水溶性荧光染料溶液脱盐浓缩的纳滤实验研究

选用NTR7450和NF270两种纳滤膜对水溶性工业荧光染料原液进行分离，选择出透过通量大、除盐效果好和染料截留率高的纳滤膜，并对该染料溶液进行了脱盐和浓缩的间歇渗滤过程研究：在温度25℃和压力1.0MPa下，膜对染料截留率达到100％，最终料液中NaCl浓度从0.214mol／L降到0.0025mol／L,料液被浓缩了2．6倍。说明纳滤膜的间歇渗滤操作过程能够实现染料溶液的脱盐浓缩。     

Reactive dye removal in dye/salt mixtures by nanofiltration membranes containing vinylsulphone dyes: effects of feed concentration and cross flow velocity

In this study, DS5 DK type nanofiltration membranes were tested to recycle the reactive dye bath effluents. Reactive black 5 (RB5), reactive orange 16 (RO16), reactive blue 19 (RB19) and NaCl were used in the experiments to prepare the synthetic dye and salt mixtures. Effects of feed concentration, pressure and cross flow velocity on the permeate flux and color removal were investigated. Permeate flux increased with increasing pressure for all NaCl solutions. Dye concentration had a significant effect on flux values. Under the fixed NaCl concentrations the flux decreased with increasing dye concentrations. Dye rejections greater than 99% were achieved. Permeate was almost colorless. A gel layer formed by the rejected dye on membrane surface operates as a resistance to the permeation of dyes due to complete rejection of high molecule weight dyes, especially for the low salt concentrations. The presence of salt concentration has an interesting effect on color removal. Color removal decreased with increasing salt concentration. Cross flow velocities had also a significant effect on flux values. The dye formed agglomerates at high NaCl concentrations. High cross flow velocities decreased this effect.     

Dye removal from colored textile wastewater using acrylic grafted nanomembrane

In this paper, the dye removal ability of the acrylic grafted polysulfone nanomembrane using ultraviolet radiation was studied to remove dyes from colored textile wastewater. Acrylic acid was used to modify polysulfone ultrafiltration membrane. The effect of different operating parameters such as pressure, salt concentration and chemical structure of dyes was evaluated. Data indicated that the photografted membrane has acceptable performance both in terms of flux and rejection. The dye rejection and hydraulic permeability were 86–99.9% and 7.6 L m^{− 2} h^{− 1} bar^{− 1}, respectively. It was found that the rejection of dyes decreased with salt concentration due to a decrease of the Donnan effect. Also, the low molecular weight dyes and highly charged dyes were more sensitive in the presence of salts. Addition of 80 mM Na₂SO₄ in dye solution decreased the dye rejection more than 15%. The rejection enhancement for all cases was negligible by increasing driving pressure from 1 to 4 bar. Dyes with low charger were more sensitive to operating pressure than that of dyes with higher charges. All findings supported that acrylic grafted nanomembrane is potentially capable to separate dyes from colored textile effluent.     

The reuse of reactive dye liquors using charged ultrafiltration membrane technology

A closed-loop recycle system using a charged ultrafiltration membrane to decolourise reactive dye effluents from a textile yarn and fabric dyeing process is described. The economics of the process depend on the value of the electrolyte ($5 to $10 per M³). Conventional reactive dyeing technology was examined and modified to facilitate dye liquor reuse. The performance of the membrane was examined in terms of electrolyte rejection, colour rejection and permeate flux under varying conditions of solution pH, ionic strength and operating pressure.     

聚电解质静电沉积改性制备高性能反渗透膜

利用次氯酸钠溶液对商品反渗透膜表面进行氯化处理,然后将聚阳离子电解质壳聚糖通过静电吸附作用沉积在RO膜的表面,系统地研究了氯化过程的pH、氯化时间、次氯酸钠浓度、壳聚糖浓度及其沉积时间对膜性能的影响,以制备出高通量、高截留率的RO膜。在压力1.55 MPa、原料液温度（298±1）K的条件下,测定RO膜处理2000 μg·g^-1氯化钠溶液的水通量和截留率。结果表明,当pH=9、氯化时间为30 min、次氯酸钠浓度为1000 mg·L^-1时,水通量较原膜提高了约19.89%,截留率略有提高;当壳聚糖浓度为0.1%（质量分数）、沉积时间为30 min时,改性膜的接触角降低到34.88°,亲水性提高,水通量较氯化后的RO膜几乎保持不变,为60.55 L·m^-2·h^-1,截留率达到了99.56%。经过氯化和沉积改性后的RO膜水通量和截留率均得到了提高。     

高通量聚醚砜纳滤膜的制备及对染料浓缩脱盐

以聚醚砜（PES）为膜材料,以嵌段式聚醚 Pluronic F127为添加剂,利用特制刮膜设备通过相转化法制备出高通量PES/Pluronic F127复合纳滤膜,并将其用于染料的浓缩脱盐。研究了添加剂含量、溶剂蒸发温度和蒸发时间对膜结构和膜性能的影响,考察了不同操作压力和操作温度下膜对染料的分离性能。扫描电镜 （SEM）、接触角、孔隙率数据和蛋白吸附测试结果表明,Pluronic F127改善了膜孔结构,提高了孔隙率,并且显著提高了膜的抗污染性能。纯水通量、截留率以及膜表面孔径表征结果表明,当Pluronic F127含量为3%、溶剂蒸发温度为90℃、 蒸发时间为18 s时,膜的分离性能最佳。在0.6 MPa下该膜对低分子量染料的截留率可达99.9%,且通量达到110.2 L·m^-2·h^-1,对NaCl的截留率仅为5.5%。在12 h的染料浓缩脱盐中,膜对染料的通量维持在较高水平且截留率始终保持在99%左右,具有良好的稳定性和抗污染性。     

Electrolyte removal by mixed matrix membranes based on polyurethane

The membrane processes play a significant role in the water and wastewater treatment to remove dissolved solids, especially electrolytes. In this study, the asymmetric mixed matrix membranes based on polyurethane and SAPO-5 zeolite were used on electrolyte (NaCl) removal from water. Using a low operating pressure, the membrane performances (i.e., pure water permeation, flux and salt rejection) were measured. All membranes were showing an increase in water flux when the pressure was increased. This situation shows that the produced membranes were stable in producing flux and were suitable to be used to proceed for membrane testing process. Based on the results obtained, rejection of salt water increased as the pressure given increased for each membrane. The mixed matrix membranes showed the high rejection for the salt water (NaCl 0.02 M). This shows the good performance in both flux and rejection, and even achieves 98% rejection for the NaCl 0.02 M. Based on the experimental results, it is believed that these mixed matrix membranes are suitable for the electrolytes removal applications.     

DYE RECOVERY BY LOW PRESSURE ULTRAFILTRATION†

Ultrafiltration or textile dyes using polyacrylonitrile hollow fibers is reported. Experiments were carried out in recirculating system with various flow intensities along the fiber. Dependence of rejection and membrane flux on concentration of bulk solution is presented. Due to aggregation of dye particles and good separation characteristics of membranes used high water recovery and concentration of dyes were obtained.     

DYE RECOVERY BY LOW PRESSURE ULTRAFILTRATION†

Ultrafiltration or textile dyes using polyacrylonitrile hollow fibers is reported. Experiments were carried out in recirculating system with various flow intensities along the fiber. Dependence of rejection and membrane flux on concentration of bulk solution is presented. Due to aggregation of dye particles and good separation characteristics of membranes used high water recovery and concentration of dyes were obtained.     

Green and feasible fabrication of loose nanofiltration membrane with high efficiency for fractionation of dye/NaCl mixture by taking advantage of membrane fouling

Loose nanofiltration membrane emerges as required recently, since it is hard for conventional nanofiltration membrane to fractionate mixture of dyes and salts in textile wastewater treatment. However, the polymeric membranes unavoidably suffer from membrane fouling, which was caused by the adsorption of organic pollutants (like dyes). Normally, the dye fouling layer will shrink membrane pore size, thus resulting in flux decline and rejection increase. It is thought that membrane fouling may be a double-edged sword and can be an advantage if properly utilized. Thereby, loose nanofiltration membranes were constructed here by a green yet effective method to fractionate dyes/salt mixture by taking advantage of membrane fouling without using poisonous ingredients. A commercially available polyacrylonitrile (PAN) ultrafiltration membrane with high permeability was chosen as the substrate, and dyes were used to contaminate PAN substrate and formed a stable barrier layer when adsorption of dyes reached dynamic equilibrium. The resultant PAN-direct red 80 (DR80) composite membranes displayed superior permeability (~128.4 L m⁻² h⁻¹) and high rejection (~99.9%) to DR80 solutions at 0.4 MPa. Moreover, PAN-DR80 membranes allowed fast fractionation of dyes/sodium chloride (NaCl) mixture, which maintained a negligible dye loss and a low NaCl rejection (~12.4%) with high flux of 113.6 L m⁻² h⁻¹ at 0.4 MPa. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47438.     

用活性炭吸附强化超滤过程脱除废水中染料的研究(英文)

In this study, orange G dye was efficiently removed from aqueous solution by ultrafiltration (UF) mem-brane separation enhanced with activated carbon adsorption. The powdered activated carbon (PAC) was deposited onto the UF membrane surface, forming an intact filter cake. The enhanced UF process simultaneously exploited the high water permeation flux of porous membrane and the high adsorption ability of PAC toward dye molecules. The influencing factors on the dye removal were investigated. The results indicated that with sufficient PAC incor-poration, the formation of intact PAC filtration cake led to nearly complete rejection for dye solution under opti-mized dye concentration and operation pressure, without large sacrificing the permeation flux of the filtration process. Typically, the dye rejection ratio increased from 43.6% for single UF without adsorption to nearly 100% for the en-hanced UF process, achieving long time continuous treatment with water permeation flux of 47 L·m 2·h 1. The pre-sent study demonstrated that adsorption enhanced UF may be a feasible method for the dye wastewater treatment.     

聚酰胺非对称纳滤膜在印染废水深度处理中的应用

利用自制的聚酰胺非对称纳滤膜处理水溶性阴离子染料废水,并与NF270商品膜性能进行了比较研究。在0.7 MPa和25℃的条件下,所制纳滤膜对3种阴离子染料的截留率均大于95%。24 h染料连续脱盐运行条件下,膜的水通量保持在50 L.m-2·h-1,染料截留率96%以上,脱盐率稳定在5%以下,具有较好的选择分离性和耐污染性。2种纳滤膜的性能对比研究表明,所制PMIA非对称纳滤膜的染料截留能力和耐高温性优于NF270商品膜,但膜通量稍低。     

Concentration and diafiltration of aqueous fluorescent whitener solution by nanofiltration

Concentration and desalination of NT dye solutions by nanofiltration were studied experimentally with a spiral-wound nanofiltration membrane element. The decrease of permeation flux and increase of the observed NaCl rejection were observed due to the formation of the gel layer and possibly the precipitate layer on the membrane surface due to the high bulk NT concentration. By analyzing concentration polarization of NaCl at the membrane-solution interface, a simple empirical correlation between the permeation flux and the interfacial mass transport coefficient was obtained and coupled with a simplified S-K model for prediction of concentration and desalination of NT solutions. The concentration polarization was investigated using the simplified model that complied with the theoretical understanding. Several operations were compared, which resulted in an optimized technology for potential field implementation.     

Removal of dyes by poly(p-phenylene terephthamide)/polyvinylidene fluoride hollow fiber in-situ blend membranes

In order to obtain the compatible poly(p-phenylene terephthalamide) (PPTA)/polyvinylidene fluoride (PVDF) blend membranes, the casting solution was synthesized via the in situ polycondensation process and flat sheet blend membranes were successfully prepared through the immersion precipitation phase inversion method in our previous study. In this study, the polycondensation solution was directly used as the spinning dope to fabricate PPTA/PVDF hollow fiber in-situ blend membrane by the dry-wet spinning technique. Hollow fiber membranes were employed to remove the dyes including Congo red (CR) and methylene blue (MB) from the dyeing liquor. Effects of operation conditions on dye rejection and membrane water flux were investigated. With the increase of operation pressure, feed concentration and feed temperature, dye rejection rates gradually decreased, but the rejection value of CR and MB still remained above 99.5%. On the contrary, the permeation water flux basically increased. During the continuous dye filtration of 300 min, hollow fiber membrane can maintain high dye rejection rates and stable water flux. The combination method of physical backwashing and chemical cleaning can effectively alleviate membrane fouling and recover membrane water flux. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48569.     

超声作用对NaCl和MgSO4溶液在纳滤膜内传质的影响

将超声波用于强化电解质溶液在纳滤膜内的传质过程,研究超声作用下NaCl和MgSO₄溶液在聚酰胺纳滤膜内的传质机理,考察超声作用对膜通量、截留率和跨膜电位随跨膜压差变化规律的影响。实验结果表明,与无超声作用相比,施加在膜表面的超声作用增大了膜通量,降低了截留率,提高了跨膜电位。     

高浓度含盐草甘膦溶液的纳滤分离实验研究

为了考察纳滤技术分离含高浓度单价盐的草甘膦溶液的可行性,采用商业化Desal-DK纳滤膜对含有高浓度NaCl的草甘膦溶液开展了分离实验研究和模拟计算。首先研究了物料浓度、跨膜压差等因素对NaCl和草甘膦的单组分溶液的体积通量及截留率的影响,并通过拟合SK（Spiegler-Kedem）方程计算得到了膜的特征参数;其次探究了Desal-DK纳滤膜对高浓度NaCl和不同浓度草甘膦混合溶液的分离效果,实验结果说明Desal-DK纳滤膜对NaCl呈现较高的透过性,而对草甘膦则呈现较高的截留性,从而能够有效实现草甘膦和NaCl的分离;最后通过对含有100 g/L NaCl和1 g/L草甘膦的混合溶液进行预浓缩-连续恒容渗滤过程的模拟计算,得到了较高浓度的草甘膦溶液和相对较纯的NaCl溶液,证明通过纳滤渗滤过程实现含草甘膦浓盐水的资源化利用是可行的。     

Nanofiltration for the possible reuse of water and recovery of sodium chloride salt from textile effluent

During the reactive dyeing of cotton, salts such as sodium chloride (NaCl) are placed in a dyebath to aid the exhaustion of various dyes onto the fabric while bases are added to raise the pH from around neutral to pH 11 to achieve fixation. Afterwards, the used dyebath solution, called dyebath spent liquor, is discharged with almost all the salts and bases added as well as unfixed dyes. Consequently, many raw materials are lost in the waste stream ending up in the environment as pollutants. In this study possibilities of reusing the water and salts of dyebaths were investigated using a nanofiltration membrane. When the NaCl concentration in the spent liquor was increased from 10 to 80 g/L, the NaCl rejection by the membrane was found to decrease initially; however, the NaCl rejection increased over time, which was not expected. The aggregation of dye was also studied and found to decrease in the concentrate when the salt concentration was increased. This information is useful for the textile industry in evaluating the treated water quality for the purpose of reuse.     

反渗透、纳滤过程的物理化学研究（Ⅱ） 多孔荷电膜的溶质分离规律

在多孔膜溶质的脱除率方程和溶液渗透通量方程的基础上由溶液电中性条件导出了荷电膜的单价电解质、中性分子混合溶液体系离子的脱除率方程,中性分子的脱除率方程,溶液渗透体积通量方程和离子、中性分子的浓缩比表达式。由方程的函数性质讨论了荷电膜的单价电解质、中性分子混合溶液的溶质组分脱除率和溶液渗透体积通量随离子浓度、pH值的变化规律。预测了盐和中性分子的脱除率和溶液渗透体积通量随浓度变化曲线出现极大和极小值的现象,由此得出了下列结果：随pH值的增加,单价电解质溶液的阳离子、阴离子和氢离子的脱除率变化顺序为由 R _M⁺ > R _X^- > R _H⁺变化到R _M⁺ =R _X^-> R _H⁺再变化到R _X^->R _M⁺> R _H⁺,离子脱除率变化曲线将出现极大和极小值;有机酸的总脱除率表达式阐明了文献中的可电离有机分子与pH值的关系式中参数的物理意义,解释了该关系式的对氨基苯甲酸水溶液的脱除率随pH值变化的拟合曲线高于脱除率实验值的原因,解释了对氨基苯甲酸的甲醇溶液的溶质脱除规律;离子的浓缩比依赖于料液中离子组成和离子所对应盐的浓缩比。     

A melamine-based covalent organic framework nanomaterial as a nanofiller in polyethersulfone mixed matrix membranes to improve separation and antifouling performance

This research reported developing a polyethersulfone (PES) membrane using covalent organic frameworks (COFs) nanoparticle with a mean dimension of 30 nm. The SNW-1 (Schiff-based network) COF was synthesized using precursors of melamine and terephthalic acid and then characterized by XRD, SEM, TEM, and FTIR analyses. The influence of different loadings of the COF was evaluated on the permeability, antifouling behavior and dye/salt rejection. The addition of SNW-1 caused a reduction in surface roughness and an improvement in hydrophilicity of the nanocomposite membranes, which improved their flux and fouling resistance considerably. The improvement of water flux, 2.6 times, was observed by adding 0.5 wt% COF to the membrane matrix. The 0.5 wt% COF membrane presented the best water permeability, 38.9 L/m² h bar BSA solution flux, dye rejection of 98.7% for Reactive Green 19 and 62.6% for Reactive yellow 39, 52.9% Na₂SO₄ and 24.5% NaCl salt rejections. Zeta potential and salt rejection trend indicated a negative surface charge on the nanocomposite membrane. Fouling experiments by BSA protein solution exhibited that the FRR reached 88.9% for 2 wt% COF membrane. Thus, employing SNW-1 into PES matrix resulted in a promising nanofiltration membrane for dye separation and moderate salt separation with suitable antifouling properties.     

Grafted polypropylene membranes for purification of water containing sodium alkylbenzenesulfonate

The possibility of eliminating sodium alkylbenzenesulfonate (ABS) from water by reverse osmosis was examined by operating with polypropylene membranes grafted with poly(acrylic acid). Flux through the membranes decreases with increasing thickness. For 23μ thickness and 0.5 1./hr-m² flux, the rejection is 100% (operating pressure, 50 atm: concentration, 1 g ABS/l.). For 5μ thickness the rejection is lower and is related to ABS concentration: rejection increases with increasing concentration and reaches 60% for concentrations higher than 5 g ABS/l. (flux, 51./hr-m²; operating pressure, 50 atm). This is ascribed to the prevailing ultrafiltration as regards the reverse osmosis. ABS, at higher concentrations than the critical value, gives micelles whose dimensions might be compared to pores. The membrane behavior is influenced by previous treatments; when the membrane has been conditioned in NaCl solution, it is more selective and more permeable; the rejection reaches 90% with fluxes of 6.8 l./hr-m² for concentrations of 5 g ABS/1. (operating pressure, 50 atm). In order to relate the properties to the structure of membranes, we have examined them by electron microscope. The ion exchange which takes place between membrane and NaCl and between membrane and ABS has also been studied.