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.     

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.     

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.     

反渗透用于APT离子交换废水的处理与回用

试验分别研究了反渗透膜Duraslick RO2540和RE2540-TE对APT冶炼离子交换废水的处理效果。研究结果表明,在最佳压力条件下,Duraslick RO2540膜对Cl-的截留率为91.4%,产水率为16.9%;RE2540-TE膜对Cl-的截留率为93.4%,产水率为17.2%。在压力为1.7MPa,温度为25℃时,浓缩实验结果表明,产水中Cl-浓度和膜的截留率随着时间变化而逐渐增加,但膜通量逐渐减小,且RE2540-TE膜通量下降幅度较大。清洗后,RE2540-TE膜通量损失达到6%,而Duraslick RO2540膜通量恢复幅度为98%。     

Fluoride removal from brackish groundwater by direct contact membrane distillation

The direct contact membrane distillation applied for fluoride removal from brackish groundwater was investigated.The self-prepared polyvinylidene fluoride membrane exhibited high rejection of inorganic salt solutes.The maximum permeate flux 35.6 kg/(m2 ·hr) was obtained with the feed solution at 80°C and the cold distillate water at 20°C.The feed concentration had no significant impact on the permeate flux and the rejection in fluoride.The precipitation of CaCO3 would clog the hollow fiber inlets and foul the membrane surface with increasing concentration factor when natural groundwater was used directly as the feed,which resulted in a rapid decline in the module efficiency.This phenomenon was diminished by acidification of the feed.The experimental results showed that the permeate flux and the quality of obtained distillate kept stable before concentration factor reached 5.0 with the acidified groundwater as feed.The membrane module efficiency began to decline gradually when the feed continued to be concentrated,which can be mainly attributed to the formation of CaF2 deposits on the membrane surface.In addition,a 300 hr continuous fluoride removal experiment of acidified groundwater was carried out with concentration factor at 4.0,the permeate flux kept stable and the permeate fluoride was not detected.     

磁场对静态纳滤过程的膜通量及CaCO3结晶的影响

使用NF270型和NF型纳滤膜研究了经磁化预处理的钙溶液的静态纳滤过程,并与未经磁化预处理钙溶液的静态纳滤结果相比较.结果表明,当水样中Ca²⁺ 浓度为3.6 mmol/L,硬度等于碱度,初始水样体积为300 mL,体积浓缩倍数为2时,普通溶液的膜通量随滤出液体积呈现单调递减趋势;但处理磁化溶液时,膜通量随滤出液的体积先下降后上升,然后才下降,且平均膜通量比普通溶液的高,表明磁化预处理可以改善纳滤膜的部分操作性能.对膜的扫描电镜分析表明,处理磁化溶液的纳滤膜膜面上生成的晶体相对较多.综合纳滤膜通量和膜面晶体生成量的观察,认为磁场的引入可使膜表面结晶速率增加,致使膜面溶质浓度降低,通量上升,同时因生成的晶体全部留在膜面上,运行一段时间后有效膜面积减少,又导致通量下降.晶体生成量较多的膜,通量却相对较高,这与平常对膜污染的认识相矛盾.通过对结晶过程的理论分析,认为一定程度的结晶对膜操作性能有改善作用.     

无机膜过滤黑液的操作条件选择

分别采用孔径为0.8,0.2μm微滤膜和50nm超滤膜过滤草浆黑液,探讨了操作条件对无机膜渗透通量的影响。结果表明,选用0 2或0.8μm孔径的膜,有利于渗透通量的提高并保证截留效果。操作压力在0.25～0.35MPa之间,错流速度不小于5.0m s,温度为60℃时,可以获得较高的渗透通量。黑液本身的性质,如浓度、COD值等,也会对渗透通量产生较大的影响。      

DOM对纳滤膜去除磺胺甲恶唑效果影响研究

试验研究几种不同可溶性有机物(DOM)对纳滤膜(NF)去除抗生素磺胺甲恶唑(SMZ)的影响效果.试验所用DOM选定腐殖酸(HA)、单宁酸(TA)和海藻酸钠(SA).结果显示3种DOM对SMZ去除率和通量影响迥异,并与DOM的亲疏水性有密切的关系.为更好了解DOM对NF去除SMZ的影响机理,试验对臭氧化HA也进行了研究.臭氧化HA相对于臭氧前HA亲水性显著提高,对SMZ去除率的影响相应提高.结果表明在有多种DOM共同存在的天然原水中,SMZ的去除机理十分复杂,DOM的本身物理化学性质对于目标物的去除效果十分重要.     

Drinking water treatment using a submerged internal-circulation membrane coagulation reactor coupled with permanganate oxidation

A submerged internal circulating membrane coagulation reactor(MCR) was used to treat surface water to produce drinking water. Polyaluminum chloride(PACl) was used as coagulant,and a hydrophilic polyvinylidene fluoride(PVDF) submerged hollow fiber microfiltration membrane was employed. The influences of trans-membrane pressure(TMP), zeta potential(ZP) of the suspended particles in raw water, and KMnO_4 dosing on water flux and the removal of turbidity and organic matter were systematically investigated. Continuous bench-scale experiments showed that the permeate quality of the MCR satisfied the requirement for a centralized water supply, according to the Standards for Drinking Water Quality of China(GB 5749-2006), as evaluated by turbidity(1 NTU) and total organic carbon(TOC)(5 mg/L)measurements. Besides water flux, the removal of turbidity, TOC and dissolved organic carbon(DOC) in the raw water also increased with increasing TMP in the range of 0.01–0.05 MPa. High ZP induced by PACl, such as 5–9 mV, led to an increase in the number of fine and total particles in the MCR, and consequently caused serious membrane fouling and high permeate turbidity.However, the removal of TOC and DOC increased with increasing ZP. A slightly positive ZP, such as 1–2 mV, corresponding to charge neutralization coagulation, was favorable for membrane fouling control. Moreover, dosing with KMnO_4 could further improve the removal of turbidity and DOC, thereby mitigating membrane fouling. The results are helpful for the application of the MCR in producing drinking water and also beneficial to the research and application of other coagulation and membrane separation hybrid processes.     

NF270截留17α-乙炔基雌二醇过程

研究了操作压力、电解质及pH等因素对聚酰胺复合纳滤膜组件NF270截留水溶液中100 μg/L 17α-乙炔基雌二醇(EE2)过程的影响,同时考察了NF270对葡萄糖配水中100 μg/L EE2的截留情况.结果表明:NF270能实现对微量甾体雌激素EE2的有效截留;截留初始阶段,EE2在膜面的吸附作用增强了NF270的截留效能,组件运行6 h后膜截留性能稳定. 出水ρ(EE2)随着操作压力的增大略有增大,当操作压力为0.5 MPa时,出水ρ(EE2)为31.09 μg/L. 加入MgSO₄和CaCl₂等电解质,截留率略有提高,出水ρ(EE2)为27.10 μg/L. 酸性条件对NF270截留EE2影响较小,当pH为11时EE2稳定截留率为88.81%,比中性条件高19.91%. 0.5 MPa条件下NF270对葡萄糖配水中EE2截留效果明显提高,出水ρ(EE2)仅为11.96 μg/L.      

荷电超滤膜对天然有机物去除及膜污染行为的影响

以Aldrich 腐殖酸溶液为水样,研究比较了溶液环境(pH值、离子强度和钙离子)对荷电改性再生纤维素超滤膜和传统中性未改性再生纤维素超滤膜过滤过程的影响.结果表明, ①pH值主要通过质子化作用影响荷电膜以及腐殖酸分子的荷电量,进而影响荷电超滤过程.溶液pH值从7.5下降到3.5时,荷电超滤膜对腐殖酸的截留率从92%减少到79%,超滤4 h时,膜通量下降从26%增加到36%.②离子强度的改变是通过影响腐殖酸分子的物化性质和静电屏蔽作用来影响超滤过程的.当溶液离子强度为0、 3和100 mmol/L时,初始截留率依次降低,分别为92%、 87%和48%,超滤4 h时,荷电超滤膜的通量下降依次增加,分别为26%、 35%和63%.③Ca2+浓度的影响,需要综合考虑静电屏蔽作用、Ca2+的架桥作用以及滤饼层的压实性等各方面的影响.④pH值、离子强度和钙离子对中性超滤膜过滤行为的影响趋势与荷电超滤膜相似,但其影响程度有着较大的差别.研究结果对荷电超滤膜技术在实际应用中选择合适环境条件提供了参考.     

操作条件对TMBR性能的影响

为了探讨TMBR处理高浓度废水时操作条件对其性能的影响,用内径为8 mm聚偏氟乙烯(PVDF)管式超滤膜制作外置式管式膜生物反应器(TMBR)处理垃圾渗滤液。实验结果表明,增加跨膜压差(TMP)可以增加膜通量,当TMP超过适宜值后表现为通量与TMP无关的特性。提高膜面流速可以削弱污染层的形成,当超过适宜流速后也表现出通量与流速无关的特性。不同的污泥浓度(MLSS)存在适宜的TMP和适宜膜面流速。快速冲洗和化学清洗可分别使膜的通量恢复至新膜的78%和89%。     

SDS、SDBS胶团强化超滤Cu~(2+)的比较

采用模拟含Cu2+废水,以阴离子表面活性剂SDS和SDBS胶团强化超滤分离Cu2+(Cu2+固定为0.6 mmol/L),通过对渗透通量、渗透浓度、去除率、富集率的比较,从而得出SDS、SDBS分离效果的优劣.结果表明,添加SDS的渗透通量始终高于SDBS[其中SDS平均渗透通量为29.92 L.(m2.h)-1,而SDBS只有16.55 L.(m2.h)-1],渗透浓度始终低于SDBS,当渗透液Cu2+浓度接近为0时,SDBS、SDS所需浓度分别为2 mmol/L和6 mmol/L.SDS的Cu2+去除率和平均富集率高于SDBS(SDS平均去除率为85.06%,平均富集率为4.18;SDBS对应值分别为69.05%,4.05).此外,SDS自身的平均富集率也高于SDBS(SDS为3.89,SDBS为3.13).由此可见,SDS比SDBS更适合去除Cu2+.     

黄淮地区纳滤膜苦咸水软化分离性能研究

针对我国黄淮地区华北山前冲积平原与中部冲积平原交接部位的模拟苦咸水,构建纳滤(NF)膜法软化系统,考察了跨膜压差(0.6~2.1 MPa)、进水端切向流速(0.09~0.38 m/s)和进水温度(7~35 ℃)等操作条件对NF膜软化分离性能的影响。结果表明:在跨膜压差为1.2 MP,进水端切向流速为0.28 m/s,进水温度为15 ℃时,NF膜软化系统有较高的膜产水通量〔52.04 L/(m ²·h)〕,对主要成垢离子Ca ²⁺、Mg ²⁺、$CO_{3}^{2-}$和$SO_{4}^{2-}$的去除率分别达44.13%、73.72%、81.05%和99.13%,对总硬度的平均去除率达53.31%,NF膜有良好的软化性能;随着跨膜压差、进水端切向流速的增加及进水温度的下降,NF膜产水的pH逐渐降低,而浓水的pH呈逐渐升高的趋势。     

亲水荷电超滤膜的制备及对腐殖酸的分离性能

为改善聚醚砜(PES)超滤膜的抗污染性能和提高对腐殖酸(HA)的截留率,以介孔二氧化硅(MS)为添加剂,采用相转化法制备了亲水性PES/MS复合超滤膜,并对膜表面进行荷电改性.研究了MS对膜的断面结构、表面化学性质和过滤性能的影响,考察了荷电改性PES/MS超滤膜对水中HA的分离性能以及溶液pH值、离子强度和钙离子浓度等因素对荷电膜超滤过程的影响.SEM表征结果显示,MS颗粒在PES/MS复合膜的表面分散均匀,膜孔的连通性改善.亲水荷电改性后,膜表面接触角由68°降至57°,zeta电位由-6.31mV降至-11.45mV,膜对HA的去除率由72%提高到95%,通量衰减率由29.8%减小到4.9%.结果表明,对PES超滤膜进行亲水荷电改性可有效提高对HA的截留率,同时减轻膜污染;另外,溶液的pH值、离子强度和钙离子浓度对荷电超滤膜的过滤性能有较大影响,调节合适的溶液环境可在提高截留率的同时,减轻膜污染.     

Arsenic (V) removal from groundwater by GE-HL nanofiltration membrane: effects of arsenic concentration, pH, and co-existing ions

A laboratory-scale investigation was performed to study arsenic (As (V)) removal by negatively charged GE-HL nanofiltration (NF) membrane in simulated drinking water. Effects of As (V) concentration (0–200 μg·L⁻¹), pH, and co-ions and counter-ions were investigated. The NF membrane presented good stability, and the rejection rates exceeded 90%. The rejection rates of As (V) decreased with the increase of As (V) concentration, while it increased with the increase of pH (reached 96% at pH 6.75). Moreover, a negative relationship was observed between the co-existing ions of Cl⁻, Na⁺, SO₄²⁻, and Ca²⁺ and the removal of As (V), in which bivalent ions presented more significant effects than monovalent ions.     

纳滤膜去除卡马西平的影响因素研究

主要研究了纳滤膜去除饮用水中卡马西平(CBZ)的影响因素.首先比较了膜NF270和NF90去除CBZ的效果,发现孔径较小的NF90对CBZ的去除效果远优于孔径较大的NF270.其次考察了CBZ初始浓度、pH值、离子强度和水温对去除率的影响.结果表明,pH值的降低,钙离子浓度的提高以及水温的提高会导致CBZ去除率的降低....     

一体式铝盐絮体-超滤膜净水效能与机制

一体式膜工艺以其占地面积小、污染物去除效率高等优点在水处理工艺中逐渐应用.然而,长期运行后,传统颗粒性吸附剂存在加剧膜表面损伤的风险,同时大多数研究所用吸附剂价格较高,如纳米铁、碳纳米管等.针对上述问题,本文将铝盐混凝剂水解后形成的松散絮体直接注入膜池,基于腐殖酸(HA)和密云水库原水,考察了一体式絮体-超滤膜工艺运行效能及膜污染行为.结果表明,仅HA过膜时,第12 d跨膜压差(transmembrane pressure,TMP)急剧增至76. 4 k Pa,将膜组件取出经自来水清洗膜表面后TMP降为10. 1 k Pa (13 d),表明滤饼层是膜污染的主要形式,并且运行期间HA平均去除率仅为23. 3%.絮体注入频率、曝气强度及溶液pH能显著影响该工艺运行效能,尤其溶液pH.当采用连续投加方式将43. 2mmol·L-1铝盐絮体注入到pH为6. 0、曝气速率为0. 3 L·min-1膜池内时,膜污染程度显著降低,第12 d时TMP仅增长到19. 5 k Pa,清洗之后TMP降为5. 6 k Pa (13 d),此时HA平均去除率提高至61. 2%.此外,密云水库原水实验表明,当原水直接过膜时,TMP也急剧增加,运行12 d时TMP达到38. 0 k Pa,而清洗膜表面后TMP降低至3. 8 k Pa (13 d),滤饼层仍然为主要污染方式,同时有机质平均去除率为7. 5%.在上述最佳工艺条件下(曝气0. 3 L·min-1、溶液pH 6. 0)投加43. 2mmol·L-1铝盐絮体时,TMP增长也极其缓慢,12 d时仅增至6. 1 k Pa,膜表面清洗后TMP降至2. 3 k Pa (13 d),有机质平均去除率高达58. 6%.本研究表明一体式铝盐絮体-超滤膜在水处理中具有潜在的应用价值.     

碳纳米管预涂覆低压膜去除水中腐殖酸的机理研究

以腐殖酸（Humic Acid,HA）为研究对象,通过压力辅助过滤技术将碳纳米管（Carbon Nanotubes,CNTs）预涂覆在聚醚砜（Polyethersulfone,PES）平板膜表面,制备了CNTs预涂覆低压膜,分别考察了该膜在恒压和恒流实验中对HA的去除情况及其对膜污染的缓解作用.研究表明,CNTs预涂覆膜可以有效缓解基膜的污染,保证CNTs的分散性,增加PES膜表面预涂覆CNTs的投加量,有助于缓解膜污染的发生;采用径向尺寸小的CNTs制备出的预涂覆低压膜,其抗污染能力更佳.研究进一步采用恒流膜滤装置对膜滤过程的3个阶段（新膜过滤阶段、膜污染加速阶段、堵塞膜截留阶段）进行了模拟,考察了CNTs预涂覆低压膜对HA的去除机理.结果表明,新膜过滤阶段,CNTs预涂覆低压膜运行初期,CNTs的吸附性能对HA的去除起主导作用,HA去除率随过滤时间的增加而不断减小,吸附阶段CNTs预涂覆膜的跨膜压差（Transmembrane Pressure,TMP）始终保持在较低水平（不高于15 kPa）,降低CNTs的径向尺寸和提高CNTs投加量,均有助于吸附去除HA;膜污染加速阶段,随着CNTs预涂覆膜进入膜污染加速阶段,HA的去除率由吸附阶段的不断降低开始出现上升拐点,TMP由于CNTs预涂覆膜的加快堵塞而不断升高;堵塞膜截留阶段,CNTs预涂覆低压膜在一定程度堵塞后,表现出截留去除HA的效能,且TMP仍保持在低压膜运行范围内,降低CNTs的径向尺寸,制备的预涂覆膜孔径小且分布均匀,有助于其提高截留去除HA的效能.整个恒流实验过程中,未负载CNTs的基膜对HA仅有微弱的吸附作用,且由于其较大的孔径,对HA的截留作用十分有限.本文通过对CNTs预涂覆低压膜吸附阶段和截留阶段的划分,明确了CNTs预涂覆低压膜在吸附饱和之后,能够有效截留水中HA,可作为水中腐殖质类污染物去除的一种有效手段.     

微塑料对膜蒸馏处理含锑高盐废水性能影响研究

研究了微塑料在膜蒸馏过程中不同温度、pH、微塑料浓度和微塑料粒径条件下对含锑高盐废水的处理性能及机理.结果表明,随着进料液温度的升高,饱和蒸汽压的增加提高了传质动力,不含微塑料时膜通量由17.4 L·m^-2·h^-1提高至20.7 L·m^-2·h^-1,通量提升了18.9%,含有微塑料时膜通量由15.6 L·m^-2·h^-1提高至18.5 L·m^-2·h^-1,提升了18.6%;pH由3增大至11时,由于重金属锑在不同pH条件下的价态变化及静电排斥作用,重金属锑截留率由98.2%提升至99.6%;微塑料浓度的增加会降低膜通量,提高锑截留效果,这可能是微塑料对溶液中重金属锑的吸附作用及微塑料在膜表面的积聚产生的筛分效应引起的.