Fabrication of asymmetric poly (m-phenylene isophthalamide) nanofiltration membrane for chromium(VI) removal

The feasibility of employing nanofiltration for the removal of chromium(VI) from wastewater was investigated. Poly (m-phenylene isophthalamide) (PMIA) was used to fabricate asymmetric nanofiltration membrane through the phase-inversion technique. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the obtained membrane, and the both confirmed a much smoother surface which could reduce membrane fouling. The PMIA membrane showed di erent rejections to electrolytes in a sequence of Na2SO4 > MgSO4 > NaCl > MgCl2, which was similar to the sequence of the negatively charged nanofiltration membranes. Separation experiments on chromium(VI) solution were conducted at various operating conditions, such as feed concentration, applied pressure and pH. It is concluded that chromium(VI) could be e ectively removed from chromiumcontaining wastewater by the PMIA nanofiltration membranes while maintaining their pollution resistance under alkaline condition.     

蛋白质及无机离子对纳滤膜去除PFOS的影响

以全氟辛烷磺酸（PFOS）为目标去除物,选取牛血清蛋白（BSA）为典型蛋白质类有机物,考察了BSA及其浓度,以及BSA与无机离子共存时,离子强度、离子种类对聚酰胺纳滤膜去除水中PFOS的影响.研究发现,原液中存在BSA时,PFOS的去除率有显著提高,而且BSA浓度越高,PFOS的去除率越高;当BSA与无机离子共存时,离子强度越大,PFOS去除率越高.这可能是因为BSA不但会吸附一部分PFOS,还会造成膜污染,BSA浓度越大,膜污染越严重,膜的筛分能力越强,且膜面与PFOS之间的静电排斥力越大,从而提高了PFOS的截留率.而无机离子的存在减小了BSA分子之间及与膜面之间的静电排斥力,使BSA污染层更加厚实,进一步增强了膜的筛分能力.此外,Ca²⁺提高PFOS去除率的能力优于Na⁺.     

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.     

无机结垢对纳滤膜分离水中全氟化合物的影响

选取全氟辛烷磺酸(PFOS)和全氟丁烷磺酸(PFBS)两种链长不同的典型全氟化合物(PFASs)作为目标去除物,以硫酸钙为典型无机结垢,研究硫酸钙结垢不同阶段中纳滤膜去除PFASs的特征和相关机理,简称硫酸钙试验,同时以相同离子强度的非结垢无机盐溶液开展对比试验考察目标PFASs的截留规律.结果表明,当硫酸钙和目标PFASs共存时,PFOS稳定截留率为硫酸钙试验(97.1%)>对比试验(93.0%),而PFBS稳定截留率为对比试验(46.2%)>硫酸钙试验(38.2%).对于同一PFAS,同一过滤时刻,膜面带电量:硫酸钙试验<对比试验;联合截留率、膜通量和Zeta电位综合分析可知,硫酸钙结垢过程中,PFOS的截留主要由Ca²⁺与PFOS的络合及架桥作用控制,该作用影响PFOS分离过程中的空间位阻作用强度;PFBS过滤初期的截留中静电排斥起主要作用,结垢层生成后,滤饼层强化的浓差极化作用成为PFBS截留效果下降的主要原因.     

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.     

聚酰胺复合纳滤膜去除水中PFOS的研究

利用聚酰胺复合纳滤膜去除水中的PFOS,在0.6MPa操作压力条件下过滤12h,研究PFOS浓度、离子种类、总离子强度以及海藻酸对PFOS截留效果的影响.结果表明,随着PFOS浓度增大其截留率也随之升高;溶液总离子强度越大,PFOS截留率越高,当过滤进行到12h时,溶液总离子强度为150mmol/L时,PFOS的截留率比溶液总离子强度为10mmol/L时仍高2.1%;溶液中加入1mmol/L Ca²⁺时PFOS的截留效果优于加入1mmol/L Na⁺时的效果;并且随着二价离子浓度的增加,截留率上升,过滤结束时,Ca²⁺浓度为3mmol/L的条件下PFOS的截留率约为97.5%,高于1mmol/L Ca²⁺存在时PFOS的截留率（95%）;海藻酸存在时PFOS的截留率显著增高,尤其在1mmol/L钙离子存在条件下,过滤12h后PFOS的截留率仍可达到95%以上,但海藻酸会导致膜污染的发生从而引起膜通量下降.     

San copolymer membranes with ion exchangers for Cu(II) removal from synthetic wastewater by electrodialysis

Heterogeneous membranes were obtained by using styrene-acrylonitrile copolymer (SAN) blends with low content of ion-exchanger particles (5 wt.%). The membranes obtained by phase inversion were used for the removal of copper ions from synthetic wastewater solutions by electrodialytic separation. The electrodialysis was conducted in a three cell unit, without electrolyte recirculation. The process, under potentiostatic or galvanostatic control, was followed by pH and conductivity measurements in the solution. The electrodialytic performance, evaluated in terms of extraction removal degree (rd) of copper ions, was better under potentiostatic control then by the galvanostatic one and the highest (over 70%) was attained at 8 V. The membrane efficiency at small ion-exchanger load was explained by the migration of resin particles toward the pores surface during the phase inversion. The prepared membranes were characterized by various techniques i.e. optical microscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis and differential thermal analysis and contact angle measurements.     

PVDF超滤膜进行聚乙二醇甲基丙烯酸甲酯 (PEGMA)紫外光照射接枝的膜面表征与抗污染分析

本文采用紫外光照射接枝的方法将聚乙二醇甲基丙烯酸甲酯(PEGMA)亲水单体接枝在疏水性聚偏氟乙烯(PVDF)超滤膜表面,改善PVDF膜的亲水性能.实验中以N,N-亚甲基双丙烯酰胺(MBAA)为交联剂作为对比,发现添加MBAA可以减少PEG接枝层的溶胀性.本实验研究不同改性条件对膜性能的影响,利用表面接触角(CA)、红外光谱分析(ATR-IR)、扫描电镜(SEM)等手段表征膜表面特征,同时研究了改性膜对乳化油和牛血清蛋白溶液分离效率和抗污染能力.实验结果表明,经改性后膜亲水性明显提高,对污染物的截留效果和抗污染能力均有所提高.     

介孔氮化碳对水中全氟辛烷磺酸的吸附去除研究

以SBA-15为模板、四氯化碳和乙二胺为前驱体,通过聚合反应制备了介孔氮化碳(Mesoporous Carbon Nitride,MCN).同时,采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)和元素分析等手段对MCN进行了表征分析,并考察了MCN对水中全氟辛烷磺酸(PFOS)的吸附性能.结果表明,MCN吸附PFOS的过程符合准二级动力学模型,其吸附行为遵循Langmuir等温线模型;MCN吸附去除PFOS的效率受溶液pH值、溶液温度及共存离子等因素的影响,其中,溶液pH值的影响最为显著,当溶液pH值分别为2.2和10.6时,MCN对PFOS的去除率分别为98.15%和5.59%;吸附PFOS饱和后的MCN可以用0.1 mol·L-1NaOH溶液进行解吸,经5次循环/再生后的MCN对PFOS的去除率仍在95%以上.与介孔碳(CMK-3)和活性炭(AC)相比,MCN对PFOS显示出更优越的吸附能力.     

某微污染水源自来水厂的纳滤深度处理效果研究

采用一级四段纳滤组合工艺处理南方某微污染水源自来水厂的传统净水工艺段出水,考察了纳滤膜工艺对出水水质的提升效果.结果表明,纳滤对常规水质指标与微量有机物有较好的去除效果,对混凝沉淀池出水中TOC和UV_(254)的去除率在95%以上(出水TOC≤0.3 mg·L~(-1),UV254≤0.005 cm~(-1));对卤乙酸、三卤甲烷前体物、多环芳烃和有机氯农药的截留率分别在62%、85%、50%和95%左右,使用UMU-SOS测试的出水遗传毒性低于检出限,不同段纳滤膜对相对分子质量较大的消毒副产物前体物与有机氯农药的去除率未呈现明显差异,但对相对分子质量较小的多环芳烃去除效果呈现明显差异,表明纳滤主要依靠物理截留去除水中相对分子质量较大的有机物,对相对分子质量较小的有机物则存在较大的局限性.与之相比,水厂目前使用的双级臭氧-生物活性炭深度处理工艺对传统净水工艺出水中多环芳烃、有机氯农药、遗传毒性的去除截留率分别仅为17%、62%、80%左右,显示纳滤对微量有机物的去除效果更为理想.     

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.     

添加剂PEG对共混超滤膜结构和性能的影响

以不同分子量聚乙二醇 (PEG)作为PSf/A共混超滤膜的添加剂 ,测定所制备膜的水通量、截留率 .结果表明 ,膜的水通量随PEG分子量的变化呈现非线性关系 .当PEG分子量为4000时 ,水通量达到最大值115.2mL·(cm²·h)^-1,是不加PEG时的6倍 .通过超滤实验结果以及膜结构的电镜照片的观察 ,研究了PSf/A共混超滤膜体系中PEG作用的规律 .PEG分子量的增加改变了PSf/A铸膜液体系的相平衡关系 ,使铸膜液成为热力学不稳定体系 ,加速了相分离的发生 ;另外 ,PEG分子量的增加提高了铸膜液的粘度 ,引起相分离的延迟,这2种作用影响了膜的最终结构和性能.     

Removal of haloacetic acids by nanofiltration

Haloacetic acids, disinfection byproducts (DBPs) formed during drinking water chlorination process are carcinogens. The e cacy of nanofiltration (NF) was examined for the removal of five regulated haloacetic acids (HAA5): chloro-, dichloro-, and trichloro-acetic acid (CAA, DCAA, and TCAA); bromo-, and dibromo-acetic acid (BAA, and DBAA) in synthetic water. NF with the dense negatively charged membrane (ES 10), is the most e cient in removing HAA5 than the loose negatively charged membrane (NTR 7410) and neutral surface membrane (NTR 729HF), due to the greater electrostatic repulsion (Donan exclusion) and sieve e ect. Excellent HAA5 removal e ciency of 90%–100% could be obtained even at a low pressure of 1 105 Pa with ES 10. Changes in cross-flow velocity did not e ect the performance of membranes with a small pore size such as ES 10 and NTR 729HF. The increase in HAA5 concentration exhibited the adverse e ect on the performance of three membranes by strengthening the concentration polarization, which was the driving force for the di usion of HAA anions across the membrane.     

有机大分子对聚酰胺复合纳滤膜偏硅酸钠污染的影响

选用腐殖酸(HA),海藻酸钠(SA),牛血清蛋白(BSA)和偏硅酸钠分别模拟水体中有机大分子和无机污染物对聚酰胺复合纳滤膜进行了膜污染试验.结合原子力显微镜(AFM)及自制的胶体探针定量测定了不同条件下,膜-偏硅酸钠以及偏硅酸钠-偏硅酸钠之间的作用力.分析了污染膜的表面结构特征及其通量恢复率,系统考察了膜表面吸附不同有机大分子后,对随后硅酸盐污染行为的影响.结果表明:膜表面吸附HA和SA后,膜面负电位增加,与偏硅酸钠之间静电斥力变大,导致其结合能力减弱,减缓了结垢污染.然而,吸附BSA后的膜与无有机条件膜相比,负电位基本一致,故对纳滤膜结垢过程几乎无影响.     

纳滤膜对有机物的截留机理研究

选用美国ＴｒｉＳｅｐ公司ＴＳ８０纳滤膜，在操作压力０．７ＭＰａ下考察了纳滤膜对有机物的截留机理，ＴＳ８０纳滤膜平均去除率为９０．３％，根据色谱质谱联机分析结果可知．ＴＳ８０纳滤膜能使色谱质谱峰丰度降低５０％左右，其对有机物的去除是由有机物的结构特征（如分子量、极性）与有机物问膜问的相互作用关系共同决定的。     

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.     

Preparation and application of amino functionalized mesoporous nanofiber membrane via electrospinning for adsorption of Cr3+ from aqueous solution

Novel amino (-NH₂) functionalized mesoporous polyvinyl pyrrolidone (PVP)/SiO₂ composite nanofiber membranes were fabricated by a one-step electrospinning method using poly (vinyl alcohol) and tetraethyl orthosilicate (TEOS) mixed with cationic surfactant, cetyltrimethyl ammonium bromide (CTAB) as the structure directing agent. Ureidopropyltriethoxysilane was used for functionalization of the internal pore surfaces. The membranes were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) images, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), element analyzer and N2 adsorption-desorption isotherms. The nanofiber diameters, average pore diameters and surface areas were 100-700 nm, 2.86 nm and 873.62 m²/g, respectively. These mesoporous membranes functionalized with -NH₂ groups exhibited very high adsorptions properties based on the adsorption of Cr³⁺+ from an aqueous solution. Equilibrium adsorption was achieved after approximately 20 min and more than 97% of chromium ions in the solution were removed. The membrane could be regenerated through acidification.     

新型纳滤膜在水处理与水回用中的研究进展

近年来,纳滤膜（NF）以其较高水渗透性能、良好水/盐选择性和相较于反渗透膜（RO）低工作压力等优势被广泛应用于水处理和水回用中。然而传统的商品NF的分离性能具有局限性,例如对人体有益的矿物质去除率过高、对污染物去除率偏低,而且渗透性能-选择性能的制衡等问题严重制约了NF的发展及潜在的应用。详细介绍了NF膜在水处理和水回用中的应用及NF结构优化和改性的最新进展;回顾了通过对NF膜除盐层的孔隙率、亲水性、表面官能团及表面带电性等改性方式来提高NF的渗透性、选择性、抗污染、抗菌和耐氯能力等取得的研究成果;最后展望了新型NF膜在水处理和水回用领域的发展。     

UIO-66改性聚酰胺正渗透复合膜的制备及性能研究

采用界面聚合方法将UIO-66纳米颗粒引入复合膜中制备出改性的聚酰胺复合膜,并利用傅里叶红外光谱（FT-IR）、扫描电子显微镜（SEM）、原子力显微镜（AFM）、X射线衍射光谱（XRD）和接触角仪等仪器对材料和复合膜进行测定表征.以去离子水为原料液,1mol/L氯化钠溶液为汲取液进行渗透性能测试.选取BSA及SA作为污染物进行污染实验,并利用自制探针,借助原子力显微镜（AFM）测定了污染物与膜面的微观作用力.研究发现,相较于原始的聚酰胺复合膜,当UIO-66材料的添加量为0.04wt%时,改性复合膜在FO模式下的纯水通量由10.28L/（m²·h）增大到13.67L/（m²·h）, PRO模式下纯水通量由17.68L/（m²·h）增大到20.41L/（m²·h）,渗透性能改善效果显著,并具有较好的选择性能.此外,污染实验发现相较于原始膜,改性复合膜的通量衰减趋势较缓且与污染物之间粘附力都较小,说明UIO-66改性聚酰胺复合膜的抗污染性能有所提升.     

纳滤处理含铜废水的试验和经济性分析

采用纳滤对含Cu^2＋废水进行试验研究,讨论了初始浓度、操作压力、运行时间、阴离子种类、浓差极化对处理效果的影响。试验结果表明NF90膜对含Cu^2＋废水有良好的处理效果,在试验的进水浓度范围内,Cu^2＋去除率超过了98％,出水Cu^2＋浓度低于2．0mg／L,达到中国（GB8978—1996）总铜排放低于2．0mg／L的标准,可以达标排放;随着废液体积的浓缩,铜离子浓缩可达十倍以上,可回用于镀件漂洗,从而实现铜金属的再生利用。与传统的化学沉淀法处理工艺相比,纳滤一次投资大,但由于其运行费用低,具有明显的环境优势和经济效益,值得在重金属废水处理中推广应用。