聚酰胺薄层复合膜的界面聚合制备过程调控研究进展

界面聚合法制备的聚酰胺薄层复合膜凭借着渗透通量以及分离选择性高、化学稳定性佳等优点在水处理等领域有着广泛应用。聚酰胺分离层的物理结构和化学性质决定着复合膜的分离性能,通过调控界面聚合过程来优化聚酰胺层的理化性质可提高复合膜的分离性能。本文聚焦聚酰胺分离层性质与复合膜性能之间的关系,从基膜改性、调控单体反应过程、聚酰胺层后处理三个方面综述了近年来调控界面聚合制膜过程的研究进展。通过分析单体传质对界面聚合反应的影响以及膜结构与性能间的构-效关系,总结了界面聚合制备聚酰胺复合膜的调控机理和方法,为进一步提升聚酰胺复合膜的分离性能提供理论依据和发展方向。     

二次界面聚合法制备聚酰胺-脲-酰亚胺反渗透复合膜

本论文采用二次界面聚合法制备得到一种新型的聚酰胺-脲-酰亚胺反渗透复合膜。先将关键功能单体5-异氰酸酯-异酞酰氯（ICIC）与4-甲基-间苯二胺（MMPD）经单面界面聚合形成初生态的基膜,之后将关键功能单体N,N’-二甲基间苯二胺（DMMPD）与初生态基膜上残留的ICIC及未反应完的酰氯基团（-COCl）进行二次界面聚合,再经热处理、水漂洗制得一种新型的聚酰胺-脲-酰亚胺（MMPD-ICIC-DMMPD）反渗透复合膜。采用傅立叶衰减全反射红外光谱（ATR-FTIR）和X射线光电子能谱分析了膜活性分离层的化学结构,利用扫描电镜（SEM）和原子力显微镜（AFM）观察了所成膜的表面形态,同时测试了膜的耐氯性能,并以单次聚合聚酰胺-脲（MMPD-ICIC）膜作对比。结果表明：采用二次界面聚合法在功能化基膜MMPD-ICIC上引入一超薄ICIC-DMMPD层,使得所成二次聚合膜MMPD-ICIC-DMMPD的活性分离层相对稍厚,表面更光滑,且亲水性和耐氯性能更好。     

正交实验法优化制备复合荷电镶嵌膜

以聚醚砜为基膜,以聚环氧氟丙烷胺及2,5-二胺基苯磺酸混合水溶液(无机相)与三酰氯的正己烷溶液(有机相)通过界面聚合反应,制备了一种新型的复合荷电镶嵌膜.采用正交设计实验方法,研究了界面聚合条件如界面聚合单体的浓度及界面聚合反应时间对膜性能的影响.结果表明:三酰氯的浓度对膜性能的影响最为显著,其次是界面聚合时间,而聚环氧氟丙烷胺的浓度对膜性能的影响最小.优化后所制备的复合膜对盐类的截留率较低(均低于40%).膜能截留低相对分子质量有机物而透过盐,说明该膜可用于盐类与有机物的分离.     

界面聚合在渗透汽化膜分离领域的应用进展

蒸馏、萃取等传统分离方法能耗高,污染环境,而渗透汽化由于低能耗、高效、环保等优势,为共沸物、近沸点混合物的分离提供了新的思路,但渗透汽化膜制备过程中面临的最大问题是获得性能优异且稳定的膜材料。在众多制备方法中,界面聚合法具有反应活性高、常温下生成膜层稳定、制备活性层致密等特点而备受关注。通过对界面聚合过程的调控,可以优化活性层,从而制备出兼具高通量和高选择性的渗透汽化膜。本文综述了界面聚合的原理、在渗透汽化膜制备方面的优势和近年来国内外的研究进展,详细阐述了复合膜制备过程中底膜的选择与改性、界面聚合条件的调控对渗透汽化膜结构和分离性能的影响机制,并对界面聚合制备渗透汽化膜所面临的问题及前景进行了总结与展望。     

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。     

耐污染性复合纳滤膜制备技术研究进展

商业化纳滤膜绝大多数采用由二元胺与多元酰氯在非织造布基超滤膜表面界面聚合得到的复合纳滤膜。复合纳滤膜以其基膜和功能层材料可以分别设计,能够在较低压力下同时获得高脱盐率和水通量的优点,而被广泛应用在膜法水处理领域中。然而由于因环境中无机盐结垢、胶体、有机物和生物膜引起的膜污染,造成产水水质及膜通量的下降,膜寿命大大降低且运行成本增加,迫切需要提高复合纳滤膜的耐污染性。本文从新型单体开发、功能层及新型基膜这三大方面探讨目前复合纳滤膜耐污染性的研究进展,并对其制备方法中亟需深入研究的内容和其应用前景进行了展望。     

高性能聚砜中空纤维纳滤膜基膜的研制

采用干-湿法工艺制备聚砜基膜,研究了聚砜铸膜液中聚砜含量、添加剂种类、溶剂组成及含量和凝固浴温度对膜性能的影响。研究结果表明,铸膜液中聚砜含量和添加剂含量对膜性能影响较大;使用混合溶剂可有效改善膜的孔结构和提高聚砜基膜的性能;控制凝胶浴温度可以得到较高性能的基膜。通过选择最佳铸膜液组成及工艺条件,可以制备较高性能的基膜。     

功能性中间层对聚酰胺膜水处理性能影响

含聚酰胺层（PA）的复合膜自被发明以来，就广泛应用于纳滤（NF）、反渗透（RO）、正渗透（FO）等水处理领域。但是，聚酰胺膜的渗透性和选择性的相互制约使得对其的研究亟待产生新的突破。近年来，一种位于基膜和选择层之间的中间层成为膜制备研究的热点。这种中间层会影响聚酰胺层的形貌以及界面聚合过程，因而较先前的聚酰胺膜及纳米材料复合膜在通量及截留率方面均有一定提高，是解决目前聚酰胺膜渗透性和选择性矛盾的重要途径。综述了近年来有关中间层对聚酰胺膜水处理性能的影响和机理，介绍了基于有机涂层、纳米材料及二者结合的不同类型中间层的结构和性能，以及以此制备的聚酰胺膜的性能变化，为制备高性能的聚酰胺膜提供依据。     

新型PVA/PA复合膜的微结构及其成膜条件

将不同材料分别用作复合膜的分离层和支撑体,是制备优良选择渗透性分离膜的重要方法之一.采用浇铸工艺将具有亲水性和高分离因子的聚乙烯醇(PVA)涂覆在高度透水性的反渗透(RO)聚酰胺(PA)膜表面,制备成渗透汽化(PV)分离有机物水混合物的PVA/PA复合膜.扫描电子显微镜(SEM)和原子力显微镜(AFM)以及红外光谱分析表明,PVA-PA层结构为一体化,膜表面光滑、致密,分离层上的微囊高度下降到4 nm左右.可以认为膜的优异传质性能取决于良好微结构包括PVA的化学交联和膜的结构形貌.铸膜液中PVA和交联剂的浓度以及热处理条件对复合膜分离性能的影响是明显的.这一新型的复合膜在环境温度下PV分离异丙醇(IPA)/水混合物的渗透通量(J)接近100 g·m-2·h-1,渗透物中的水含量(CP-H2O)大于99.5%.     

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。     

Highly permeable reverse osmosis membranes incorporated with hydrophilic polymers of intrinsic microporosity via interfacial polymerization

Enhancing the water permeation while maintaining high salt rejection of existing reverse osmosis (RO) membranes remains a considerable challenge. Herein, we proposed to introduce polymer of intrinsic microporosity, PIM-1, into the selective layer of reverse osmosis membranes to break the trade-off effect between permeability and selectivity. A water-soluble a-LPIM-1 of low-molecular-weight and hydroxyl terminals was synthesized. These designed characteristics endowed it with high solubility and reactivity. Then it was mixed with m-phenylenediamine and together served as aqueous monomer to react with organic monomer of trimesoyl chloride via interfacial polymerization. The characterization results exhibited that more “nodule” rather than “leaf” structure formed on RO membrane surface, which indicated that the introduction of the high free-volume of a-LPIM-1 with three dimensional twisted and folded structure into the selective layer effectively caused the frustrated packing between polymer chains. In virtue of this effect, even with reduced surface roughness and unchanged layer thickness, the water permeability of prepared reverse osmosis membranes increased 2.1 times to 62.8 L·m^-2·h^-1 with acceptable NaCl rejection of 97.6%. This attempt developed a new strategy to break the trade-off effect faced by traditional polyamide reverse osmosis membranes.     

反渗透膜脱硼技术研究进展

硼是生命体中必不可少的微量元素,但是摄入过量的硼会危害动植物的生长发育。在现有脱硼技术中,反渗透膜脱硼被认为最具应用前景,但受硼酸分子的分子直径小和不带电荷等影响,反渗透膜对硼的脱除仍不能满足实际要求,因此制备高脱硼反渗透膜具有重要意义。本文综述了近年来反渗透膜脱硼技术的研究进展,重点阐述了提高反渗透膜脱硼率的机制,主要思路包括优化反渗透膜结构和利用硼酸特殊性质;改善反渗透膜脱硼性能的有效途径包括开发新型膜材料,优化界面聚合工艺和物理化学法改性等;制备高脱硼反渗透膜的主要障碍是水硼传输的trade-off现象和缺少针对水和硼传输的模型。另外,硼酸分子具有独特的物理化学性质,可以借助硼酸分子研究聚酰胺反渗透膜的网络结构、水硼在膜内的传输机制和引起trade-off现象的因素。     

Recent advances in polymer and polymer composite membranes for reverse and forward osmosis processes

Semipermeable membranes are the core elements for membrane water desalination technologies such as commercial reverse osmosis (RO) process and emerging forward osmosis (FO) process. Structural and chemical properties of the semipermeable membranes determine water flux, salt rejection, fouling resistance, and chemical stability, which greatly impact energy consumption and costs in osmosis separation processes. In recent years, significant progress has been made in the development of high-performance polymer and polymer composite membranes for desalination applications. This paper reviews recent advances in different polymer-based RO and FO desalination membranes in terms of materials and strategies developed for improving properties and performances.     

反渗透膜的研究进展与展望

反渗透具有低能耗、高效率等突出优点,是目前应用最为广泛的分离技术之一。反渗透膜的性能是影响反渗透过程效率的决定因素,反渗透膜的研制一直是国内外膜领域的研究热点。特别是近年来,石墨烯、碳纳米管等新型材料展现出优异的水传递行为,成为新型反渗透膜材料的研究热点。本论文回顾了反渗透膜的研制发展历程,介绍了不同单体通过界面聚合反应成膜的研究进展,综述了国内外新型混合基质膜和无机分子筛反渗透膜材料及其成膜研究,最后提出了新型反渗透膜的研究方向。     

Fabrication of polyamide thin film nanocomposite reverse osmosis membrane incorporated with a novel graphite-based carbon material for desalination

The properties of polyamide (PA) thin film composite (TFC) membranes are affected by many variables, especially the additives in the process of interfacial polymerization that play an important role in the properties of membranes. In this study, a new type graphite carbon was added into organic phase containing trimesoyl chloride for interfacial polymerization with aqueous phase containing m-phenylenediamine to prepare modified polyamide thin film nanocomposite (TFN) membranes for reverse osmosis (RO) adhibition. Polysulfone ultrafiltration membranes were used as the carrier of the interfacial polymerization. The concentration of graphite carbon was selected from 0.002 to 0.01 wt%. The polyamide nanocomposite membrane prepared with the concentration of 0.004 wt% graphite carbon showed the best RO desalination performance, which the water flux of this TFN membrane is over 2.3 times as much as pristine TFC membrane, and the salt rejection is over 99%. This article provides a well-performing polyamide thin film nanocomposite membrane modified by a new-type carbon nanoparticles consequently.     

Effect of surface properties of polysulfone support on the performance of thin film composite polyamide reverse osmosis membranes

In this work, influence of initial conditions and surface characteristics of porous support layer on structure and performance of a thin film composite (TFC) polyamide reverse osmosis (RO) membrane was investigated. The phase inversion method was used for casting of polysulfone (PSf) supports and interfacial polymerization was used for coating of polyamide layer over the substrates. The effect of PSf concentrations that varied between 16 wt % and 21 wt %, and kind of the solvent (DMF and NMP) used for preparation of initial casting solution were investigated on the properties of the final RO membranes. SEM imaging, surface porosity, mean pore radius, and pure water flux analysis were applied for characterization of the supports. The substrate of the membrane, which synthesized with 18 wt % of PSf showed the most porosity and the synthesized RO membrane had the lowest salt rejection. In case of the solvents, the membranes synthesized with DMF presented better separation performance that can be attributed to their lower thickness and sponge‐like structure. The best composition of support for TFC RO membranes reached 16 wt % PSf in DMF solvent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44444.     

Temperature Effects on Concentration Polarization Thickness in Thin‐Film Composite Reverse Osmosis Membranes

Continuous research and development of reverse osmosis (RO) technologies has led to the production of membranes that are very effective with high salt rejection abilities. As temperature is one of the factors that affects salt rejection capabilities in membranes, this paper investigates the effect of temperature on the thickness of the concentration polarization layer (CPL) deposited on thin‐film composite seawater RO membranes. Two types of membranes were studied: those with ex situ macromolecules and those with in situ macromolecules. FilmTec's reverse osmosis system analysis design software was used to predict the variation of salt rejection and permeate flow rate with temperature. The impact of these variations on the thickness of the CPL was analyzed for different polyamide concentrations in the membrane.     

Preparation and characterization of thermally crosslinked chlorine resistant thin film composite polyamide membranes for reverse osmosis

Currently, polyamide reverse osmosis membranes are highly effective for desalination, industrial process water, and home drinking water. However, they have poor resistance to strong oxidants especially chlorine due to chain cleavage of aromatic polyamide. In general, aromatic polyamide RO membranes are essentially random copolymers consisting of the linear and crosslinked structures. The amide ring is sensitive to attack by chlorine because it is an electron-rich region. Therefore, the activated carbon or sulfite addition processes are essential to remove the chlorine in the separation processes. Many research groups have studied to improve the chlorine-resistance RO membrane having hydrophilic groups (− SO₃H and − COOH) or nitro groups (− NO₂) such as electron acceptors. In this study, thin film composite polyamide RO membranes were prepared by interfacial polymerization method including cross-linking agents having hydroxyl groups to improve the chlorine-resistance. The chlorine-resistance of polyamide RO membrane was influenced by the thermal cross-linking conditions (temperature and time) and cross-linking density of polyamide membranes.     

Chiral separation of D,L‐serine racemate using a molecularly imprinted polymer composite membrane

Molecularly imprinted (MIP) composite membranes were prepared using conventional interfacial polymerization technique that has been often used for the preparation of reverse osmosis (RO) membrane. Target molecules (D ‐serine) were used together with the piperazine (PIP) and Trimesoyl chloride (TMC) for the interfacial polymerization of the active layer with chiral spaces in it on the surface of the polysulfone ultrafiltration membranes. After formation of the polyamide composite membranes, the target molecules in the active layers were removed and MIP composite membranes were prepared. The MIP membranes prepared so were then characterized with analytical methods and proved to be effective for the selective permeation of D ‐serine. When serine racemate was used for optical resolution, the diffusion rate of the D ‐serine appeared to be faster than that of the L ‐serine and in permeates, the concentration of the D ‐serine increased with operation time. When the operating time reached 60 h, enantiomeric excess (% ee) of the serine mixture in permeates became about 80%. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1866–1872, 2007