氧化石墨烯-陶瓷复合纳滤膜的层层自组装制备及其性能

氧化石墨烯（GO）的片层边缘含有 COOH等含氧官能团,因而带负电荷,可以在带正电荷多孔基体上通过层层自组装实现快速沉积。以由3-氨丙基三乙氧基硅烷（APTES）修饰的多孔氧化铝管式陶瓷膜为基膜,令GO和聚乙烯亚胺（PEI）以溶液形态在其表面交替沉积实现自组装,继以环氧氯丙烷（ECH）交联之,制备新型氧化石墨烯-陶瓷复合纳滤膜。最佳制备工艺是,PEI浓度5 g·L^-1、pH=9,NaCl浓度0.3 mol·L^-1,GO浓度0.6 mg·ml^-1、pH 4.5,层数2层,ECH用量6.25 ml·L^-1,50℃条件下处理70 min。层数为1～4层的自组装膜在0.6 MPa操作压力下对2 g·L^-1的MgCl₂的截留率分别为90.16%、93.71%、97.54%、92.93%,其中1层自组装膜的渗透通量为21.92 L·m^-2·h^-1。氧化石墨烯-陶瓷复合纳滤膜对4种无机盐的截留率大小为MgCl₂ >MgSO₄ > NaCl >Na₂SO₄,符合典型正电荷纳滤膜的特征。     

Ionic liquid-induced deep grafting of polyelectrolyte to reform polyamide layer for antifouling nanofiltration membrane

Surface grafting has been widely used to tune hydrophilicity and chargeability of nanofiltration membranes for reducing membrane fouling potential. However, surface grafting typically leads to a significant pore narrowing and resultant permeability loss, and monocharged surface still struggles to resist mixed foulants with different charges. Herein, ionic liquid (IL)-ethanol (EtOH) solution containing polyethyleneimine (PEI) is used to rearrange the nascent polyamide layer. The high affinity of IL to the PA layer and the low diffusion steric hindrance of EtOH contribute to the polyamide swelling and PEI deep grafting, during which the “self-regulation” effect (larger pores would be filled with more PEI molecules) narrows the pore size distribution and enhances hydrophilicity. The nearly charge-neutral and smooth separation layer shows impressive antifouling capacity to hydrophobic macromolecules and mixed charged molecules, along with long-term operating stability for real wastewater treatment. This study emphasizes the importance of solvent properties on the membrane grafting behavior.     

耐溶剂复合纳滤膜的研究进展

耐溶剂纳滤是一种新型的膜分离技术,用于有机混合物的分离。商品耐溶剂纳滤膜大多是采用相转化法制备的整体皮层非对称膜,膜皮层较厚,通量较低。耐溶剂复合纳滤膜由基膜和分离层组成,具有薄皮层、高溶剂通量和高溶质截留率的优点。耐溶剂复合纳滤膜的制备与改性也因此成为近年来的研究热点。本文从界面聚合、表面涂覆、层层自组装、原位生长、有机-无机杂化和表面改性六个方面介绍耐溶剂复合纳滤膜的研究进展,最后对其发展前景进行展望。     

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。     

活性紫染料纳滤脱盐精制的研究

对某染料厂提供的活性紫粗制染料液进行了纳滤膜筛选和脱盐浓缩精制的间歇恒容渗滤实验研究。膜筛选实验表明:DK膜较之DL膜和NF270膜更适合于活性紫染料脱盐浓缩精制的渗滤过程。间歇恒容渗滤操作参数为:活性紫粗制染料液含染料质量分数 5%,含盐质量分数 0 8%;染料含盐质量分数为 16%,渗滤操作压力 1 0MPa,膜面循环通量 1 4m3 /h,渗滤浓缩 2倍,渗滤时间 80h,结果含盐质量分数降至 0 75%,染料纯度达到 99%以上;最后将料液浓缩 3倍,以降低后续喷雾干燥的能耗。该实验研究为工业化提供了依据。     

新型还原氧化石墨烯/氮化碳复合纳滤膜制备及其性能

高性能石墨烯基复合膜的制备是目前国际研究热点,但是石墨烯基纳滤膜在脱盐中水通量较低,限制其在脱盐中的应用。采用聚多巴胺(PDA)改性聚砜(PSF)膜为基膜,将还原氧化石墨烯(rGO)和超薄氮化碳(uCN)纳米片通过真空抽滤法在基膜表面自组装制备新型还原氧化石墨烯/氮化碳复合纳滤膜。通过场发射扫描电子显微镜、透射电子显微镜、X 射线衍射仪、傅里叶变换红外光谱仪和X射线光电子能谱仪等研究uCN添加对膜结构和形貌的影响,并考察不同uCN添加比例、rGO用量及压力复合纳滤膜性能变化规律。结果显示当在100 mg·L^-1的rGO中添加uCN为20 mg·L^-1时所制备的rGO/uCN复合纳滤膜不仅保持良好盐离子截留率(对Na₂SO₄截留率85.86%,对NaCl截留率30.17%),且水渗透系数是rGO膜的2.15倍(88.50 L·m^-2·h^-1·MPa^-1)。     

Solvation-amination-synergy that neutralizes interfacially polymerized membranes for ultrahigh selective nanofiltration

Molecular desalination is broadly used in chemical, food, and textile industries, which needs efficient and anti-fouling separation technologies to reach this goal. Interfacial polymerization is one of the most promising routes to construct ultrahigh selective nanofiltration membranes. However, the irreversible hydrolysis of residual acyl chlorides makes Donnan charges of nascent films distribute unevenly which hinders fine molecular desalination and anti-fouling. Here, we propose a pioneering solvation-amination-synergy strategy to synchronously inhibit the hydrolysis of residual acyl chlorides and promote their amination. The electroneutral nanofiltration membrane with high water permeance (13.2 L m⁻² h⁻¹ bar⁻¹) is quantitatively fabricated that has superb anti-fouling abilities and minimizes Donnan impacts on competitive ion penetrations, so it transmits Na₂SO₄ and NaCl while fully obstructs cationic or anionic dyes (< 500 Da). The ultrahigh molecule to ion selectivities outperform state-of-art nanofiltration membranes, which may provide a paradigm shift for scalable membrane fabrication for various industrial product desalination.     

TiO2-incorporated polyelectrolyte composite membrane with transformable hydrophilicity/hydrophobicity for nanofiltration separation

The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane. In this work, a hydrophilic PDA-[PDDA/TiO₂]⁺ Cl⁻ membrane was prepared by a one-step codeposition of poly(diallyldimethylammonium chloride) (PDDA) polyelectrolyte solution containing positively charged TiO₂@PDDA nanoparticles with the assistance of dopamine (DA). Such positively charged membrane can be transformed into a hydrophobic membrane PDA-[PDDA/TiO₂]⁺ PFO⁻ via the counterion exchange between Cl⁻ and PFO⁻ (perfluorooctanoate). The transformation between hydrophilicity and hydrophobicity is reversible. For both hydrophilic and hydrophobic membranes, the nanofiltration performances were respectively investigated by the aqueous solution and ethanol solution of dyes including methyl blue (MB), Congo red (CR) and Evans blue (EB), and as well metal salt aqueous solution. The consecutive running stability and anti-fouling performance of both hydrophilic and hydrophobic membranes were explored. The results revealed that both membranes showed high nanofiltration performances for retention of dyes in (non)aqueous solution. For the hydrophilic membrane, the rejection of salts in a sequence is MgSO₄ > Na₂SO₄ > MgCl₂ > NaCl. Moreover, both of the hydrophilic and hydrophobic membranes showed high stability and antifouling property.     

纳滤膜分离技术在废水处理中的应用

纳滤作为一种新型分离技术，在处理废水的同时能够回收有用物质，因而在废水处理中得到了越来越广泛的应用。首先简介了纳滤膜分离技术的原理及特点，然后论述了纳滤膜的分离机理，接着介绍了用于表述膜的结构与性能之间关系的空间电荷、固定电荷和细孔等数学模型，最后对纳滤膜在生活污水、石油工业废水、化学工业废水、食品工业废水、造纸废水、印染废水、酸洗废液、重金属废水和电厂二次废水处理中的应用作了较全面的综述。     

适用于镁锂分离纳滤膜的筛选

纳滤膜广泛应用于各分离领域,市售纳滤膜种类繁多,分离性能差异很大。对6种市售的纳滤膜（NT102、NT103、NT201、NF90、NF270、XN-45）进行镁锂分离实验,通过改变原料液稀释倍数、镁锂比、温度、pH及操作压力等条件,测得在不同条件下6种纳滤膜对镁锂的分离性能。结果表明：6种纳滤膜对镁锂分离性能具有明显差异,NT201和NT103最好,NF270和XN-45次之,NF90和NT102最差,可见NT201、NT103纳滤膜对镁锂分离性能最为优异。     

用于喷墨印花染料纯化的自组装GO/TiO2复合纳滤膜的制备

数码喷墨打印技术对墨水高纯度和低含盐量要求,不断促使染料纯化技术的开发与研究。基于氧化石墨烯(GO)/纳米二氧化钛(TiO₂)自组装的纳滤膜材料的开发,探究了纳米TiO₂颗粒尺寸和与GO共混比例,所获最优GO/TiO₂复合纳滤膜中TiO₂颗粒尺寸为60 nm,与GO共混比例为1∶1。其纯水通量为10.69 L/(m²·h·bar),对NaCl和Na₂SO₄的截留分别为12.6%和15.7%,对铬黑T、刚果红和考马斯亮蓝R的截留均高于99%。采用自制的连续恒容渗滤装置对粗品墨水进行染料脱盐浓缩的实验,所获染料的浓度由最初的2.0 g/L浓缩至9.74 g/L,NaCl和Na₂SO₄浓度则由起始10 g/L分别下降至5.3 mg/L和11 mg/L,满足数码印花对墨水高纯度以及低盐度的要求。     

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。     

Fe3+交联聚乙烯亚胺-单宁酸复合纳滤膜研究

利用聚乙烯亚胺(PEI)、单宁酸(TA)与Fe³⁺之间的螯合作用,通过层层自组装技术,制备了PEI-TA复合纳滤膜,对其表面形态及性能进行了表征,并研究了TA、Fe³⁺含量和组装层数对膜性能的影响。结果表明,当PEI、TA、Fe³⁺的质量浓度分别为2、3、3 g/L,组装层数为6层时,复合膜性能为优。优化膜对Na₂SO₄、MgCl₂、NaCl的截留率分别为97.34%、65.46%、73.11%,水通量达24.91 L/(m²·h)。该复合膜制备工艺简单、绿色,在脱盐、水质软化等水处理领域具有应用潜力。     

纳滤膜在盐湖提锂领域的研究进展

中国锂（Li）资源消耗量占全球消耗量的40%,然而其产能仅能满足工业需求的20%,80%的Li需要进口,研究新一代提Li技术需迫在眉睫。纳滤（NF）膜具有选择性离子分离能力,在Mg2+、Li+的选择性分离中表现出突出的潜力。商用NF膜多荷负电,受Donnan效应和静电引力影响,其对正离子的分离能力有限。近年来,人们发现荷正电NF膜可以有效分离具有相似水合物离子半径的Mg2+和Li+。该文介绍了NF膜中离子传输理论和选择性筛分机理,综述了商用NF膜在盐湖提Li领域的研究现状及不足,分析了荷正电NF膜的制备方式（包括胺单体的选取、纳米材料掺杂、引入中间层及表面接枝等）对提升Mg2+、Li+的选择性分离性能的影响规律。最后,总结了荷正电NF膜在实际工程应用中的挑战和前景。     

Preparation and separation properties of polyamide nanofiltration membrane

Utilizing an interfacial polymerization technique for the preparation of a polymeric composite nanofiltration membrane, both high permeation flux of water and high salt rejection can be achieved. Synthesis conditions, such as concentration of monomer, reaction time, and swelling agent, significantly affected the separation performance of composite membranes. The composite polyamide membrane had a permeation rate of ～2–5 gallon/ft²/day (gfd) and a salt rejection rate of ～94–99% when 2000 ppm aqueous salt solution was fed at 200 psi and 25°C. Also, a higher performance nanofiltration membrane could be prepared by suitably swelling the support matrix in the period of polymerization. The results of various feed concentrations showed that permeate flux decreased with increasing salt concentration in the feed solution. This result may be due to concentration polarization on the surface of polyamide membranes. The separation performance of polyamide membranes showed an almost independent relationship with operation pressure until it was up to 200 psi. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1112–1118, 2002     

纳滤膜法除硫酸根技术进展

从工艺及工程角度比较了去除SO4^2-的几种方法,对纳滤膜法脱除SO4^2-的技术进行了详细论述,并探讨了该技术的后处理方法。     

聚酰亚胺膜的制备及对有机物系的纳滤分离

针对以均苯四甲酸二酐(PMDA)和4,4′-二氨基二苯醚(ODA)为原料合成聚酰亚胺的过程,研究了亚胺化方法、凝胶浴组成与温度等条件对膜的结构和分离性能的影响。实验结果表明,当聚酰胺酸铸膜液质量分数为15%、凝胶浴为30%乙醇(质量)的醇水溶液时,所制得的聚酰亚胺纳滤膜具有最佳的分离性能。操作压力为2MPa下稳态操作时,该膜对酮苯脱蜡工艺后的溶剂与润滑油基础油混合物的截留率达66%,通量为4.26L/(m2.h),为有机溶剂体系的纳滤膜分离技术的工业应用提供了基础。     

Preparation and performance of novel thermal stable composite nanofiltration membrane

The novel thermal stable composite nanofiltration membranes were prepared through the interfacial polymerization of piperazine and trimesoyl chloride on the poly (phthalazinone ether) ultrafiltration substrate. The effects of polymerization and testing conditions on membrane performance were studied. The surface morphologies of the substrate and the composite membranes were observed by means of scanning electron microscopy (SEM) and atomic force microscopy (AFM). The separation properties of membranes for dyes and salts were tested. The composite membranes show good thermal stability. The rejection for Na2SO4 was kept over 96%, while the flux reached 400 L·m⁻²·h⁻¹ when it was tested at 1.0 MPa and 80°C. When tested at 1.0 MPa and 60°C, the rejection of the composite membrane for dyes was kept at high level, and the flux reached 180–210 L·m⁻²·h⁻¹, while the rejection for NaCl was lower than 20%. __________ Translated from the Journal of Functional Materials, 2007, 38(12): 2025–2027, 2031 [译自: 功能材料]     

利用纳滤膜分离精制饱和卤水的研究

针对饱和卤水直接制碱过程需要去除硫酸根、钙离子、镁离子（SO₄^2-、Ca²⁺、Mg²⁺）等杂质离子的问题,探索了利用纳滤膜分离精制饱和卤水新工艺。通过考察NF270、DL2540、ESNA1 3种类型纳滤膜的透过通量和离子截留率,确定了选用DL2540为实验用膜;分析了DL2540纳滤膜对离子的截留性能和对盐田饱和卤水的分离性能及其对饱和卤水精制的效果。结果表明,增加同离子浓度、降低压力有利于不同价态阳离子、阴离子间的分离,DL2540纳滤膜对盐田饱和卤水中SO₄^2-、Ca²⁺、Mg²⁺截留率分别达到95%以上、30%~50%、30%~70%,对Na⁺、Cl^-截留率均低于15%,进一步证明DL2540纳滤膜具有较好的稳定性和二价离子截留效果,在饱和卤水精制上展示出较好的应用前景。     

Studies on integration of ion exchange and nanofiltration for water desalination

This work addresses an integrated treatment to produce drinking water involving the ion exchange (IEX) and nanofiltration processes. In the first stage, the experimental procedure consisted of evaluating the IEX equilibrium and the dynamics of fixed-bed saturation/regenerations, for the system Cl^?/SO₄², using an anionic resin, Purolite A850, in the form sulphate. A mathematical model which considers axial dispersion for the liquid phase and linear driving force for intraparticle mass transfer predicted well the breakthrough curves of Cl^? and SO₄^2?. In the second stage, the selective separation of Cl^?, Na⁺ and SO₄^2? ions through a flat membrane nanofiltration TS80 was assessed.