碳酸盐溶液纳滤过程中的H+负截留现象

以自配的具有暂时硬度的碳酸盐溶液为水样,使用NF270型和NF-型纳滤膜在5种pH值条件(6.0,6.5,7.0,7.5和8.0)下进行了纳滤实验.结果显示,当压力为1.0MPa,流量为6 L·min-1,温度恒定在25℃的条件下,2种膜的通量随进料液pH值的降低而升高,表明对进料液进行酸化可使膜过滤获得相对较高的通量.整个过滤过程中,透过液pH值始终低于浓缩液pH值,即H+表现为负截留,这是因为小体积、荷正电的H+易透过小孔径、荷负电的纳滤膜所致.H+的负截留作用会加速HCO3-离解,生成更多的CO32-,使膜面发生CaCO3结晶的可能性加大,不利于膜操作.荷负电量高的纳滤膜有利于H+的透过,因此在纳滤软化水过程中,应当综合多方面因素考虑膜的选择及相应的预处理,在满足水质处理要求的前提下,采用荷负电量稍低的膜有利于减小H+负截留对纳滤软化水过程的影响,从而延缓膜面结垢.     

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.     

膜法技术在印染废水深度处理中的应用和研究

采用超滤-纳滤、超滤-反渗透2种膜集成工艺对印染废水二级生物法的处理出水进行深度处理,比较2种不同材料和结构的超滤膜预处理的效果,并研究了纳滤和反渗透对出水水质的影响.研究结果表明,作为纳滤和反渗透预处理的有效手段,超滤能有效去除部分COD.PES超滤膜综合性能较PVC超滤膜好;在深度脱盐方面,与反渗透膜相比纳滤膜在较...     

微涡旋絮凝-逆流气浮-纳滤集成工艺去除水中腐殖酸的研究--以聚合氯化铝(PACl)为絮凝剂

研究了微涡旋絮凝-逆流气浮-纳滤集成工艺去除水中腐殖酸的工艺特征和效果.试验结果表明,微涡旋絮凝-逆流气浮工艺去除水中腐殖酸时,在最佳投药点(PACl),出水水质符合纳滤系统预处理单元的要求,而且该工艺需要PACl絮凝剂的量较低.该预处理系统与纳滤系统组合的集成工艺可以使水中的腐殖酸浓度大大降低,且含TQ56-36FC型纳滤膜的流程1比含M-N1812A型纳滤膜的流程2效果好.前者出水的TOC值可达0.28～0.45mg·L-1,CODMn值为0.47～0.8mg·L-1,UV254nm值为0～0.0033,且有95%以上的脱盐率;后者出水的TOC值为0.52～1.25mg·L-1,CODMn值为0.66～1.0 mg·L-1,UV254nm值为0.008-0.012,脱盐率很低.另外,尽管保安过滤器/活性炭预处理有利于纳滤膜出水水质的提高,但活性炭柱与纳滤膜能去除的有机物种类有些重合,活性炭柱的存在也降低了纳滤膜对有机物的去除率.水中颗粒物的粒度分布表明,原水、絮凝后和气浮出水中颗粒物粒度分布的中位直径(d50)分别为5～6μm、10～14μm和8～13 μm.经过保安过滤器或保安过滤器/活性炭柱,水样中的颗粒物的d50为0到几个μm.经过纳滤膜后出水无颗粒物.     

无机纳滤膜处理低水平放射性废水的试验研究

选择相对分子质量2 000～5 000的水溶性聚丙烯酸钠作为无机纳滤膜处理主要含⁹⁰Sr、¹³⁷Cs、⁶⁰Co放射性核素的低水平放射性废水的辅助药剂.重点考察了非放模拟废水的pH值及聚丙烯酸钠投加量对废水中锶、铯、钴等稳定核素截留率及膜通量的影响,并就影响机理做了初步探讨.得到较优的试验条件为:pH值7～8,聚丙烯酸钠体积浓度不低于0.1%.在优化的条件下,进行实际放射性废水的处理试验.结果表明,聚丙烯酸钠辅助无机纳滤膜处理低水平放射性废水是可行的,对总β和总γ的净化率均达到95%左右,且可得到满意的膜通量.     

JMS-CCDAF-NF工艺去除水中腐殖酸的研究

试验研究了JMS-逆流气浮-纳滤集成工艺去除水中腐殖酸的工艺特征和效果。试验结果表明:JMS-逆流气浮工艺去除水中腐殖酸时,在最佳投药点(PACl),出水水质符合纳滤系统预处理单元的要求。该预处理系统与纳滤系统组合的集成工艺可以使水中的腐殖酸有机物浓度大大降低,且含TQ56-36FC型纳滤膜的流程比含M-N1812A型纳滤膜的流程效果好。前者出水的TOC值可达0.28￣0.70mg/L。后者出水的TOC值在0.59￣1.30mg/L。另外,尽管保安过滤/活性炭预处理有利于纳滤膜出水水质的提高,但活性炭柱与纳滤膜能去除的有机物种类是有些重合。     

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.     

微涡旋絮凝-逆流气浮-纳滤集成工艺去除水中腐殖酸的研究之二——以聚合氯化铁(PFC)为絮凝剂

试验研究了微涡旋絮凝-逆流气浮-纳滤集成工艺去除水中腐殖酸的工艺特征和效果.试验结果表明,微涡旋絮凝-逆流气浮工艺去除水中腐殖酸时,在聚合氯化铁(PFC)的最佳投药点0.62 mmol·L-1(Fe3 )下,出水水质符合纳滤膜系统预处理单元的要求,而且该工艺需要PFC絮凝剂的量较低.该预处理系统与纳滤系统组合的集成工艺可以使水中的腐殖酸有机物浓度大大降低,且含TQ56-36FC型纳滤膜的流程1比含M-N1812A型纳滤膜的流程2效果好.前者出水的TOC值可达0.48 mg·L-1,CODMn值为0.64～0.69mg·L-1,UV254值为0,且有95%以上的脱盐率.后者出水的TOC值为0.61～1.00mg·L-1,CODMn值为0.72～0.97mg·L-1,UV254值为0～0.0109,脱盐率很低.另外,尽管保安过滤/活性炭预处理有利于纳滤膜出水水质的提高,但活性炭柱的存在也降低了纳滤膜对有机物的去除率.动态实验结果表明,该集成工艺在本试验中运行周期为72h.水中颗粒物粒度分布表明,原水、絮凝后和气浮出水中颗粒物粒度分布的中位直径(d50)分别为2～5 μm、21 μm和16μm;经过保安过滤器或保安过滤器/活性炭柱,水样中的颗粒物的d50为0到几个μm;经过纳滤膜后,出水基本无颗粒物.初步研究表明,微涡旋絮凝过程中投药量对絮体的分形维数有着显著影响.     

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...     

纳滤技术在饮用水处理中的研究进展与应用

纳滤技术作为一种新型的膜分离技术,近年来成为水处理研究的热点.论文介绍了纳滤膜的特点及分离机理,详细阐述了纳滤膜技术在饮用水净化过程中的技术特点,如降低饮用水的硬度,去除饮用水中的重金属物质、有机污染物、藻类、细菌病毒等成分.同时探讨了纳滤的膜污染问题以及引起膜污染的因素.列举了比利时、日本、美国以及中国山东长岛等地纳滤膜技术的工程实例,说明了纳滤膜技术在饮用水处理中应用的处理效果.     

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.     

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.     

聚离子液体刷接枝改性PVDF膜及其对药物硫酸氢氯吡咯雷分离性能研究

以聚偏氟乙烯(PVDF)超滤膜为底膜,通过浸渍法使多巴胺(DOPA)在膜表面形成聚多巴胺(PDOPA)层,然后由化学反应固定溴代卤化物,并通过原子转移自由基聚合(ATRP)反应在膜表面接枝聚离子液体刷(PBIVm-Br),以制备聚离子液体刷改性PVDF膜,即PVDF-g-PBIVm-Br膜.结果表明,改性PVDF膜的接触角下降至60°以下且显示出良好的荷正电性.改性膜的药物通量和截留率均大于未改性PVDF膜,分离10 mg·L~(-1)的硫酸氢氯吡咯雷时,改性膜(M4)的药物通量可达27.62 L·m~(-2)·h~(-1),截留率为89.03%,通量恢复率为95.32%.经过60 h分离实验后,膜M4对硫酸氢氯吡咯雷溶液的分离通量维持在18.05 L·m~(-2)·h~(-1),截留率从89.03%上升到92.19%.以上结果表明,聚离子液体刷改性膜在荷正电有机污染物的分离方面具有一定的应用前景.     

Effects of protein properties on ultrafiltration membrane fouling performance in water treatment

Protein-like substances always induce severe ultrafiltration (UF) membrane fouling. To systematically understand the effect of proteins, regenerated cellulose UF membrane (commonly used for protein separation) performance was investigated in the presence of bovine serum albumin (BSA) under various water conditions. Results showed that although trypsin enhanced the membrane flux via proteolysis, catalysis took a long time. Membrane fouling was alleviated at high solution pH and low water temperature owing to the strong electrostatic repulsion force among BSA molecules. Both Na⁺ and Ca²⁺ could increase membrane flux. However, Ca²⁺ played a bridging role between adjacent BSA molecules, whereas membrane fouling was alleviated via a hydration repulsion force with Na⁺. The order of influence on membrane fouling was as follows: Ca²⁺ concentration > Na⁺ concentration > pH > temperature > trypsin concentration. Furthermore, a polyvinylidene fluoride UF membrane experiment showed that Ca²⁺ could reduce the fouling induced by BSA. Thus, the differences in UF membrane performance will have application potential for alleviating UF membrane fouling induced by proteins during water treatment.     

XDLVO理论解析不同离子条件下海藻酸钠微滤膜污染

应用extended Derjaguin-Laudau-Verwey-Overbeek(XDLVO)理论定量解析海藻酸钠微滤膜污染中界面微距作用力,探讨不同离子条件对膜污染影响的主控机制.结果表明,对于亲水性膜表面,范德华力促进膜污染,极性作用力阻碍膜污染;而对于疏水性膜表面,范德华力减缓膜污染,极性作用力加速膜污染.海藻酸钠与微滤膜接触时双电层作用力对膜污染贡献相对微弱.离子强度及钙离子对海藻酸钠微滤膜污染的影响主要是通过改变极性作用力来实现的.较高的离子强度会降低极性作用力的排斥性或升高极性作用力的吸引性,从而加重海藻酸钠微滤膜污染.虽然钙离子使出水通量急速下降,但钙离子的存在使得物理清洗效率提高.不同离子条件下初始阶段及后期阶段污染趋势K分别与膜-海藻酸钠粘附自由能及海藻酸钠-海藻酸钠粘聚自由能具有良好的线性相关性,表明XDLVO理论适用于描述不同离子条件下海藻酸钠微滤膜污染行为.     

Fatty acid fouling of forward osmosis membrane: Effects of pH, calcium, membrane orientation, initial permeate flux and foulant composition

Octanoic acid (OA) was selected to represent fatty acids in effluent organic matter (EOM). The effects of feed solution (FS) properties, membrane orientation and initial permeate flux on OA fouling in forward osmosis (FO) were investigated. The undissociated OA formed a cake layer quickly and caused the water flux to decline significantly in the initial 0.5 hr at unadjusted pH 3.56; while the fully dissociated OA behaved as an anionic surfactant and promoted the water permeation at an elevated pH of 9.00. Moreover, except at the initial stage, the sudden decline of water flux (meaning the occurrence of severe membrane fouling) occurred in two conditions: 1. 0.5 mmol/L Ca^2 +, active layer facing draw solution (AL-DS) and 1.5 mol/L NaCl (DS); 2. No Ca^2 +, active layer-facing FS (AL-FS) and 4 mol/L NaCl (DS). This demonstrated that cake layer compaction or pore blocking occurred only when enough foulants were absorbed into the membrane surface, and the water permeation was high enough to compact the deposit inside the porous substrate. Furthermore, bovine serum albumin (BSA) was selected as a co-foulant. The water flux of both co-foulants was between the fluxes obtained separately for the two foulants at pH 3.56, and larger than the two values at pH 9.00. This manifested that, at pH 3.56, BSA alleviated the effect of the cake layer caused by OA, and OA enhanced BSA fouling simultaneously; while at pH 9.00, the mutual effects of OA and BSA eased the membrane fouling.     

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.     

DOM纳滤膜污染及对膜截留卡马西平性能的影响

研究了天然原水中溶解性有机物(DOM)对HL和ESNA1-K两种纳滤膜造成的膜污染及其对膜截留卡马西平(CBZ)性能的影响.结果表明,DOM的存在造成了严重的膜污染和通量衰减.膜污染对CBZ截留率的影响与膜本身的特性和污染物特性有关,DOM通过在膜表面形成污染滤饼层和进入膜孔内部造成的膜孔堵塞,影响弱疏水性的CBZ从水中的分离,青草沙水库原水中的DOM引起的膜污染提高了两种纳滤膜对CBZ的截留效果,而太湖DOM造成的膜污染会降低CBZ的截留效果.研究还发现,中等相对分子质量(1 500~10 000)有机物会紧密地黏附在膜表面形成滤饼层,从而改变膜表面的疏水性能,小分子主要通过进入膜孔导致膜孔径堵塞.滤饼层的疏水性和浓差极化作用以及膜孔径的堵塞造成膜通量衰减并影响CBZ去除率.应用XDLVO理论对DOM造成的膜污染的分析结果表明,太湖DOM的疏水性明显强于青草沙DOM,其分子间的聚合自由能更负,与膜的黏附自由能更负,因而造成的膜污染和通量衰减更严重.     

MWCNTs预涂覆及预吸附处理缓解低压膜腐殖酸污染的机制研究

以腐殖酸(Humic Acid,HA)为研究对象,采用多壁碳纳米管(Multiwalled Carbon Nanotubes,MWCNTs)对聚偏氟乙烯(Polyvinylidene Fluoride,PVDF)平板超滤膜进行预涂覆改性处理,并与等量MWCNTs分散状态时吸附处理HA对膜污染的缓解效果进行了对比,考察了MWCNTs在处理HA过程中缓解膜污染的机制.同时,分析了MWCNTs投量和溶液离子变化对MWCNTs吸附及截留作用缓解膜污染的影响.结果表明,MWCNTs预涂覆与吸附相比,能够更有效地缓解膜污染,其中,分散剂为乙醇的MWCNTs预涂覆层对膜污染的缓解效果最好.增加MWCNTs投量不能无限地提高其对HA的吸附及截留效果;添加Na~+会造成MWCNTs对HA的吸附及截留效果变差;添加Ca~(2+)能够提高MWCNTs对HA的吸附及截留效果.膜表面污染照片及膜电镜观测结果表明,乙醇分散MWCNTs在超滤膜(UF)表面形成的预涂覆层呈均匀的层状结构,HA被拦截在MWCNTs层的多孔结构内,不易进入PVDF膜膜孔,反洗时易脱附,可逆性高;纯水分散MWCNTs在超滤膜表面形成的预涂覆层易于团聚,HA容易透过MWCNTs涂覆层进而堵塞PVDF膜膜孔,可逆性低;MWCNTs预吸附处理后形成MWCNTs和HA的包裹体,不经微滤膜滤除,会在PVDF膜表面产生复合污染.     

城市污水二级出水超滤膜污染与膜特性的研究

以城市污水二级出水为过滤介质,考察了PVA、PVP、PMMA等与PVDF的二元及三元共混超滤膜的过滤污染行为.结果表明,共混优化了PVDF超滤膜的结构参数,添加剂PVP、PVA可有效改善膜的亲水化程度,提高膜渗透通量.超滤膜的亲水性和结构特性对膜抗污染性能影响较大;堵孔阻力是二级出水过滤膜污染不可逆的主要原因.亲水性较强的超滤膜,二级出水过滤初期易因浓差极化而导致滤饼层污染,造成一定的通量衰减,但易清洗恢复,不可逆污染指数(rir)为0,抗污染性能好.致密的超滤膜表面有利于防止二级出水中的中低分子量污染物进入膜内部,而断面通透大孔和疏松海绵层结构的超滤膜,能减少二级出水中的污染物在膜中沉积形成堵孔阻力.膜表面多孔,内部大孔发育不充分,易形成堵孔污染,通量衰减大且不易清洗恢复,膜污染不可逆.