纳滤膜新型材料研究

纳滤是一种介于超滤与反渗透之间的重要膜分离过程,具有工作压力低、无相转变及分离效率高等独特优势。膜污染及渗透性/选择性之间的平衡是纳滤膜在使用和研发过程中面临的亟待解决的两个主要问题。膜材料是膜与膜分离技术的核心,开发新型的纳滤膜材料是解决上述问题的重要手段。本文从新型纳滤膜材料的设计与选择的角度出发,总结归纳了近年来新型材料在纳滤膜的制备与应用研究现状,包括新型有机纳滤膜材料、新型无机纳滤膜材料和新型有机-无机杂化纳滤膜材料三个方面,拓展了对纳滤膜材料的认知,探讨了新型纳滤膜材料的共性及其存在的主要问题,并对未来高性能纳滤膜材料的研制方向进行了展望。     

耐溶剂纳滤膜*

纳膜分离过程是一种选择性高、操作简单、能耗低的分离技术,已在各工业领域和科学研究中得到广泛的应用。纳滤过程的诸多优点,使其在石油化工、医药、食品等领域的非水溶液体系中具有极大的潜在应用价值,而传统的纳滤膜难以拓宽到非水溶液体系中使用,为此进一步研究和发展耐溶剂纳滤膜,对于拓宽纳滤过程的应用极其重要。目前,耐溶剂纳滤膜已成为膜分离科学领域的研究热点,在现有报道的文献基础上,本文综述了有关在非水溶液体系中使用的耐溶剂纳滤膜制备的研究进展,并对将来的发展方向提出了建议。     

解读纳滤:一种具有纳米尺度效应的分子分离操作

纳滤膜是20世纪80年代末期发展起来的一种广泛用于液体分离的新型分离膜。早期研究中,先后提出的基于筛分效应的细孔模型,基于静电效应的电荷模型,以及同时考虑上述两种效应的静电位阻模型和道南位阻模型等为人们更好地理解纳滤膜分离机理和指导纳滤膜过程应用发挥了十分重要的作用。然而由于这些具有“疏松型反渗透膜”特点的纳滤膜没有相应的膜性能预测评价软件,使得针对具体应用过程的纳滤膜的大规模标准化应用受到了一定的制约。为此,结合上述模型,根据一些特定实验拟合确定混合盐体系同号离子间的竞争作用和异号离子间的调节作用,提出了一个适于混合盐体系的纳滤膜分离性能评价模型,促进了纳滤膜技术在水处理过程的大规模推广。最近,根据纳滤膜对离子选择性分离性能及其伴随的动电性质的细致而深入的实验研究,发现仅考虑筛分效应和静电效应并不能完全合理地解释纳滤膜的分离性能,且在动电性质的解析上也存在一定缺陷,进而对纳滤膜纳米级孔径引起的特殊效应和溶液体系中复杂相互作用引起的荷电性质变化有了更为深刻的认识和理解,提出并定量分析了离子透过纳滤膜时存在的介电排斥效应。     

层状MoS2复合膜的制备及其纳滤与光热抗菌性能研究

二维纳米片构建的层状纳滤膜在工业染料和含盐废水的净化处理中显示出广泛的应用前景,但纳米片间松散的层状结构会影响过滤通道的稳定性,导致对盐类的截留效果不理想.本文以均苯三甲酰氯(TMC)交联单宁酸(TA)官能化的二硫化钼(MoS_2)纳米片构建薄层复合纳滤膜,以解决二维材料构建层状纳滤膜的常见问题.所制备的纳滤膜不仅对荷负电染料(伊文思蓝,分子量960.8)有很高的截留率(98.5%),也能很好地选择性分离染料-盐混合溶液(NaCl截留率15%).同时,该膜还能在严苛环境中保持优秀的稳定性.此外,在近红外光照射下,MoS2纳米片显著的光热转换效应赋予薄层复合纳滤膜一定的抗菌能力,使得该膜在实际应用中具有巨大潜力.     

荷正电聚乙烯亚胺纳滤膜的制备与应用

纳滤是介于超滤与反渗透之间的膜分离技术,具有操作压力低,无相变,分离效率高及运行成本低等优点,广泛地应用于饮用水制备、污水处理、化工、制药和食品等领域.近年来,随着分离体系复杂程度的增加及对膜分离性能要求的提高,荷正电纳滤膜越来越受到研究者的关注.聚乙烯亚胺(PEI)是一类重要的多胺类荷正电纳滤膜材料,具有优异的亲水性、高荷电密度及反应活性.开发具有高分离性、高稳定性、耐酸碱性、耐溶剂性、抗菌性和耐污染性的荷正电PEI纳滤膜(P-PEI-NFM)日益成为研究的热点.本文对近年来P-PEI-NFM的制备方法进行归纳,总结了P-PEI-NFM在水软化、重金属脱除、碱性染料的分离及浓缩、抗生素分离和耐溶剂纳滤的应用.探讨了P-PEI-NFM存在的主要问题,并对未来的研究方向进行了展望.     

二胺结构对聚酰胺复合纳滤膜性能的影响

分别以邻苯二胺、间苯二胺、对苯二胺为水相单体,均苯三甲酰氯(TMC)为油相单体,聚醚砜超滤膜为基膜,界面聚合法制备了复合纳滤膜.在纳滤膜对Na<,2>SO<,4>,MgSO<,4>,MgCl<,2>和NaCl四种盐的脱盐率中,间苯二胺膜最高,对苯二胺膜居中,邻苯二胺膜最差;在纳滤膜耐氯性能方面,对苯二胺最佳,邻苯二胺居...     

荷电高聚物纳滤膜

本文对荷电聚合物纳纳滤膜的制备、性能及应用进行了全面的介和评述，反映了近年来荷电聚合笺纳滤膜研究的最新进展和动向。     

用流动电位法表征纳滤膜的结构及性能

利用测量流动电位的方法考察了纳滤膜的表面电学性能对纳滤膜的截留性能的影响.首先,采用不同功能层材料制备了复合纳滤(NF)膜,考察功能层的交联时间、单体结构等对表面电性能的影响,研究纳滤膜对不同无机盐的选择截留性能与表面电性能的关系.通过流动电位法测定纳滤膜的表面电学参数,如流动电位(ΔE)、zeta电位(ζ)和表面电荷密度(σd).实验表明,这些电学参数的变化与功能层交联时间和纳滤膜截留率的变化一致,在交联时间为45 s时,3种电学参数的绝对值均最大,而纳滤膜对无机盐的截留率也最大.复合纳滤膜zeta电位的绝对值(|ζ|)按照Na2SO4>MgSO4>MgCl2变化,同截留率的变化相同.带侧基单体交联后得到的纳滤膜的表面电性能参数的绝对值小于不带侧基单体的.因此,流动电位法可用于研究复合纳滤膜的截留机理和功能层结构.     

纳滤膜对电解质溶液分离特性的理论研究(II): 混合电解质溶液

假定纳滤膜具有狭缝状孔, 使用纯水透过系数、膜孔径及膜表面电势来表征纳滤膜的分离特征, 用流体力学半径和无限稀释扩散系数表征了离子特性. 采用扩展Nernst-Planck方程、Donnan平衡模型和Poisson-Boltzmann理论描述了混合电解质溶液中离子在膜孔内的传递现象, 计算了三种商用纳滤膜(ESNA1-LF, ESNA1和LES90)对同阴离子、同阳离子和含四种离子的混合电解质体系中离子的截留率, 并与实验数据进行了比较. 计算结果表明, 电解质溶液中离子在纳滤膜孔内传递的主要机理是离子的扩散和电迁移, 纳滤膜对混合电解质溶液中离子的分离效果主要由空间位阻和静电效应决定. 该模型在低浓度时对含一价离子的混合电解质溶液通过纳滤膜的截留率计算结果比较准确, 但对高浓度或含高价离子的混合电解质溶液则偏差较大.     

纳滤膜分离机理及其应用研究进展

综述了纳滤膜的分离机理及其应用研究现状和进展,纳滤膜分离过程是一个不可逆过程,其分离机理可以运用电荷模型（空间电荷模型和固定电荷模型）和细孔模型,以及近年才提出的静电排斥和立体阻碍模型等来描述。纳滤膜应用研究现状的介绍包括低聚糖分离和精制、果汁的高浓度浓缩、多肽和氨基酸的分离、抗生素的浓缩与纯化、牛奶及乳清蛋白的浓缩、农产品的综合利用以及纳滤膜生化反应器的开发等。     

纳滤膜的研究进展

纳滤膜是一种新型分离膜,其截流分子量介于反渗透膜和超滤膜之间,且对无机盐有一定的截流率。国内外纳滤膜制备方法有L-S相转化法、复合法、荷电化法和无机改性等。纳滤膜研究中存在着膜通量小、膜制作成本较高及抗污染性差等问题,因此选择和制备纳滤膜的材料,优化纳滤技术水处理工艺设计,提高纳滤性能,降低制膜成本,减轻膜污染等已成为当今科学研究的重要课题。     

膜技术的研究进展和应用前景

介绍了膜技术的现状、应用及发展。对膜材料的分类、膜反应机理和膜技术的应用进行了探讨,并提出了所面临的问题及对前景的展望。     

全氟磺酸质子交换膜的溶解及再铸膜性能分析

全氟磺酸树脂溶液在质子交换膜燃料电池和电化学中很有用途 .利用二甲基亚砜 ,在 170～ 180℃和氮气保护的条件下对Nafion 115进行了溶解实验 ,获得了两种膜溶液 .利用膜溶液制得了再铸膜 ,并测定了再铸膜的交换容量、含水率和电导率等 .结果表明 :再铸膜的交换容量、含水率和电导均低于其母膜Nafion 115 ,说明在溶解过程中有部分磺酸集团被破坏     

渗透汽化分离苯—乙醇混合物

以甲基硅橡胶及甲基丙烯酸十二酯－甲基丙烯酸异丁酯的共聚物共为膜材料，以聚丙烯睛多孔膜为底膜制成复合膜，对苯－乙醇混合物进行渗透汽化分离。考察了膜材料的组成、分离温度、原料液组分等因素对膜性能的影响。     

纤维素亲和膜用于内毒素的去除

报道了用于内毒素去除的３种新型纤维素亲和膜的制备及应用,并对它们的性能进行了比较。结果表明,这３种亲和膜均能有效去除盐溶液中的内毒素,去除率在９０％以上。对人血清白蛋白溶液,季铵盐和壳聚糖亲和膜对内毒素的去除率较高,仍然在９０％以上,金属螯合物亲和膜的去除效果不如前两种,去除率仅为８３．３％。实验选择不同的亲和膜,考察了它们对内毒素的吸附容量、样品处理量以及再生效果,结果表明吸附量在 ２．４×１０６ＥＵ／ｇ以上,样品处理量较大,适合用于小批量医药制剂的生产过程;再生效果较好,可重复使用。     

Effect of membrane parameters on the size and uniformity in preparing agarose beads by premix membrane emulsification

Agarose microbeads were prepared by premix membrane emulsification with Shirasu-Porous Glass (SPG) membrane and Polyethylene (PE) membrane. The effects of membrane parameters, including pore size, pore size distribution, contact angle between membrane surface and the water phase, shape of pore opening and membrane thickness on size and uniformity of agarose beads were investigated in this study. The results showed that pore size distribution and shape of pore opening did not affect the emulsification results apparently within a wide range in premix membrane emulsification, not as the result in general emulsification. The contact angle between the water phase and the membrane surface must be large enough to obtain uniform-sized agarose beads in both direct membrane emulsification and premix membrane emulsification. The results also showed that the membrane pore size and thickness affected the size distribution of emulsion. Thicker membrane resulted in more uniform and smaller emulsion when the number of pass through membrane is controlled. There was a linear relationship between the number average diameter of agarose beads and membranes pores size in premix membrane emulsification. Agarose beads with diameters from 3.06 to 9.02 μm were prepared by controlling membranes pore size. The ratio of the number average diameter of agarose beads to membrane pore diameters was found to be 0.486.     

Dielectric analysis of nanofiltration membrane in electrolyte solutions: influences of electrolyte concentration and species on membrane permeation

Dielectric properties of a nanofiltration membrane immersed in dilute aqueous electrolyte solutions were measured, and frequency dependence of capacitance and conductance of the systems was analyzed, based on the interfacial polarization theory, giving values of permittivity and conductivity of the membrane and the solutions. Permittivity, epsilon m, of the membrane slightly decreased whereas conductivity, km, of the membrane increased with increasing electrolyte concentration, as a result of entrance of ions into the membrane. The ratio of membrane/solution conductivity, km/kw, also depended on the electrolyte concentration, showing that distribution of ions in the membrane and in solutions follow Donnan equilibrium, due to the presence of negative fixed charges in the membrane. New expressions were derived from Donnan equilibrium principle to explain this phenomenon, and negative fixed charge concentration ce of the membrane was obtained; thus the Donnan potential, DeltaPhi Don, of the membrane in solutions at various concentrations could be calculated. The new expressions could be expected to be usable to analyze ion permeation property through membrane.     

Preparation and characterization of Nafion/SPEEK layered composite membrane and its application in vanadium redox flow battery

In order to reduce the cost of membrane used in vanadium redox flow battery (VRB) system while keeping its chemical stability, Nafion/sulfonated poly(ether ether ketone) (SPEEK) layered composite membrane (N/S membrane) consisting of a thin layer of recast Nafion membrane and a layer of SPEEK membrane were prepared by chemical crosslink the sulfonic acid groups of different ionomer membranes. Scanning electron microscopy (SEM) and IR spectra analysis of the membrane showed that Nafion layer was successfully deposited on the SPEEK membrane surface and an integral layered membrane structure was formed. The area resistance and permeability of vanadium ions of membrane were also measured. It was found that N/S membrane have a very low permeability of vanadium ions accompanied by a little higher area resistance compared with Nafion membrane. As a result, the VRB single cell with N/S membrane exhibited higher coulombic efficiency and lower voltage efficiency compared with VRB single cell with Nafion membrane. Although N/S membrane delivered relatively lower energy efficiency compared with Nafion membrane, its good chemical stability and low cost make it a suitable substitute for Nafion membrane used in VRB system.     

Membrane formation and structure development by dry-cast process

The various types of porous membranes were prepared by dry-cast process in several cellulose acetate/acetone/nonsolvent systems. The nonsolvents used were 2-methyl-2,4-pentanediol, hexanol and octanol. Because of the high boiling points of the nonsolvents used in this work, only the solvent (acetone) evaporated during the membrane formation. The effects of the nonsolvent weight fraction in the cast solution, the polymer weight fraction, membrane thickness and kinds of the nonsolvents on the membrane structures were studied. As the nonsolvent weight fraction increased, the membrane morphology changed in the order of entirely dense, asymmetric and entirely porous structures. The increase in the polymer weight fraction and the decrease in the membrane thickness suppressed the asymmetric structures. These kinds of nonsolvents significantly influenced the membrane morphology.In order to understand the change of the obtained membrane structures, the phase diagrams for ternary systems were clarified experimentally and theoretically. Moreover, the mass transfer process was analyzed and the changes in the polymer volume fractions during the membrane formation were simulated. Based on both these thermodynamic and kinetic properties, the membrane structures obtained were discussed in detail. The asymmetrc structures obtained in this work were found to be attributable to the kinetic difference in the increase rates of the polymer fractions across the binodal line.     

全钒氧化还原液流电池用Nafion/有机硅复合膜

采用原位化学反应的方法制备了Nafion/有机硅复合膜, 并对所制备复合膜的离子交换容量(IEC)、电导率和水渗透率等进行了测试. 结果表明, 所制备复合膜具有优异的阻水性能. 以Nafion/有机硅复合膜作为离子交换膜的钒电池的库仑效率(CE)和能量效率(EE)都得到了大幅度提高. 此外, 以所制备复合膜为离子交换膜的VRB单电池充放电80次后性能几乎无衰减, 说明所制备Nafion/有机硅复合膜即使在强酸和强氧化性的钒电池体系中也可以稳定使用, 表明Nafion/有机硅复合膜是一种性能优异的适用于全钒氧化还原液流电池的新型质子交换膜.