纳滤膜对电解质溶液分离特性的理论研究(Ⅰ):单一电解质溶液

电解质溶液在纳滤膜中的截留率对于膜法海水淡化和重金属离子的脱除非常重要.本文假定膜具有狭缝状孔,采用扩展Nernst-Planck方程、Donnan平衡模型和Gouy-Chapman理论来描述电解质溶液中离子在膜孔内的传递现象.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,这三个参数可通过Levenberg-Marquardt方法由实验数据关联得到.本文使用该模型计算了两种商用纳滤膜(NF45和SU200)对1-1型(NaCl,KCl,LiCl),2-1型(K2SO4)和2-2型(MgSO4)单一电解质溶液的截留率,并与实验数据进行了比较,两者吻合较好.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电解质溶液通过纳滤膜的截留率计算结果较准确,但对高浓度电解质溶液则偏差较大.     

纳滤膜对电解质溶液分离特性的理论研究(I): 单一电解质溶液

电解质溶液在纳滤膜中的截留率对于膜法海水淡化和重金属离子的脱除非常重要. 本文假定膜具有狭缝状孔, 采用扩展Nernst-Planck方程、Donnan平衡模型和Gouy-Chapman理论来描述电解质溶液中离子在膜孔内的传递现象. 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, 这三个参数可通过Levenberg-Marquardt方法由实验数据关联得到. 本文使用该模型计算了两种商用纳滤膜(NF45和SU200)对1-1型(NaCl, KCl, LiCl), 2-1型(K₂SO₄)和2-2型(MgSO₄)单一电解质溶液的截留率, 并与实验数据进行了比较, 两者吻合较好. 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电解质溶液通过纳滤膜的截留率计算结果较准确, 但对高浓度电解质溶液则偏差较大.     

聚酰胺纳滤膜对黄连中生物碱的截留性能

以盐酸小檗碱为模型分子,考察循环时间、操作压力、料液浓度和离子强度等因素对聚酰胺纳滤膜截留盐酸小檗碱性能的影响。实验表明:聚酰胺纳滤膜对盐酸小檗碱的截留率80min后基本稳定;随着操作压力的增加,膜通量和截留率都增大;随着料液浓度的增加,聚酰胺纳滤膜通量下降,对盐酸小檗碱的截留率先增大后下降;随着溶液中离子强度的增加,膜通量和截留率都减小。在黄连提取液中生物碱含量为0.025g/L、操作压力为0.4MPa条件下,聚酰胺纳滤膜5min可使黄连提取液中生物碱浓缩6.27倍。     

紫外辐照接枝制备亲水性荷正电纳滤膜

通过在酚酞基聚芳醚酮超滤膜表面紫外辐照接枝亲水性单体二烯丙基二甲基氯化铵(DADMAC)制备了一种表面荷正电的纳滤膜. ATR-FTIR和表面水接触角的研究结果表明膜表面的接枝率和亲水性随着辐照时间和单体在接枝溶液中的浓度的增加而增加. 荷正电纳滤膜对盐溶液有很好的截留, 对盐溶液中的高价阳离子和低价阳离子的截留率分别为95%和65%. 但当溶液中存在高价负离子时, 膜的截留性能会明显下降. 表明静电效应在荷电纳滤膜的分离过程中起了重要的作用.     

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.     

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.     

UV辐照接枝制备酚酞基聚芳醚酮纳滤膜——链转移剂的作用

酚酞基聚芳醚酮(PEK-C)超滤膜的表面通过紫外辐照接枝丙烯酸(AA)可以制备对II价盐有很好截留率的亲水性纳滤膜. FTIR-ATR、表面接触角、SEM和AFM的研究结果表明, 在接枝单体溶液中加入异丙醇(i-PrOH)作为链转移剂并不影响AA在PEK-C超滤膜表面的接枝反应. 得到的改性膜同样具有优良的纳滤性能. 与不加i-PrOH的AA改性膜相比, 新合成的膜有较高的滤出液通量, 该膜对盐离子的截留率虽有所降低, 但可以通过增加接枝反应时间和辐照光源的强度来提高. i-PrOH的浓度对膜的分离性能的影响很大, 在低浓度时, 改性膜对离子的截留率会有所下降, 继续提高i-PrOH的浓度, 膜的截留率不再变化而滤出液通量会有成倍的增加, 表明链转移剂的存在可能会提高膜的接枝密度, 增加膜的表面电荷, 使膜对离子的截留率保持不变.     

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。     

1-1型单组分盐溶液中荷电膜膜电位的研究

根据固定电荷模型和非线性最小二乘法, 研究膜体积电荷密度为定值和其大小随电解质主体溶液浓度呈指数变化的两种初始条件下, 五种纳滤膜(NTR 7450, ESNA 1, ESNA 1-LF, LES 90和UTC 60)在不同浓度的氯化钠和氯化钾溶液中的膜电位, 获得膜体积电荷密度与电解质主体溶液浓度的关系. 结果表明, 当体积电荷密度随浓度呈指数变化时, 拟合的膜电位与实验结果更接近, 得到的固定电荷密度更精确. 膜电位的大小与膜两侧电解质溶液浓度的比值相关. 在较高浓度时, 膜电位的值还与扩散系数相关; 其中阴阳离子的扩散系数之比大于1.0是膜电位反号的标志. 在中间浓度时, 膜电位随电解质主体溶液浓度近似呈线性变化.     

聚电解质层层自组装纳滤膜*

层层自组装技术能够方便地对膜的微观结构和组成进行调控,已在制备复合型纳滤膜方面取得了迅速的发展。本文综述了近年来用于聚电解质层层自组装纳滤膜的制备方法,种类以及影响因素。介绍了静态层层交替沉积、压力驱动自组装和电场强化自组装等三种制备方法;归纳了均聚型、共聚型和有机/无机杂化型等三类用于层层自组装纳滤膜的聚电解质的特点;讨论了聚电解质的荷电性、电荷密度和电离程度等因素对其自组装膜分离性能的影响。总结了聚电解质自组装纳滤膜在水处理和有机溶剂中物质的分离等方面的应用。同时,对提高聚电解质自组装纳滤膜的组装效率,分离性能和发展方向提出了设想和建议。     

The effect of gel layer thickness on the salt rejection performance of polyelectrolyte gel-filled nanofiltration membranes

The effect of gel layer thickness on salt separation of positively charged pore-filled nanofiltration membranes has been examined both theoretically and experimentally. The extended Nernst-Planck (ENP) equation coupled with the Teorell-Meyer-Sievers (TMS) model were used to calculate the pressure-driven sodium chloride rejections for membranes having gel densities in the range typically used in nanofiltration applications. It was found that salt rejection was dependent on membrane (gel-layer) thickness with salt rejections increasing rapidly with thickness up to 50–75 μm. Further increases in thickness beyond this point had a much smaller effect on salt rejection. The theoretical predictions were examined experimentally by preparing a series of membranes with cross-linked poly(3-acrylamidopropyl)-trimethylammonium chloride (PAPTAC) gels with varying densities within the pores of a thin microporous polyethylene (PE) support. The membranes were characterized by their polymer volume fractions (gel concentration), thicknesses and effective charge densities. The effect of membrane thickness was examined by using single and stacks of two membranes. The pure water fluxes and salt rejections of the membranes and membrane stacks were determined in the pressure range 50–550 kPa. The single salt rejections of the membranes which were very dependent on the thickness of the membrane or membrane stack, were fully in accord with the calculated salt rejections of the membranes.     

Influence of steric, electric, and dielectric effects on membrane potential

The membrane potential arising through nanofiltration membranes separating two aqueous solutions of the same electrolyte at identical hydrostatic pressures but different concentrations is investigated within the scope of the steric, electric, and dielectric exclusion model. The influence of the ion size and the so-called dielectric exclusion on the membrane potential arising through both neutral and electrically charged membranes is investigated. Dielectric phenomena have no influence on the membrane potential through neutral membranes, unlike ion size effects which increase the membrane potential value. For charged membranes, both steric and dielectric effects increase the membrane potential at a given concentration but the diffusion potential (that is the high-concentration limit of the membrane potential) is affected only by steric effects. It is therefore proposed that membrane potential measurements carried out at high salt concentrations could be used to determine the mean pore size of nanofiltration membranes. In practical cases, the membrane volume charge density and the dielectric constant inside pores depend on the physicochemical properties of both the membrane and the surrounding solutions (pH, concentration, and chemical nature of ions). It is shown that the Donnan and dielectric exclusions affect the membrane potential of charged membranes similarly; namely, a higher salt concentration is needed to screen the membrane fixed charge. The membrane volume charge density and the pore dielectric constant cannot then be determined unambiguously by means of membrane potential experiments, and additional independent measurements are in need. It is suggested to carry out rejection rate measurements (together with membrane potential measurements).     

Flow of Multicomponent Electrolyte Solutions through Narrow Pores of Nanofiltration Membranes

The slow flow of a multicomponent electrolyte solution in a narrow pore of a nanofiltration membrane is considered. The well-known semiempirical method of subdivision of electrical potential into quasi-equilibrium and streaming parts and the definition of streaming concentrations and pressure are discussed. The usefulness of this tool for solving the electrohydrodynamic equations is shown and justified: the use of a small parameter enables a system of electrohydrodynamic partial differential equations to be reduced to a system of ordinary differential equations for streaming functions. Boundary conditions for streaming functions at both the capillary inlet and outlet are derived. The proposed model is developed for the flow of a multicomponent electrolyte solution with an arbitrary number of ions. This is coupled with (i) the introduction of specific interactions between all ions and the pore wall and (ii) the inclusion of the dissociation of water in both conservation and transport equations. Effective distribution coefficients of ions are introduced that are functions of both the specific interaction potentials and the surface potential of the nanofiltration membrane material. The axial dependency of surface potential is expressed by the use of a charge regulation model from which the discontinuity in electric potential and ion pore concentrations at the pore inlet and outlet can be described.A relation between the frequently used capillary and homogeneous models of nanofiltration membranes is developed. An example of application of the homogeneous model for interpretation of experimental data on nanofiltration separation of electrolyte solutions is presented, which shows a reasonable predictive ability for the homogeneous model.     

Modeling the separation performance of nanofiltration membranes for the mixed salts solution

A new model is proposed to evaluate the separation performance of nanofiltration (NF) membranes for the mixed salts solution. In the model, the observed transmission of an ion through a NF membrane is applied to express the separation performance of the membrane for the ion in the mixed salts solution, which has a relationship with the total concentration, the equivalent fraction and the species of each ion in the mixed salts solution. The verification of the model was carried out in the permeation experiments of some mixed salts solutions ((1) Na⁺, Cl⁻ and F⁻; (2) Na⁺, K⁺ and Cl⁻; (3) Na⁺, F⁻, Cl⁻ and NO₃⁻; (4) Na⁺, Cl⁻, NO₃⁻ and SO₄²⁻) through three commercial NF membranes (ESNA 1-LF, ESNA 1 and LES 90). According to the permeation experiments of three NF membranes for some binary salts solutions, the competition coefficients of ions were obtained. The model evaluation results agreed quite well with the experimental data. Finally, the model was applied to evaluate the observed transmission of each ion in the mixed salts solution (Na⁺, F⁻, Cl⁻, NO₃⁻ and SO₄²⁻) through three NF membranes. The agreement between the model evaluation results and the experimental data indicated that the model is suitable for evaluating the separation performance of three NF membranes for the mixed salts solution.     

Study on transmembrane electrical potential of nanofiltration membranes in KCl and MgCl2 solutions

The transmembrane electrical potential (TMEP) across two commercial nanofiltration membranes (ESNA1-K and Filmtec NF) was investigated in KCl and MgCl(2) solutions. TMEP was measured in a wide range of salt concentrations (1-60 mol·m(-3)) and pH values (3-10) at the feed side, with pressure differences in the range of 0.1-0.6 MPa. A two-layer model based on the Nernst-Planck equation was proposed to describe the relation between TMEP and permeation flux. From the pattern of these curves, the information of membrane structure could be deduced. In the concentration range investigated, TMEP in KCl solutions was always positive and decreased as the salt concentration increased. The contribution of the membrane potential to the TMEP decreased. TMEP was greatly affected by the feed pH. When the feed pH increased, the mobility of cations increased, which indicated that the charges of NF membranes were more negative. The zero point of TMEP and the minimum of rejection in KCl solution were consistent and occurred at the isoelectric point of NF membranes, while in MgCl(2) solution the zero point of TMEP located at a higher pH value. The TMEP in MgCl(2) solutions changed its sign at a given concentration, and by calculating the transport number the location of the minimum rejection could be determined.     

Electroviscous Effects in Ceramic Nanofiltration Membranes

Membrane permeability and salt rejection of a γ‐alumina nanofiltration membrane were studied and modeled for different salt solutions. Salt rejection was predicted by using the Donnan‐steric pore model, in which the extended Nernst–Planck equation was applied to predict ion transport through the pores. The solvent flux was modeled by using the Hagen–Poiseuille equation by introducing electroviscosity instead of bulk viscosity. γ‐Alumina particles were used for ζ‐potential measurements. The ζ‐potential measurements show that monovalent ions did not adsorb on the γ‐alumina surface, whereas divalent ions were highly adsorbed. Thus, for divalent ions, the model was modified, owing to pore shrinkage caused by ion adsorption. The ζ‐potential lowered the membrane permeability, especially for membranes with a pore radius lower than 3 nm, a ζ‐potential higher than 20 mV, and an ionic strength lower than 0.01 m . The rejection model showed that, for a pore radius lower than 3 nm and for solutions with ionic strengths lower than 0.01 m , there is an optimum ζ‐potential for rejection, because of the concurrent effects of electromigration and convection. Hence, the model can be used as a prediction tool to optimize membrane perm‐selectivity by designing a specific pore size and surface charge for application at specific ionic strengths and pH levels.     

Negative rejection of ions in pressure-driven membrane processes

Negative rejections of ions in pressure-driven membrane processes can be caused by several distinct mechanisms. In a number of cases, in a final count, the phenomenon is brought about by increased concentration of an ion in the membrane phase. In the case of charged membranes, the increased concentration has to be accompanied by a weakening of electric field of filtration potential, which normally retards counter-ions and prevents the increased concentrations from manifesting themselves in negative rejections. This occurs in charge-mosaic membranes due to the so-called current circulation phenomenon or in electrolyte mixtures due to the presence of more mobile counter-ions. Negative rejections can also occur for ions whose concentration is decreased in the membrane phase. This occurs in electrolyte mixtures due to the acceleration of such ions by the electric field of diffusion potential arising because of strong rejections of other mixture components. This phenomenon is most pronounced for single-charge ions in the presence of predominant amounts of ions of higher charge of the same sign. All those mechanisms are considered within the scope of a common theoretical framework. An attempt is made of a tentative classification of mechanisms of negative rejections. An overview of available literature data is provided and it is shown that in a number of cases the published information is not sufficiently detailed for a reliable identification of the mechanisms. It is concluded that the studies of negative rejections could be a valuable membrane characterization tool but they need to be more systematic and targeted to fulfil this role.     

Membrane potential in charged porous membranes

For charged porous membranes, the separation efficiency to charged particles and ions is affected by the electrical properties of the membrane surface. Such properties are most commonly quantified in terms of zeta-potential. In this paper, it is shown that the zeta-potential can be calculated numerically from the membrane potential. The membrane potential expression for charged capillary membranes in contact with electrolyte solutions at different concentrations is established by applying the theory of non-equilibrium thermodynamic to the membrane process and considering the space-charge model. This model uses the Nernst–Planck and Navier–Stokes equations for transport through pores, and the non-linear Poisson–Boltzmann equation, which is numerically solved, for the electrostatic condition of the fluid inside pores. The integral expressions of the phenomenological coefficients coupling the differential flow (solute relative to solvent) and the electrical current with the osmotic pressure and the electrical potential gradients are established and calculated numerically. The mobilities of anions and cations are individually specified. The variations of the membrane potential (or the apparent transport number of ions in the membrane pores) are studied as a function of different parameters: zeta-potential, pore radius, mean concentration in the membrane, ratio of external concentrations and type of ions.