纳滤膜在水处理中的应用

纳滤与传统水处理方法相比具有独特的分离性能,处理效果好,能耗低,同时能回收有用物质,是水处理的有效方法。在饮用水净化处理、污废水排放和回用处理等领域有广泛的研究应用。文章简要介绍了纳滤膜技术的特点,综述了纳滤在饮用水净化、生活污水及垃圾渗滤液处理、工业水和农业水处理中的研究应用现状,并对纳滤技术的应用前景进行了展望。     

藻类对纳滤膜去除萘普生的影响

传统的饮用水处理工艺不能有效地去除水中痕量有机物PPCPs,纳滤(NF)膜工艺对其有较好的去除效果。水中有机物(DOM)的存在对NF膜去除PPCPs有较大的影响,藻类有机物(AOM)的组成及特性不同于天然有机物,它在膜处理工艺中对膜污染有重要的影响。试验研究了2种藻类(鱼腥藻、小球藻)AOM对纳滤膜去除萘普生(NPX)的影响效果。结果显示2种藻类AOM均能促进NF膜对NPX的分离,提高NPX的去除率,但会显著降低膜通量。AOM的分子量分布和亲疏水性与其对NPX去除率的影响有关,AOM中亲水性的多糖和蛋白类有机物质是造成膜污染和影响NPX去除率的主要物质。滤饼层的形成改变了膜表面的亲疏水性能和截流分子量(MWCO),也是造成膜通量衰减和NPX去除率提高的重要原因。     

纳滤膜去除饮用水中微量三唑磷的研究

分别采用NF200、NF90纳滤膜去除饮用水中的微量三唑磷,研究了操作压力、原水中三唑磷浓度、pH和离子强度等因素对其去除效果的影响,并探讨了两种纳滤膜截留三唑磷的机理.结果表明:两种纳滤膜均可有效去除饮用水中的微量三唑磷,NF200膜的去除率在90%左右,NF90膜的去除率可达97%以上;操作压力对NF200、NF9...     

聚醚砜纳滤膜的制备及改性研究进展

聚醚砜是一种性能优异的纳滤膜材料,具有耐热、耐压、耐燃、耐辐射、抗酸、抗氧化、抗溶剂、生物相容性好等优点,应用前景十分广阔。文章重点介绍了相转化法、共混法、荷电法、复合法等聚醚砜纳滤膜制备方法,以及表面涂覆、材料共混等物理改性方法和膜材料本体改性、膜表面接枝改性等化学改性方法,阐述研究现状,并予以评价,同时提出探索新的制膜及改性方法,降低膜成本,提高制膜过程中的环境友好性,是聚醚砜纳滤膜制备及改性的重要发展方向。     

纳滤膜在地下水除氟中对Cl^-／F^-的选择性分离

荷负电型纳滤（NF）膜在地下饮用水除氟中,对离子F^-的截留率（65％-78％）要高于对离子Cl^-的截留率,且表现出较好的Cl^-／F^-的选择性（离子选择性系数S〉1．5）和Donnan排斥作用。当水溶液中离子F^-和Cl^-单独存在时,随原水F^-浓度增加,NF膜对F^-的截留率由64．3％增至73．0％,当原水F^-浓度小于3．3mg／L时,NF膜出水F^-浓度小于1．0mg／L;而随Cr浓度增加,NF膜对Cl^-截留率由44．7％减小至20％以下。当F^-和Cr共存时,受F^-浓度增加的影响,NF膜Cl^-的截留率逐渐减小;受Cl^-浓度增加的影响,NF膜F^-截留率同样表现出减小的趋势。由S值随r浓度的增加而增大,可知NF在地下水除氟中F^-与Cl^-之间存在明显的竞争关系。     

TA修饰GO-ZIF复合纳滤膜对染料MB的去除

采用层层自组装法,在氧化石墨烯（GO）中原位生长ZIF-8,GO-ZIF复合纳滤膜中的GO层间距被成功扩大.通过单宁酸（TA）的修饰,GO-ZIF-TA复合纳滤膜的渗透通道被进一步优化以提高通量和抗污染性能.采用SEM、XRD、FTIR等对复合膜材料进行表征和死端过滤对膜性能进行测试.GO-ZIF复合纳滤膜过滤50 mg·L^-1甲基蓝（MB）时水通量达到40.01 L·m^-2·h^-1,是GO膜水通量的2.4倍,其MB截留率为92.63%.采用TA对GO-ZIF复合纳滤膜进一步改性优化,得到的复合纳滤膜过滤MB时水通量达到47.09 L·m^-2·h^-1,并保持92.13%的MB截留率.TA沉积使膜表面更光滑并改善膜的亲水性,GO-ZIF-TA复合膜表现出良好的抗污染性.     

纳滤对煤矿矿井水处理的试验研究

介绍了用纳滤膜处理含悬浮物矿井水的工艺流程,考察了纳滤膜不同操作特性对膜过滤性能的影响及组合工艺对矿井水的处理效果。试验结果表明:纳滤膜在过滤周期为30min采用反曝气方式冲洗,能够有效减少膜污染,恢复膜通量。该工艺对煤矿井水的处理效果明显,高锰酸盐去除率为97.1%,浊度去除率为99.3%,硬度和含盐量去除率分别为95.1%和73.1%,色度去除率为91.7%。细菌的去除率为86%。     

纳滤膜在水处理中的应用

综述了纳滤膜的特点 ,包括孔径范围处于纳米级 ,膜体带有电性基团 ,操作压力低 ,对二价和高价离子的截留率明显高于单价离子等。介绍了纳滤膜在水处理中的应用 ,包括软化水处理、饮用水净化、地下水中硝酸盐的去除、二级污水的深度处理、工业废水的处理等。     

疏松型纳滤膜对饮用水中无机阳离子的截留特性及分离选择性

选用典型疏松型纳滤膜NF270对离子强度为1.5~24 mmol·L^-1的3种无机盐（MgCl₂、CaCl₂、NaCl）的单一盐溶液、混合盐溶液（MgCl₂/CaCl₂+NaCl）及某地下水进行纳滤实验,解析该膜在不同离子环境中的阳离子截留特性,并考察Ca²⁺/Mg²⁺在膜表面的吸附及对膜表面电荷的屏蔽作用对静电效应和盐离子截留率的影响.结果表明,NF270膜表面负电荷密度较高,对Ca²⁺和Mg²⁺都具有较强的吸附效应.NF270过滤相同离子强度的3种单一盐溶液时（特别是离子强度为1.5~6 mmol·L^-1）,道南效应较为显著,限定性离子Cl^-发挥了重要作用,截留率关系为NaCl >MgCl₂≈CaCl₂.混合盐溶液中,Ca²⁺/Mg²⁺显著降低了膜表面电势的绝对值,在道南效应、空间位阻效应和介电效应的综合作用下,Ca²⁺/Mg²⁺在反离子竞争中占据优势,截留率关系为Ca²⁺/Mg²⁺>Na⁺.地下水中同样存在反离子竞争效应,且由于SO₄^2-的存在,提高了各反离子的截留率.     

亲水聚合物改性微滤膜在膜生物反应器中的膜污染研究

采用经过聚合多巴胺和氨基聚乙二醇(mPEG-NH_2)表面改性的PVDF微滤膜,通过浸没在膜生物反应器(MBR)中验证改性微滤膜的抗污染性能.同时,采用多种分析手段对改性膜进行表征,包括膜表面微观形貌、润湿性、粗糙度和表面官能团等.实验同时考察了改性膜在MBR中运行的水通量衰减、污染膜的阻力分布,以及对膜面污染物的胞外多聚物组分的影响.结果发现,所采用的膜改性方法明显改善了膜表面的亲水性.短期过滤实验结果表明,多巴胺涂覆膜的稳定通量比原膜高47%,PEG改性膜则在水通量方面有进一步提高;在长期恒通量过滤阶段,多巴胺涂覆膜和PEG接枝膜的比膜通量分别比原膜高37%和88%.实验还发现,改性膜表面滤饼层中蛋白质和多糖含量均低于原膜.     

纳滤在水处理与回用中的应用现状与展望

纳滤(nanofiltration,NF)作为一种分离效果介于超滤和反渗透之间的膜过滤技术,在过滤过程中同时兼具物理孔隙产生的筛分效应和膜面电荷产生的道南效应作用.纳滤对水中的大多数有机物和多价盐离子具有很高的截留率,而对单价离子截留率较低,因而对单价多价盐具有良好的选择分离特性,近年来在饮用水软化、污水深度处理与回用、工业过程浓缩分离等方面得到了较为广泛的应用.据估计,到2019年纳滤膜的全球市场份额将达到4.451亿美元,同时在2015—2019年间将保持高达15.6%的年复合增长率(compound annual growth rate,CAGR).本文总结了目前市场上的纳滤膜品种、产品性能以及纳滤膜在水处理与回用中应用情况,并针对纳滤膜在应用中存在的问题提出了可行的方法和建议,最后对纳滤膜未来的发展方向提出了展望.     

Effect of water matrices on removal of veterinary pharmaceuticals by nanofiltration and reverse osmosis membranes

This study explored the removal of five veterinary pharmaceuticals (VPs) (sulfamethoxazole (SMETOX), trimethoprim (TMP), ciprofloxacin (CIPRO), dexamethasone (DEXA) and febantel (FEBA)) from different water matrices (Milli-Q water, model water, tap water and real pharmaceutical wastewater using four types of nanofiltration (NF) membranes (NF90, NF270, NF and HL) and two reverse osmosis (RO) membranes (LFC-1 and XLE). All VPs were added to different water matrices at a concentration of 10 mg/L. Rejections of VPs and water flux were measured. The rejection increased with increase of molecular weight. The highest rejections were obtained with RO membranes (LFC-1, XLE) and tight NF (NF90) membrane. In general, the rejection of VPs was higher in model water and tap water than in Milli-Q water, but the water flux was lower. This was mainly explained by ion adsorption inside the membranes pores. Narrower pore size counteracted the effect of presence of low concentration of natural organic matter (NOM) in tap water. The NOM was assumed to enhance the adsorption of VPs onto membrane surface, increased the size exclusion and electrostatic repulsion also appeared during the transport. Investigated water matrices had influence on water flux decline due to their complexity.     

Effects of ion concentration and natural organic matter on arsenic(V) removal by nanofiltration under different transmembrane pressures

The removal of As(V) from synthetic water was studied using four different nanofiltration (NF) membranes (ESNA-1-K1, NF270, ESNA-1-LF, and HODRA-CORE). The influences of ion concentration, transmembrane pressure (TMP), and the presence of natural organic matter (humic acid, HA) on the arsenic removal efficiency and permeate flux were investigated. The arsenic rejection of ESNA- 1-LF was higher than those of the other membranes in all experiments (> 94%), and the HODRA-CORE membrane gave the lowest removal of arsenic (< 47%). An increase in the ion concentration in the feed solution and addition of HA decreased the arsenic rejection of the HODRA-CORE membrane. However, both increasing of the ion concentration and addition of HA made the rejection increased for the other membranes (ESNA-1-K1, NF270, and ESNA-1-LF). With increasing TMP, for all four NF membranes, increases in both arsenic rejection and permeate flux were observed. The permeate fluxes of the four NF membranes decreased to some extent after addition of HA to the solutions for operating time of 6 hr.     

Advanced treatment of municipal wastewater by nanofiltration: Operational optimization and membrane fouling analysis

Municipal sewage from an oxidation ditch was treated for reuse by nanofiltration (NF) in this study. The NF performance was optimized, and its fouling characteristics after different operational durations (i.e., 48 and 169 hr) were analyzed to investigate the applicability of nanofiltration for water reuse. The optimum performance was achieved when transmembrane pressure = 12 bar, pH = 4 and flow rate = 8 L/min using a GE membrane. The permeate water quality could satisfy the requirements of water reclamation for different uses and local standards for water reuse in Beijing. Flux decline in the fouling experiments could be divided into a rapid flux decline and a quasi-steady state. The boundary flux theory was used to predict the evolution of permeate flux. The expected operational duration based on the 169-hr experiment was 392.6 hr which is 175% longer than that of the 48-hr one. High molecular weight (MW) protein-like substances were suggested to be the dominant foulants after an extended period based on the MW distribution and the fluorescence characteristics. The analyses of infrared spectra and extracellular polymeric substances revealed that the roles of both humic- and polysaccharide-like substances were diminished, while that of protein-like substances were strengthened in the contribution of membrane fouling with time prolonged. Inorganic salts were found to have marginally influence on membrane fouling. Additionally, alkali washing was more efficient at removing organic foulants in the long term, and a combination of water flushing and alkali washing was appropriate for NF fouling control in municipal sewage treatment.     

Preparation, characterization and performance of poly(m-phenylene isophthalamide)/organically modified montmorillonite nanocomposite membranes in removal of perfluorooctane sulfonate

Nanocomposite membranes containing poly(m-phenylene isophthalamide) (PMIA) and organically modified montmorillonite (OMMT) were prepared by a combination of solution dispersion and wet-phase inversion methods, and the effects of OMMT addition on the properties and performance of fabricated nanofiltration membranes were investigated. The membranes were characterized by contact angle measurements, scanning electron microscopy (SEM), atomic force microscopy (AFM), thermogravimetric analysis, and zeta potential. The performance of the membranes was elucidated by the removal of perfluorooctane sulfonate (PFOS) at neutral pH. Increasing OMMT concentration improved the thermal stability and hydrophilicity of the membranes. The permeation and rejection of PFOS were significantly improved. The performance of fabricated nanofiltration membranes in removal of PFOS varied depending on the solute and membrane properties as well as solution conditions. Finally, a comparison between fabricated membranes and a commercial NF membrane (ESNA1-K1, Hydecanme) proved that the OMMT addition is a convenient procedure for producing nanocomposite membranes with superior properties and performance.     

微滤-纳滤组合工艺在饮用水深度处理中的大型工程应用

张家港第三水厂供水规模为20万m3/d,日常采用混凝+沉淀+过滤+氯消毒的常规饮用水处理工艺。基于纳滤膜对于中小分子有机物与钙、镁、硫酸根等盐离子的高效截留能力,该项目创新性地在国内首次采用现状常规工艺+压力罐式微滤+纳滤的净水工艺,对张家港第三饮用水厂深度处理大型工程（设计产水规模为10万t/d）进行升级改造设计。经改造后,预计纳滤系统对于COD以及TOC的去除率可达到90%以上,消毒副产物的去除率可达到70%~80%,色素类物质的去除率可达到70%以上,臭味物质的去除率为50%~70%,整体脱盐率为30%~40%;纳滤系统回收率整体可达到90%。预计压力罐式微滤系统和纳滤系统的能耗分别为0.003,0.197 kW·h/t;在实现高品质供水的同时,可提高水厂应对突发污染风险的能力。     

溶液特性及共存物对纳滤膜去除水中全氟辛酸的影响

利用聚酰胺复合纳滤(NF)膜去除水中的持久性有机污染物—全氟辛酸(PFOA),分别研究了PFOA浓度、溶液离子强度、pH值、典型大分子有机物—牛血清蛋白(BSA)以及BSA与Na+共存对PFOA截留率的影响.结果表明,在0.8MPa下过滤24h,随着PFOA浓度增大,PFOA截留率提高;溶液离子强度、pH值越高,PFO...     

SGO改性复合纳滤膜的制备及分盐性能

近年来,水资源短缺,水源污染严重,国家对水处理末端的资源化利用提出了更高的要求,分盐过程也受到越来越多的关注.纳滤膜表面通常带有电荷,可以选择性地透过不同价态的离子.基于纳滤膜表面电荷特性不同,为很好地实现盐的分离,将制备的带有磺酸基团的氧化石墨烯引入到纳滤膜材料中,采用界面聚合法,制备了SGO改性复合纳滤膜. Zeta电位分析表明所制备的复合纳滤膜表面的电荷比不添加SGO的纳滤膜更负;红外光谱分析中酯基基团特征峰的出现表明磺酸基团参与了聚合反应; SEM结构表面,膜表面出现了明显的图灵结构,在0. 2 MPa压力下,纯水通量可达45. 85 L·(m~2·h)-1,对Na2SO4截留率为98. 23%,对Na Cl截留率为24. 93%,10 h运行可以很好地实现对SO_4~(2-)、Cl~-的有效分离,可实现盐的资源化回收.