳滤膜在制备及应用方面的研究进展,着重介绍了溶胶-凝胶法、化学气相沉积法、原子层沉积法及表面接枝等陶瓷纳滤膜制备方法。溶胶-凝胶法反应温度低、操作过程相对简单且精确可控,是目前国内外陶瓷纳滤膜制备的常用方法;化学气相沉积法及原子层沉积法则需借助气相化学反应在多孔基底表面进行材料沉积,从而修复缺陷,减小平均孔经;表面接枝技术可改变陶瓷膜表面亲疏水性,同时将陶瓷基膜孔径减小至纳滤范围。此外简单介绍了陶瓷纳滤膜的应用,并对未来陶瓷纳滤膜研究方向提出了建议,指出陶瓷纳滤膜微结构参数与分离性能之间的关系建立,以及探讨陶瓷纳滤膜在溶剂体系中的分离机理将成为今后一段时间内的研究热点。