Polymer-based membranes for solvent-resistant nanofiltration:A review

Separation of organic mixture is an inevitable process in most modern industrial processes. In the quest for a more sustainable and efficient separation, solvent-resistant nanofiltration(SRNF) has emerged as a promising answer. This is because SRNF is a membrane-based process which offers the key advantages of high efficacy and low energy intensity separation. In particular, polymer-based membranes can offer compelling opportunities for SRNF with unprecedented cost-effectiveness. As a result, intensive research efforts have been devoted into developing novel polymer-based membranes with solvent-resistant capacities as well as exploring potential applications in different types of industries. In this review, we aim to give an overview of the recent progress in the development of the state-of-the-art polymer-based membranes for SRNF in the first section. Emerging nanomaterials for mixed matrix and thin film nanocomposite membranes are also covered in this section. This is followed by a discussion on the current status of membrane engineering and SRNF membrane commercialization. In the third section, we highlight recent efforts in adopting SRNF for relevant industrial applications such as food, bio-refinery, petrochemical, fine chemical and pharmaceutical industries followed by separations of enantiomers in stereochemistry, homogeneous catalysis and ionic liquids. Finally, we offer a perspective and provide deeper insights to help shape future research direction in this very important field of SRNF.

Fabrication of Solvent-Resistant Nanofiltration Membrane via Interfacial Polymerization Based on Cellulose Acetate Membrane

Although a great progress has been achieved for the development of NF membranes and technologies and SRNF do show a great potential in the separation of organic components, an NF membrane with good separation performance and good resistance to organic solvents are urgently needed for a more complicated situation in practical. In this study, a kind of solvent-resistant nanofiltration (SRNF) membrane was fabricated via interfacial polymerization on a laboratory optimized cellulose acetate (CA) basic membrane. The effects of interfacial polymerization parameters, such as water phase concentration, immersed time in the water phase and in the organic phase, on the pure water flux and rejection rate of C-2R yellow dyestuffs were investigated. A highest dye rejection rate of 72.9% could be obtained by water phase solution containing 1% m-xylylenediamine (mXDA) and organic phase solution with 0.2% trimesoyl chloride (TMC) under immersed time in water phase of 6 minutes and in organic phase of 40 seconds. This membrane demonstrated better resistance to methyl alcohol compared to commercial membrane. This study may offer an avenue to develop a solvent-resistant nanofiltration membrane.

Tannic acid/Fe^(3+)interlayer for preparation of high-permeability polyetherimide organic solvent nanofiltration membranes for organic solvent separation

Organic solvent nanofiltration(OSN)membranes have a great application prospect in organic solvent separation,but the development of OSN membranes is mainly restricted by trade-off between permeability and rejection rate.In this work,a TA/Fe^(3+)polymer was introduced into polyetherimide(PEI)ultrafiltration membranes crosslinked with hexamethylene diamine as the intermediate layer,and OSN membranes with high separation performance and solvent permeability were obtained through interfacial polymerization and solvent activation.The interlayer with high surface hydrophilicity and a fixed pore structure controlled the adsorption/diffusion of the amine monomer during interfacial polymerization,forming a smooth(average surface roughness<5.5 nm),ultra-thin(separation layer thickness reduced from 150 to 16 nm)and dense surface structure polyamide(PA)layer.The PA-Fe^(3+)_3-HDA/PEI membrane retained more than 94%of methyl blue(BS)in 0.1 g·L^(-1)BS ethanol solution at 0.6 MPa,and the ethanol permeation reached 28.56 L^(-1)·m^(-2)·h^(-1).The average flux recovery ratio(FRR)of PA-Fe^(3+)_(3)-HDA/PEI membrane was found to be 84%,which has better fouling resistance than PA-HDA/PEI membrane,and it was found to have better stability performance through different solvent immersion experiments and continuous operation in 0.1 g·L^(-1)BS ethanol solution.Compared with thin-film composite nanofiltration membranes,the PA-Fe^(3+)_(3)-HDA/PEI membrane can be manufactured from an economical and environment-friendly method and overcomes the trade-off between permeability and rejection rate,showing great application potential in organic solvent separation systems.

Ultrathin polyamide nanofiltration membrane prepared by triazine-based porous organic polymer as interlayer for dye removal

Separation membrane with high flux is generally encouraged in industrial application,because of the tremendous needs for decreasing membrane areas,usage costs and space requirements.The most effective and direct method for obtaining the high flux is to decrease membrane thickness.Polyamide(PA)nanofiltration membrane is conventionally prepared by the direct interfacial polymerization(IP)on substrate surface,and results in a thick PA layer.In this work,we proposed a strategy that constructing triazine-based porous organic polymer(TRZ-POP)as the interlayer to prepare the ultrathin PA nanofiltration membranes.TRZ-POP is firstly deposited on the polyethersulfone substrate,and then the formed TRZ-POP provides more adhesion sites towards PA based on its high specific surface areas.The chemical bonding between terminal amine group of TRZ-POP and the amide group of PA further improves the binding force,and strengthens the stability of PA layer.More importantly,the high porosity of TRZPOP layer causes the higher polymerization of initial PA owning to the stored sufficient amino monomer;and H-bonding interaction between amine groups of TRZ-POP and piperazine(PIP)can astrict the release of PIP.Thus,IP process is controlled,and the thinnest thickness of prepared PA layer is only<15 nm.As expected,PA/TRZ-POP membrane shows a more excellent water flux of 1414 L·m^(-2)·h^(-1)·MPa^(-1)than that of the state-of-the-art nanofiltration membranes,and without sacrificing dye rejection.The build of TRZPOP interlayer develops a new method for obtaining a high-flux nanofiltration membrane.

Performance comparison of lithium fractionation from magnesium via continuous selective nanofiltration/electrodialysis

Although selective nanofiltration(SNF)and selective electrodialysis(SED)have been widely adopted in the field of Mg^(2+)/Li^(+)separation,their differences have not been illustrated systematically.In this study,for the first time,SNF and SED processes in continuous mode were studied for Li+fractionation from the same brine with high Mg/Li ratios and their differences were discussed in detail.For a fair analysis of the two processes,typical factors were optimized.Specifically,the optimal operating pressure and feed flow rate for SNF were 2.4 MPa and 140 L·h^(-1),respectively,while the optimal cell-pair voltage and replenishment flow rate for SED were 1.0 V and 14 L·h^(-1),respectively.Although the Li^(+)fractionation capacity of the two processes were similar,the selectivity coefficient of SNF was 24.7% higher than that of SED and,thus,the Mg/Li ratio in purified stream of the former was 19.0% lower than that of the latter.Due to higher ion driving force,SED had clear advantages in recovery ratio and concentration effects.Meanwhile,the specific energy consumption of SED was 20.1% lower than that of SNF.This study provided a better understanding and guidance for the application and improvement of the two technologies.

Recent developments in nanofiltration membranes based on nanomaterials

Nanofiltration membranes are the core elements for nanofiltration process. The chemical structures and physical properties of nanofiltration membranes determine water permeability, solute selectivity, mechanical/thermal stability, and antifouling properties, which greatly influence the separation efficiency and operation cost in nanofiltration applications. In recent years, a great progress has been made in the development of high performance nanofiltration membranes based on nanomaterials. Considering the increasing interest in this field, this paper reviews the recent studies on the nanofiltration membranes comprising various nanomaterials, including the metal and metal oxide nanoparticles, carbon-based nanomaterials, metal–organic frameworks(MOFs), water channel proteins, and organic micro/nanoparticles. Finally, a perspective is given on the further exploitation of advanced nanomaterials and novel strategy for fabricating nano-based nanofiltration membranes. Moreover,the development of precision instruments and simulation techniques is necessary for the characterization of membrane microstructure and investigation of the separation and antifouling mechanism of nanofiltration membranes prepared with nanomaterials.

Removal of haloacetic acids by nanofiltration

Haloacetic acids, disinfection byproducts （DBPs） formed during drinking water chlorination process are carcinogens. The efficacy of nanofiltration （NF） was examined for the removal of five regulated haloacetic acids （HAAs）： chloro-, dichloro-, and trichioro-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 efficient in removing HAAs than the loose negatively charged membrane （NTR 7410） and neutral surface membrane （NTR 729HF）, due to the greater electrostatic repulsion （Donan exclusion） and sieve effect. Excellent HAAs removal efficiency of 90%-100% could be obtained even at a low pressure of 1×10^5 Pa with ES 10. Changes in cross-flow velocity did not effect the performance of membranes with a small pore size such as ES 10 and NTR 729HF. The increase in HAAs concentration exhibited the adverse effect on the performance of three membranes by strengthening the concentration polarization, which was the driving force for the diffusion of HAA anions across the membrane.

Separation and estimation of nanofiltration membrane transport parameters for cerium and neodymium

Lanthanides are widely used in various commercial applications, which results in public exposure to them, and it is a matter of concern. Many methods were used to remove lanthanides from wastewaters generated from their commercial use. In the present work, nanofiltration membrane process was used to remove the cerium and neodymium from their respective feed solutions. The feed and permeates were analyzed for solute concentration by inductively coupled plasma-atomic emission spectroscopy. Irreversible thermodynamics Spiegler-Kedem model, in combination with the film theory, was used to estimate the membrane transport parameters, viz., reflection coefficient of membrane and solute permeability, and mass transfer coefficient to study their dependence on feed solute concentration.

Fouling of nanofiltration membrane by effluent organic matter:Characterization using different organic fractions in wastewater

The UF membrane with molecular weight cutoff （MWCO） ranging from 2 to 100 kDa and XAD-8 resin were employed to identify the characteristic of molecular weight （MW） distribution of wastewater effluent organic matter （EfOM） in terms of TOC and UV254, as well as the amounts of the hydrophilic/hydrophobic organic fractions in different MW ranges. Then, the nanofiltration （NF） membrane fouling experiments were carded out using the above fractionated water to investigate the effect of MW distribution and hydrophihc/hydrophobic characteristics of EfOM on the membrane flux decline using the fractionated water samples. The experimental results have shown that 45.61% of the total organics belongs to the low MW one, among which the percentage of the hydrophilic organics with low MW （less than 2 kDa） was up to 28.07%, while that of the hydrophobic organics was 17.54%. In particular, the hydrophilic fraction was found to be the most abundant fraction in the effluents. MW distribution has a significant effect on the membrane fouling. When the MW was less than 30 kDa, the lower the MW, the larger was the specific flux decline, while in the case of MW higher than 30 kDa, the higher the MW, the larger was the specific flux decline, and the decline degree of low MW organics was larger than the high MW one. With the same MW distribution range, specific flux decline of the hydrophilic organic was considerably slower than that of the hydrophobic organic, which indicated that the hydrophobic organic fractions dominantly contribute to the flux decline.

Gradient nanoporous phenolics as substrates for high-flux nanofiltration membranes by layer-by-layer assembly of polyelectrolytes

Thin film composite(TFC) membranes represent a highly promising platform for efficient nanofiltration(NF)processes. However, the improvement in permeance is impeded by the substrates with low permeances. Herein,highly permeable gradient phenolic membranes with tight selectivity are used as substrates to prepare TFC membranes with high permeances by the layer-by-layer assembly method. The negatively charged phenolic substrates are alternately assembled with polycation polyethylenimine(PEI) and polyanion poly(acrylic acid)(PAA)as a result of electrostatic interactions, forming thin and compact PEI/PAA layers tightly attached to the substrate surface. Benefiting from the high permeances and tight surface pores of the gradient nanoporous structures of the substrates, the produced PEI/PAA membranes exhibit a permeance up to 506 L? m-2?h-1?MPa-1, which is ~2–10 times higher than that of other membranes with similar rejections. The PEI/PAA membranes are capable of retaining N 96.1% of negatively charged dyes following the mechanism of electrostatic repulsion. We demonstrate that the membranes can also separate positively and neutrally charged dyes from water via other mechanisms.This work opens a new avenue for the design and preparation of high-flux NF membranes, which is also applicable to enhance the permeance of other TFC membranes.

Investigation of Mg^2＋/Li^＋ Separation by Nanofiltration

The Mg2+/Li+/Cl solutions were filtrated with a commercially available DK nanofiltration membrane to investigate the possibility to enrich the lithium component.The investigation was significant as such an approach might be a competing substitute for the present lithium purification industry and the environmental protection purpose.The Donnan steric pore model(DSPM) was implemented for the prediction.The separation of Mg2+/Li+was mainly affected by the working pressure(or the permeation flux) and a limiting separation factor was found around 0.31.The effective membrane charge density was evaluated and its dependence on the permeation flux as well as the ion pattern was discussed.For predicting an actual separation of electrolytes,the experimental investigation seems necessary for the reliability and efficiency.

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.

Performance of Nanofiltration and Reverse Osmosis Membranes in Metal Effluent Treatment

The performance of different nanofiltration （NF） and reverse osmosis （RO） membranes was studied in treating the toxic metal effluent from metallurgical industry. The characteristics and filtration behavior of the processes including the wastewater flux, salt rejection and ion rejection versus operating pressure were evaluated. Then the wastewater flux of RO membrane was compared with theoretical calculation using mass transfer models, and good consistency was observed. It was found that a high rejection rate more than 95% of metal ions and a low Chemical Oxygen Demand （COD） value of 10 mg·L^-1 in permeate could be achieved using the RO composite membrane, while the NF rejection of the salt could be up to 78.9% and the COD value in the permeate was 35 mg·L^-1. The results showed that the product water by both NF and RO desalination satisfied the State Reutilization Qualification, but NF would be more suitable for large-scale industrial practice, which offered significantly higher permeate flux at low operating pressure.

Pilot Study on Nanofiltration Combined with Ozonation and GAC for Advanced Drinking Water Treatment

A pilot-scale study of advanced drinking water treatment was carried out in test site, and a combination of ozonation, granular activated carbon (GAC) and nanofiltration was employed as the experimental process. By optimizing the operational parameters of ozonation and GAC, a large quantity of micro-pollutants in drinking water was removed, which made the post-positioned nanofiltration operate more reliably. It was evident that nanofiltration shows good performance for removing residual organic matter, meantime partial minerals can also be retained by nanofiltration. Therefore the quality of drinking water can be further improved. In addition, NF membrane fouling and scaling can be solved by concentrate recycling, anti-scalant dosing and chemical rinsing effectively. By GAC adsorption for the residue chlorine and ozone self-decomposition, their oxidation on NF membrane material can be eliminated completely.

Recent advances in nanofiltration,reverse osmosis membranes and their applications in biomedical separation field

In the face of human society's great requirements for health industry,and the much stricter safety and quality standards in the biomedical industry,the demand for advanced membrane separation technologies continues to rapidly grow in the world.Nanofiltration(NF)and reverse osmosis(RO)as the highefficient,low energy consumption,and environmental friendly membrane separation techniques,show great promise in the application of biomedical separation field.The chemical compositions,microstructures and surface properties of NF/RO membranes determine the separation accuracy,efficiency and operation cost in their applications.Accordingly,recent studies have focused on tuning the structures and tailoring the performance of NF/RO membranes via the design and synthesis of various advanced membrane materials,and exploring universal and convenient membrane preparation strategies,with the objective of promoting the better and faster development of NF/RO membrane separation technology in the biomedical separation field.This paper reviews the recent studies on the NF/RO membranes constructed with various materials,including the polymeric materials,different dimensional inorganic/organic nanomaterials,porous polymeric materials and metal coordination polymers,etc.Moreover,the influence of membrane chemical compositions,interior microstructures,and surface characteristics on the separation performance of NF/RO membranes,are comprehensively discussed.Subsequently,the applications of NF/RO membranes in biomedical separation field are systematically reported.Finally,the perspective for future challenges of NF/RO membrane separation techniques in this field is discussed.

Positively charged nanofiltration membrane fabricated by poly(acid–base) complexing effect induced phase inversion method for heavy metal removal

Poly(arylene ether ketone)s with carboxylic groups(PAEK-COOH)is a good membrane fabrication material,a kind of polyacids,while polyethylenimine(PEI)is a weak organic base,a kind of polybases.Those polyacids and polybases would form ionic complexation at the interface of two liquid phases.In this paper,PAEK-COOH/N-methyl pyrrolidone(NMP)/1,4-dioxane(DO)mixture,employed as polymer casting solution and aqueous solution of PEI,used as coagulation bath,respectively.Then ion complexation induced phase inversion process is applied to prepare positively charged nanofiltration membrane with thinner but denser separation skin layer.The complexing reaction at the interface of two liquid phases has great influence on the kinetic aspects of phase inversion process,which in accordance would affect the morphology and performance of the membrane.The obtained membrane,fabricated via the ion complexation induced phase inversion method,is positively charged,has high water permeability,and possesses high rejection towards divalent cations,such as Mg^(2+),Ca^(2+),Pb^(2+)etc.,which could be used for removal of heavy metals from polluted water.At the optimal condition,the pure water flux of the PAEK-COOH-PEI nanofiltration membrane is 24.3 L·m^(-2)·h^(-1),with MgCl_2rejection of 92.2%.

Progress in Inorganic Nanofiltration Membranes

Inorganic nanofiltration(NF)membranes as a new kind of membranes appeared a few years ago.Thisreview presents the progress in inorganic NF membranes during recent years.Synthesis,characterization,performance,and application of inorganic NF membranes are emphatically introduced,and the trends of devel-opment are also discussed.

Preparation of pH-sensitive Composite Nanofiltration Membrane

Positively charged composite nanofiltration （NF） membranes were prepared through interfacial polymerization of poly[2-（N,N-dimethyl amino）ethyl methacrylate]（PDMAEMA） on porous polysulfone （PSF） substrate membranes. The effects of pH on swelling ratio （SR） of the pure crosslinked PDMAEMA membrane and on separation performances of the composite NF membrane were investigated. The results show that the quaternized amino groups produced through interfacial polymerization technique are soluble in both phases, which accelerate the crosslinking reaction as self-catalysts. The swelling/contracting behavior of the pure crosslinked PDMAEMA exhibited a well reversible pH sensitive property. Importantly, the rejection and flux of the composite NF membrane show pH-sensitive behavior in NF process. Furthermore, with the help of a relatively novel method to measure membrane conduction, the true zeta potentials calculated on the basis of the streaming potential measurements proved the pH-sensitive behavior of the NF membrane.

Performance of Nanofiltration (NF) and Low Pressure Reverse Osmosis (LPRO) Membranes in the Removal of Fluorine and Salinity from Brackish Drinking Water

Certain areas in Senegal have a serious problem of high fluoride and salinity in underground water because of soil properties. This water currently used for drink has a bad taste on consumption and caused diseases like dental fluorosis and skeletal fluorosis. A membrane filtration plant constructed by Pall Corporation was improved through nanofiltration (NF) and Low Pressure Reverse Osmosis (LPRO). Both NF and LPRO membranes were shown applicable for salinity and fluoride ions removal from brackish and high fluorinated drinking water in a remote community. The NF membrane has given a fluorine retention rate varying between 63.3% and 71% while the LPRO membrane allow to reach 97 to 98.9% for fluorine rejection. Highest salinity rejection rates expressed through conductivity measurements are around 46% and 97% for respectively NF and LPRO.

Treatment of Textile Dye Effluent Using a Self-made Positively Charged Nanofiltration Membrane

A selfmade positively charged nanofiltration （NF） membrane was used to treat textile dye effluent to generate water for reuse, and the factors affecting nanofiltration process such as operating pressure, feed flow and membrane cleaning were investigated. With an applied pressure of 1.0 MPa and a feed flow of 40 L/h, this NF membrane has a removal of 93.3% for CODor and a reduction of approximately 51.0% in TDS, salinity and conductivity achieving the chroma removal of 100%. The permeate obtained through this membrane is suitable for recycling. Moreover, the membrane could be reused after being cleaned with 1% NaOH solution.