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。     

分光光度法测定纳滤膜对聚乙二醇的截留率

利用分光光度法可以准确且便捷的测定不同分子量聚乙二醇（PEG）水溶液的浓度;而利用不同分子量的聚乙二醇水溶液可以检测过滤膜的分离性能。本文在利用分光光度法测定聚乙二醇水溶液的实验基础上,初步研究了纳滤膜对不同分子量聚乙二醇的截留率。     

Preparation and characterization of asymmetric polyethersulfone and thin-film composite polyamide nanofiltration membranes for water softening

In this research, two types of nanofiltration membranes were prepared and evaluated for water softening. Their nanofiltration performance was evaluated by cross-flow filtration using NaCl (1 g/l) and MgSO₄ (1 g/l) solution at 5 and 10 bar, 25 °C and 10 l/min. The morphological studies were performed with SEM and AFM instruments. In addition, the hydrophilicity of membranes was examined by contact angle measurements. In the first type, asymmetric polyethersulfone (PES) nanofiltration membranes were prepared using phase inversion induced by immersion precipitation technique. Different components such as polyvinylpyrrolidone (PVP), polyethyleneglycole (PEG), acrylic acid and Triton X-100 were used as additive in the PES casting solution, which lead to the formation of new asymmetric nanofiltration membranes. Two concentrations of PES (20 and 25 wt%) and two different non-solvents (pure water and mixture of water (80 vol.%) and IPA (20 vol.%)) were used for preparing asymmetric nanofiltration membranes. The morphological studies showed that the membranes prepared with non-solvent containing 20 vol.% IPA have smoother surface and smaller pores in surface and sub-layer compared to membranes prepared with pure water as non-solvent. The flux was decreased when higher polymer concentration and mixture of water and IPA were employed for membrane formation. However, NaCl and MgSO₄ rejections were improved. In the second type, thin-film composite polyamide nanofiltration membrane was fabricated using interfacial polymerization of 1,3-phenylenediamine (PDA) with trimesoyl chloride (TMC). A rough and dense film was formed on the PES support membrane by interfacial polymerization. The water permeability of composite membrane was 7 and 21 kg m⁻² h⁻¹ at 5 and 10 bar, respectively. Moreover, the rejection to the MgSO₄ as divalent salt (85 and 90%) was high compared to the NaCl as monovalent salt (64 and 67%).     

Prediction of the concentration polarization in the nanofiltration/reverse osmosis of dilute multi-ionic solutions

The aim of this work was to develop a simple and accurate model for predicting the concentration polarization index in the nanofiltration (NF)/reverse osmosis (RO) of dilute multi-ionic solutions. On the grounds of this model, the total flux of the ion i at the feed-solution/membrane interface consists of the sum of the diffusion, convection and migration fluxes, the former of which is determined by conventional mass-transfer correlations duly corrected to take into account the permeation through the membrane (suction effect). The coupling of the ionic fluxes is enforced by the electroneutrality requirement at the feed-solution/membrane interface. The model developed dispenses with the arbitrary assumption of the thickness of a film layer in the vicinity of the membrane surface.

Assessing the accuracy/validity of this model with multi-ionic solutions would be rather harsh, thus the model accuracy and ranges of validity were ascertained for a benchmark case: NF/RO of single salt solutions. The model predicts approximate concentration polarization indexes of the salts A⁺B⁻, A⁺₂B²⁻ and A⁺₃B³⁻ (or A²B⁻₂ and A³⁺B⁻₃) with positive deviations lower than 10% with respect to the benchmark concentration polarization index, for ions diffusivities ratios, D₁/D₂ (or D₂/D₁), in the range 0.16–5.5 and ≡J_v/k_c<3, where J_v is the permeation flux and k_c is the mass-transfer coefficient of the salt for vanishing mass-transfer rates at impermeable walls. The main assumption of the model – the individual mass-transfer coefficients of the ions are independent of each other – appears to hold in a broad range of conditions, for single salt solutions.

The model developed was expeditely applied to predict the concentration polarization in the nanofiltration of solutions containing Na⁺, Cl⁻ and a dye³⁻ (experimental data of Bowen and Mohammad [AIChE J. 44 (8) (1998) 1799–1812]), and its predictions are in fair agreement with the predictions of the extended Nernst–Planck equations in the film layer of the “slowest” ion.     

Nanofiltration membrane behavior in a supercritical medium

The permeability values of “TN” organomineral nanofiltration membranes to water, L, and to supercritical CO₂, G, were compared. The resulting values for G were an order of magnitude higher than for L. The difference may be directly related to the viscosity difference between the two fluids. Temperature- and pressure-related variations in G were also analyzed; for this purpose, Poiseuille's model satisfactorily accounts for experimental behavior, while Knudsen's model is unsuitable. A hysteresis effect was observed on the isotherms corresponding to variations in G versus pressure, suggesting partially irreversible CO₂ adsorption on the micropore walls, that would diminish the radius. This phenomenon could be enhanced by an increased fluid density and viscosity.     

Effect of electron beam irradiation on morphology and sieving characteristics of nylon-66 membranes

Nylon-66 is a typical semicrystalline polymer that can be crosslinked through electron beam (EB) irradiation. Crosslinking can dramatically change polymer properties. The objective of this research was to observe how EB irradiation affects morphology and sieving characteristics of nylon-66 membranes. EB irradiation was carried out in air at 60, 70 and 80 kGy doses. Scanning electron microscopy (SEM), swelling and gel content studies evidenced the morphological changes and crosslinking of nylon-66 membranes. Sieving characteristics were also measured using pure water permeation, and rejection of raffinose, vitamin B12, and mono- and divalent salts. These results show that nylon-66 membrane surface and permeation characteristics changed with different irradiation doses. The nylon-66 surface became denser and the gel content increased with increasing irradiation dose. Furthermore, pure water permeation decreased and small molecules were increasingly rejected with greater irradiation doses. The amount of rejection was between 33% and 88.4% for vitamin B12 and between 16% and 83% for raffinose. The highest vitamin B12 and raffinose rejection was seen with a N-80 membrane, and no rejection was measured with N-0 or N-60 membranes. Salt rejection, however, was very low, especially for NaCl, with only 10.51-46% rejected. Based on flux, permeability and uncharged solute (vitamin B12 and raffinose) rejection data, nylon-66 type N-70 and N-80 membranes were estimated to be in the nanofiltration (NF) range.     

Determination of concentration-dependent transport coefficients in nanofiltration: Experimental evaluation of coefficients

To characterize solute transport in nanofiltration (NF) the Spiegler–Kedem equation requires that two coefficients be determined for two-component solutions (a solute in water), solute permeability ω and reflection coefficient σ. For salts both coefficients strongly and in a complex way depend on concentration, which greatly complicates their evaluation from experiments. For this reason, the parameters are usually assumed constant for a given feed and the concentration dependence is assessed from flux–rejection curves for several feeds. This procedure however ignores the fact that the solute concentration and hence the coefficients significantly vary across the membrane. One way to overcome this inconsistency and address concentration dependence is to use physical models explicitly introducing exclusion mechanism(s) and fitting relevant membrane-specific parameters, such as fixed charge or dielectric properties. This procedure often fails to produce unique values of parameters for a given membrane and different salts. In the present study a new phenomenological approach is proposed and critically analyzed, based on the assumption of a similar concentration dependence of ω and 1 − σ, previously shown to be valid under fairly general conditions, thereby the Peclét coefficient A = (1 − σ)/ω may be assumed to be independent of concentration. The coefficients and their concentration dependence for a given solute may be directly and consistently evaluated by fitting flux–rejection data for several feeds and fluxes to numeric solution of the modified transport equations without the need to invoke specific physical models. The values of transport parameters deduced in this way for representative membranes and salts allow important conclusions regarding the transport mechanism. In particular, the roles of different mechanisms in overall salt exclusion could be addressed directly from the variation of ω or 1 − σ with concentration. On the other hand, the value of the Peclét coefficient, free of the effect of salt partitioning, may be analyzed in terms of hindered transport. Using the proposed method, this value was found to be very small for studied thin-film composite membranes, which may significantly simplify the transport equations.     

Effects of membrane degradation on the removal of pharmaceutically active compounds (PhACs) by NF/RO filtration processes

The impacts of membrane degradation due to chlorine attack on the rejection of pharmaceutically active compounds (PhACs) by nanofiltration and reverse osmosis membranes were investigated in this study. Membrane degradation was simulated by soaking the membranes in a sodium hypochlorite solution of various concentrations over 18 h. Changes in membrane surface properties were characterised by contact angle measurement, atomic force microscopy analysis, and streaming potential measurement. The impacts of hypochlorite exposure to the membrane separation processes were ascertained by comparing the rejection of PhACs by virgin and chlorine-exposed membranes. Overall, the reverse osmosis BW30 membrane and the tight nanofiltration NF90 membrane were much more resilient to chlorine exposure than the larger pore size TFC-SR2 and NF270 nanofiltration membranes. In fact, rejection of all three PhACs selected in this study by the BW30 remained largely unchanged after hypochlorite exposure and further characterisation did not reveal any evidence of compromised separation capability. In contrast, the effects of chlorine exposure to the two loose nanofiltration membranes were quite profound. While chlorine exposure generally resulted in reduced rejection of PhACs, a small increase in rejection was observed when a more dilute hypochlorite solution was used. Changes in the membrane surface morphology as well as observed rejection of inorganic salts and PhACs were found to be consistent with mechanisms of chlorine oxidation of polyamide membranes reported in the literature. Chlorine oxidation consistently resulted in a more negative zeta potential of all four membranes investigated in this study. Conformational alterations of the membrane polyamide active skin layer were also evident as reflected by changes in surface roughness before and after chlorine exposure. Such alterations can either loosen or tighten the effective membrane pore size, leading to either a decrease or an increase in rejection. Both of these phenomena were observed in this study, although the decrease in the rejection of PhACs was overwhelming from exposure to highly concentrated hypochlorite solution.     

The role of foulant–foulant electrostatic interaction on limiting flux for RO and NF membranes during humic acid fouling—Theoretical basis,experimental evidence,and AFM interaction force measurement

A limiting flux model has been recently developed for predicting the fouling behavior of reverse osmosis and nanofiltration membranes by organic macromolecules [C.Y. Tang, J.O. Leckie, Membrane independent limiting flux for RO and NF membranes fouled by humic acid, Environmental Science and Technology 41 (2007) 4767–4773]. Several interesting results have been observed: (a) there was a maximum pseudo-stable flux (the limiting flux) beyond which further increase in applied pressure did not translate to a greater stable flux; (b) all membrane samples attained the limiting flux under constant pressure conditions as long as their initial flux was greater than the limiting flux; (c) the limiting flux did not depend on the properties of membranes; (d) the limiting flux had strong dependence on the feedwater composition, such as pH, ionic strength, and divalent ion concentration. The current study investigates the dependence of limiting flux on intermolecular interaction between foulant molecules. It was observed that the limiting flux was directly proportional to the intermolecular electrostatic repulsive force and that conditions enhancing foulant-deposited-foulant repulsion resulted in greater limiting flux values. Such observations agree well with a theoretical model capturing both hydrodynamic and DLVO interactions. Interaction force measurements by atomic force microscopy (AFM) were also performed. The limiting flux correlated reasonably well with AFM interaction force between the model foulant and the fouled membrane surface.