Nanofiltration for drinking water treatment: a review

In recent decades, nanofiltration (NF) is considered as a promising separation technique to produce drinking water from different types of water source. In this paper, we comprehensively reviewed the progress of NF-based drinking water treatment, through summarizing the development of materials/fabrication and applications of NF membranes in various scenarios including surface water treatment, groundwater treatment, water reuse, brackish water treatment, and point of use applications. We not only summarized the removal of target major pollutants (e.g., hardness, pathogen, and natural organic matter), but also paid attention to the removal of micropollutants of major concern (e.g., disinfection byproducts, per- and polyfluoroalkyl substances, and arsenic). We highlighted that, for different applications, fit-for-purpose design is needed to improve the separation capability for target compounds of NF membranes in addition to their removal of salts. Outlook and perspectives on membrane fouling control, chlorine resistance, integrity, and selectivity are also discussed to provide potential insights for future development of high-efficiency NF membranes for stable and reliable drinking water treatment.     

Arsenic removal from drinking water by a “loose” nanofiltration membrane

The removal of arsenic from water by a “loose” nanofiltration (NF) membrane was investigated. Prior to the arsenic removal studies, the loose NF membrane was characterized for molecular weight cut-off and pore size by saccharide retention measurements, and electrokinetic charge by streaming potential measurements. In addition, separation of both single salt and mixed salt electrolyte solutions was studied to investigate the ion transport properties of the membrane. Arsenic rejection experiments included variation of pH, arsenic feed concentration, and presence of background electrolyte. In general, arsenic rejection increased with increasing pH and arsenic feed concentration, and was enhanced in the presence of 0.01 M NaCl. Arsenic was removed 60–90% from synthetic feed waters containing 10, 32, 100, and 316 μg/L As(V), resulting in permeate arsenic concentrations of 4, 6, 10, and 25μg/L, respectively. The behavior of the membrane is consistent with the extended Nernst-Planck equation model predictions for an uncharged membrane where size exclusion controls ion retention. However, separation of Arsenic species was a due to a combination of size exclusion, preferential passage of more mobile ions, and charge exclusion.     

Effect of operating conditions in removal of arsenic from water by nanofiltration membrane

The removal of arsenic from synthetic waters and surface water by nanofiltration (NF) membrane was investigated. In synthetic solutions, arsenic rejection experiments included variation of arsenic retentate concentration, transmembrane pressure, crossflow velocity and temperature. Arsenic rejection increased with arsenic retentate concentration. Arsenic was removed 93-99% from synthetic feed waters containing between 100 and 382 μg/L as V, resulting in permeate arsenic concentrations of about 5 μg/L. Under studied conditions, arsenic rejection was independent of transmembrane pressure, crossflow velocity and temperature. In surface water, the mean rejection of As V was 95% while the rejection of sulfate was 97%. The co-occurrence of dissolved inorganics does not significantly influence arsenic rejection. The mean concentration of As in collected permeated was 8 μg/L. The mean rejection of TDS, total hardness and conductivity were 75, 88 and 75% respectively.     

膜技术在饮用水除砷中的应用研究进展

以低压驱动膜的微滤膜(MF)与超滤膜(UF),和高压驱动膜的反渗透膜(RO)与纳滤膜(NF)为主,分析了目前国内外膜技术在饮用水除砷方面的效果、影响因素、浓水处理、膜污染及其清洗等方面的应用研究和进展情况,同时对膜技术优缺点及其在除砷中的应用研究方向与前景做了展望.     

Rejection of As(III) and As(V) from arsenic contaminated water via electro-cross-flow negatively charged nanofiltration membrane system

A specially designed electro-cross-flow nanofiltration (NF) membrane system was used for this investigation. To enhance the rejection of arsenic ionic species like H₂AsO₄⁻, a NF membrane having a negative surface charge was fabricated via the interfacial polymerization process. The membrane was characterized by SEM, AFM, surface charge density, molecular weight cut-off (MWCO), total and skin thickness and pure water flux. The parameters that affected the rejections of As(III) and As(V) were studied; they included the initial arsenic concentration, the applied potential, pH of the feed, the cross-flow filtration pressure and the presence of different salts in the feed. Among those parameters, the pH of the feed greatly affected As(V) rejection; As(V) ([As(V)]_o = 1000 ppb) rejection was increased from 72.3 to 98.5% when pH of the feed was changed from 3.0 to 10.0. This might be due to the fact that higher pH enhanced the formation of negative divalent anion like HAsO₄²⁻ which should be rejected more effectively by the negative surface charge of the NF membrane. Beside the effect of the negative surface charge of the membrane, applied potential increased the As(V) rejection by 48.2% when the applied potential was increased from 0 to 2.0 V for a feed containing 1000 ppb initially. For the same change of applied potential rejection of As(III) was increased from 52.3 to 70.4%; this might be the result of the formation of anionic species like H₂AsO₃⁻ from the neutral molecule of H₃AsO₃ by the applied potential.     

Comparison of polyamide nanofiltration and low-pressure reverse osmosis membranes on As(III) rejection under various operational conditions

A nanofiltration (NF) membrane and a low-pressure reverse osmosis (LPRO) membrane both with aromatic polyamide selective layer from the same manufacturer were employed for the comparison of their performances in terms of As(III) rejection and filtration flux under a variety of operational conditions. In addition to the smaller membrane pore size, the LPRO membrane possesses much more dissociable functional groups than the NF membrane. When the feed pH was below the pKa₁ value (9.22) of H₃AsO₃, for which the steric hindrance is the only rejection mechanism, the removal efficiencies by NF and LPRO were about 10% and 65%, respectively. When the feed pH was higher, for which electrostatic effect began to take effect, the removal efficiencies could reach 40% and 90% for NF and LPRO, respectively. The rejection performance of LPRO was marginally affected by the feed As(III) concentration or ionic strength, although ionic strength had a strong effect on the filtration flux. In contrast, feed As(III) concentration and ionic strength had little effect on the filtration flux but great influence on the As(III) rejection performance of NF. The filtration flux was enhanced with the increase of transmembrane pressure for either NF or LPRO. The NF model could predict the general trend of the effects of the filtration flux, the feed water chemistry and its own concentration on As(III) rejection ratio by the NF membrane, but the rejection ratios were over-predicted.     

Kinetic Modeling of Arsenic Removal from Water by Ferric Ion Loaded Red Mud

A laboratory study was conducted to investigate the ability of ferric ion loaded red mud (FRM) for the removal of arsenic species from water. The adsorbent material was characterized by scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. For an initial arsenic concentration lower than 0.3 mg/L, the FRM with a dosage of 1 g/L was able to reduce As(III) at pH 7 below 10 µg/L, the maximum contaminant level (MCL) of arsenic in drinking water set by the World Health Organization. In the case of As(V) removal, FRM was also particularly effective in reducing the initial arsenic concentration value of 1 mg/L at pH 2, below the MCL requirement of arsenic for drinking water. According to kinetic sorption data, the initial stage of adsorptions of As(III) and As(V) onto FRM were mainly governed by the external diffusion mechanism; however, upon saturation of the external adsorbent surface, the arsenic species were eventually adsorbed by intraparticle diffusion mechanism. The present results are promising for using the very inexpensive FRM as a low-cost material that is effective in remediating drinking waters contaminated with low concentrations of arsenic species. We report here the sorption kinetics and adsorption mechanisms of As(III) and As(V) on the FRM that has not been decsribed previously.     

Performance evaluation of polyamide nanofiltration membranes for phosphorus removal process and their stability against strong acid/alkali solution

In this study,a quantitative performance of three commercial polyamide nanofiltration(NF) membranes(i.e.,NF,NF90,and NF270) for phosphorus removal under different feed conditions was investigated.The experiments were conducted at different feed phosphorus concentrations(2.5,5,10,and 15 mg·L~(-1)) and elevated pHs(pH 1.5,5,10,and 13.5) at a constant feed pressure of 1 MPa using a dead-end filtration cell.Membrane rejection against total phosphorus generally increased with increasing phosphorus concentration regardless of membrane type.In contrast,the permeate flux for all the membranes only decreased slightly with increasing phosphorus concentration.The results also showed that the phosphorus rejections improved while water flux remained almost unchanged with increasing feed solution pH.When the three membranes were exposed to strong pHs(pH 1.5 and 13.5) for a longer duration(up to 6 weeks)it was found that the rejection capability and water flux of the membranes remained very similar throughout the duration,except for NF membrane with marginal decrement in phosphorus rejection.Adsorption study also revealed that more phosphorus was adsorbed onto the membrane structure at alkaline conditions(pH 10 and 13.5) compared to the same membranes tested at lower pHs(pH 1.5 and 5).In eonelusion,NF270 membrane outperformed Nf and NF90 membranes owing to its desirable performance of water flux and phosphorus rejection particularly under strong alkali solution.The NF270 membrane achieved 14.0 L·m~(-2)·h~(-1) and 96.5% rejection against 10 mg·L~(-1) phosphorus solution with a pH value of 13.5 at the applied pressure of 1 MPa.     

Nanofiltration flux, fouling and retention in filtering dilute model waters

Fouling of membranes decreases the applicability of the nanofiltration (NF) process, and thus a deeper understanding of membrane fouling is needed. Fouling and retention of different NF membranes by model feed waters was investigated in a laboratory-scale filtration unit. The model waters were composed so as to imitate the characteristics of chemically pre-treated surface water. No differences were seen in membrane flux declines when filtering feed waters containing the studied organic compounds of different characteristics. However, organic matter containing feed waters resulted in remarkably lower flux than the metal ions containing feed waters. An additional decrease in flux was seen when both organic matter and metal ions,especially silica, were present in the feed water. An increased feed water organics concentration increased the retention of organic matter, but the addition of metal ions to organics containing feed water caused a decrease in the retention of both organic matter and conductivity. The different behaviour is most probably caused by the differences in the fouling layers and foulant characteristics as well as by the electroneutrality effect. Generally, it is difficult to change feed water composition to non-fouling, but the operating pH can be used to some extent in optimising membrane performance.     

Development of an Electrochemical Device for Removal of Arsenic from Drinking Water

The forthcoming introduction of lower standards for arsenic in drinking water requires new technologies for arsenic removal. We report the development of an electrochemical unit for remediating domestic water supplies for homes without municipally treated water. Electrolysis in a two‐anode system provides oxidants to convert As(III) to As(V) in situ, and a sacrificial anode to deliver iron into solution. Conditioning tanks after each electrolysis step ensure completion of the chemical reactions. At the pH of domestic water, As(V) co‐precipitates with Fe(OH)₃; subsequent filtration leaves <10 ppb of inorganic arsenic in solution.     

不同国产纳滤膜对饮用水中氟离子的去除影响研究

选用两种国产纳滤膜NF1和VNF2进行除氟的实验研究,考察了不同的原水pH、操作压力、进水F-浓度、温度以及腐殖酸的浓度对纳滤除氟截留率以及膜通量的影响。实验结果表明:VNF2膜的截留率高于NF1膜,而膜通量则低于NF1;同时两种膜的最佳操作条件为pH在6.5~7.0,温度在18~23℃,操作压力为0.4 MPa,进水氟离子浓度为4 mg/L;而腐殖酸主要通过静电斥力和氢键影响纳滤膜的截留率和膜通量,同时出水F-浓度满足生活饮用水卫生标准(GB5749-2006)。     

进水水质对纳滤膜苦咸水软化的分离性能

针对黄淮地区苦咸水,构建了小试级别的纳滤膜法软化系统,并开展了包括pH、总溶解固体含盐量（TDS）和总有机碳（TOC）等进水水质对DL、DK型纳滤膜的软化分离实验。结果表明,pH为3~10、TDS为1317~5926 mg·L^-1和TOC为2.72~12.24 mg·L^-1的进水条件下,DL和DK纳滤膜比通量随pH的增加分别呈先上升后下降和缓慢下降的趋势,随进水TDS和TOC的增加呈整体下降趋势,而纳滤膜对硬度离子（Mg²⁺和Ca²⁺）的截留率均呈明显的上升趋势。DL膜运行至267 h时,膜比通量下降幅度超过10%,进行化学清洗,酸洗后膜比通量恢复率达到85.05%,酸洗加碱洗后该值高达97.2%,结合扫描电子显微镜和原子力显微镜表征结果,可知化学清洗对膜面污染有较好的去除效果。     

Nanofiltration of Hormone Mimicking Trace Organic Contaminants

Abstract

The removal mechanisms of three hormone mimicking organic compounds by nanofiltration (NF) membranes have been examined. Two NF membranes having different pore sizes were used in laboratory‐scale nanofiltration experiments with feed solutions spiked with a hormone mimicking compound—nonylphenol, tert‐butylphenol, or bisphenol A. Retention of the compounds was determined at various solution chemistries, namely aqueous solution pH, ionic strength, and presence of natural organic matter. The nanofiltration behavior of the selected hormone mimicking compounds appears similar to that of natural hormones as reported in our previous work. While the solution pH can dramatically influence the retention of hormone mimicking compounds by a loose NF membrane, ionic strength does not affect the nanofiltration of such contaminants. However, in the presence of natural organic matter in the feed solution, ionic strength appears to play a significant role in solute‐solute and solute‐membrane interactions, resulting in increased retention due to partitioning of the hormone mimicking compounds onto organic matter at a higher ionic strength.     

改性麦饭石去除饮用水中的砷

饮用水中砷超标会严重危害人的身体健康。该文利用MnO：对麦饭石进行改性,制备了一种高效的吸附剂;同时研究了在不同pH值、接触时间、改性麦饭石的投加量及砷的初始浓度条件下,改性麦饭石对饮用水中As（V）的去除。研究结果表明：在以上不同条件下,改性麦饭石对水中As（V）均有一定的去除效果。当pH值为6、接触时间为60min、改性麦饭石投加量为1000mg／L、水中As（V）的初始浓度为100μg／L时,改性麦饭石对饮用水中的As（V）的去除率为91％,此时水中砷的含量低于国家生活饮用水卫生标准（10μg／L）。     

Solar‐light assisted removal of arsenic from natural waters: effect of iron and citrate concentrations

The optimal conditions to remove arsenic(III) from a solution were fitted using a factorial experimental design in a reaction catalysed by visible light (black light, 360 nm) and an iron‐citrate complex. Experiments were performed by simultaneously modifying the two variables affecting the removal of arsenic, i.e. iron and citrate concentrations. The single polynomial function obtained with the factorial design methodology indicates that the iron concentration was the most critical parameter in the removal of arsenic by precipitation. Mathematically, it was determined that the optimum molar ratio for arsenic, citrate and iron was 1:4.5:18.7, respectively, over 90% of arsenic being eliminated after 4 h of irradiation. The comparison between the As(III) and As(V) co‐precipitation rates indicates that almost 80% of As(III) was removed after 1 h of irradiation with black light, while As(V) required 4 h of irradiation to reach the same value. When natural water containing approximately 1 mg L⁻¹ of arsenic, only as As(V), was irradiated with solar light under optimised conditions, approximately 95% of the arsenic was removed after 1 h of irradiation. Copyright © 2006 Society of Chemical Industry     

MIEX—DOC离子交换树脂的饮用水除砷研究

对新型阴离子交换树脂MIEX—DOC@的除砷性能进行了研究,考察了该树脂除砷容量、对三价砷[As（m）]和五价砷[As（V）]的去除能力、不同离子和水体pH值对树脂除砷[包括As（Ⅲ）和As（V）]效率的影响。结果表明,MIEX-DOC~树脂对人工配制高砷水（O．1mg·L-1）的除砷容量约为0．0051mg·mL-1;对As（Ⅲ）和As（V）的去除能力相当;常见的共存离子对树脂除砷效率有抑制或促进影响;不同pH值下,MIEX—DOC@树脂除砷效率不同,但对0．1mg·L-1的高砷水的除砷效率均达到50％以上。对农村高砷水的实地中试研究表明,当源水砷浓度约为0．1mg·L-1时,出水砷浓度低于0．05mg·L-1达到《生活饮用水卫生标准》（GB5749—2006）的农村小型集中式供水和分散式供水水质指标。成本分析结果表明,采用国产MIEX-DOC净水设备的除砷效果与进口设备相当,但除砷成本较低（0．56元·t-1）,在我国农村高砷饮用水处理中有一定应用潜力。     

Sorption on natural solids for arsenic removal

Steady state experiments were conducted on arsenic sorption from aqueous solutions by natural solids to test the feasibility of these materials to act as concentrator for arsenic removal from groundwater and drinking water. The solids considered were natural zeolites, volcanic stone, and the cactaceous powder CACMM. The arsenic species studied were As(III), As(V), dimethylarsinic acid (DMA) and phenylarsonic acid (PHA). The arsenic removed was determined from the data obtained by measuring the concentration diminution of the arsenic species in the liquid phase at equilibrium before and after the adsorption experiment by means of ICP-AES for the total concentration of arsenic and IC-ICP-MS to determine the arsenic species. The latter method allowed the detection of As(V) additionally formed as a result of the oxidation of As(III) on some of the zeolites. The sorption of the arsenic species onto zeolites was studied on both non-activated and activated zeolites, as well as on zeolites hydrogenated or modified with iron, and with respect to varying pH. The kinetics and the ability to desorb and readsorb the arsenic species were investigated for selected zeolites.     

Removal of heavy metals from wastewater by membrane processes: a comparative study

Wastewater containing copper and cadmium can be produced by several industries. The application of both reverse osmosis (RO) and nanofiltration (NF) technologies for the treatment of wastewater containing copper and cadmium ions to reduce fresh water consumption and environmental degradation was investigated. Synthetic wastewater samples containing Cu²⁺ and Cd²⁺ ions at various concentrations were prepared and subjected to treatment by RO and NF in the laboratory. The results showed that high removal efficiency of the heavy metals could be achieved by RO process (98% and 99% for copper and cadmium, respectively). NF, however, was capable of removing more than 90% of the copper ions existing in the feed water. The effectiveness of RO and NF membranes in treating wastewater containing more than one heavy metal was also investigated. The results showed that the RO membrane was capable of treating wastewater with an initial concentration of 500 ppm and reducing the ion concentration to about 3 ppm (99.4% removal), while the average removal efficiency of NF was 97%. The low level of the heavy metals concentration in the permeate implies that water with good quality could be reclaimed for further reuse.     

Is the Coagulation-Filtration Process with Fe(III) Efficient for As(III) Removal from Groundwaters?

The coagulation–filtration process using Fe(III) salts is the most frequently practiced technology for As(V) removal in full scale water treatment plants. The co-existing As(III) is usually oxidized to As(V) prior to removal. Nonetheless, research studies applying high As(III) initial concentrations showed significant As(III) removal capacities, however, the efficiency of the process for initial As(III) concentrations commonly encountered in drinking water, i.e., 10-100 μg/L is not sufficiently investigated. The experimental results of this study indicated that the coagulation–filtration process using Fe(III) can safely meet the drinking water regulation limit of 10 μg/L, only when the initial As(III) concentration is < 25 μg/L and the Fe(III) dose ≥ 5 mg/L, for experiments performed with NSF challenge water. The limitations for efficient As(III) removal are attributed to the fact that As(III), under circumneutral pH values is mostly present with the uncharged H₃AsO₃ form, which is not efficiently adsorbed onto iron oxy hydroxides (FeOOH), the product of Fe(III) hydrolysis. Adsorption isotherms data were best fitted to BET model, indicating multi-layer adsorption and low affinity of As(III) for Fe(III) hydroxides.     

Arsenic adsorption on Ti‐pillared montmorillonite

BACKGROUND: Arsenic pollution in drinking water has been found in most countries. Arsenate (As(V)) and arsenite (As(III)) are two major forms of inorganic arsenic species, and the latter is the more toxic. The removal of arsenic ions from water has attracted increased attention, and therefore further understanding and development of techniques for removal of arsenic ions are required. RESULTS: Adsorption of arsenate and arsenite from aqueous solutions using Ti‐pillared montmorillonite (Ti‐MMT) was investigated as a function of contact time, pH, temperature, coexisting ions, and ionic strength. The adsorption of both arsenate and arsenite were temperature and pH dependent, indicating different adsorption mechanisms. The effect of coexisting ions on the adsorption was also studied and, among the ions investigated, only phosphate had a noticeable influence on the adsorption of arsenate, while the effect of other ions was negligible. A pseudo‐second‐order chemical reaction model was obtained for both arsenate and arsenite; adsorption isotherms of arsenate and arsenite fitted the Langmuir and Freundlich isotherm models well. X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS) were used to study the nature of surface elements before and after adsorption. CONCLUSIONS: This work demonstrates that Ti‐pillared montmorillonite is an efficient material for the removal of arsenate and arsenite from aqueous solutions. Experimental parameters such as contact time, solution pH, temperature, initial concentration, coexisting ions, and ionic strength have been optimized. Copyright © 2010 Society of Chemical Industry