多孔纳米材料改性水处理超滤膜的研究进展

基于压力驱动的超滤膜面临渗透性和选择性的制衡及膜污染问题。多孔纳米材料是高性能超滤膜改性制备中一类重要的添加剂,是新型水处理功能膜的研究热点之一。多孔纳米材料的添加为膜提供了额外水通道,其可调的孔尺寸又为在膜内构建出具有高度选择性的纳米通道提供了潜在有利条件,进而突破膜渗透性和选择性的Trade-off效应。同时,亲水性多孔纳米材料的添加有利于提升膜的抗污染性能。本文综述了近年来多孔纳米材料对超滤膜的改性方法,总结了微孔沸石分子筛、介孔炭、介孔二氧化硅、金属有机骨架材料和共价有机骨架材料对超滤膜的改性研究进展,着重评价了不同改性材料对超滤膜在亲水性、渗透性、污染物截留和抗污染能力等方面的影响。最后对未来多孔纳米材料改性超滤膜的研究及应用的发展趋势进行了展望。     

Effects of preparation conditions on the surface modification and performance of polyethersulfone ultrafiltration membranes

The impact that some membrane preparation steps had on ultrafiltration (UF) membrane characteristics and performance was studied. Polyethersulfone (PES) was employed as base polymer, while N‐methyl pyrrolidone (NMP) was used as a solvent, and polyvinylpyrrolidone (PVP) was used as a nonsolvent pore‐forming additive. The manufacturing variables studied were solvent evaporation time and membrane surface modification, using a fluorine‐based copolymer referred to as surface‐modifying macromolecule (SMM). The flat sheet membranes, prepared via phase inversion, were characterized using solute transport data, X‐ray photoelectron spectroscopy (XPS), and contact angle measurements. Membrane performance was evaluated via filtration test protocol that included a 6‐day filtration of concentrated river water. The flux reduction with time was modeled using single and dual mechanisms of fouling. The pore blockage/cake filtration model described better the behavior of the permeation rate along the experiments. Increasing the solvent evaporation time decreased the size of the pores and the permeation rate. However, it did not significantly affect the removal of the organic compounds naturally present in the river water used as feed. XPS and contact angle measurements proved that the short evaporation periods did not allow enough SMM migration to the surface to provoke a significant effect on the membrane performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

污水处理厂提标改造关键影响因素及工艺选择

为保护广州市北部水源,新华污水处理厂出水标准由满足《城镇污水处理厂污染物排放标准》（GB 18918-2002）的一级B标准提升为一级A要求,根据对污水处理厂的运行现状进行分析,找出影响改造的关键因素,并对比各种常用的改造工艺,探讨适宜新华污水处理厂的提标改造的工艺路线。     

疏水性油水分离膜及其过程研究进展

油水分离是治理含油废水和含水油液的重要工业过程。本文概括了疏水性油水分离膜的类型与制备方法,包括常规分离膜和高度疏水/超亲油分离膜。前者为常规微滤、超滤及纳滤过程用膜;后者由构筑高度疏水（水滴接触角≥120°）表面方法得到,形式有金属网膜、纤维膜、滤纸、复合膜及不对称膜,其为制备耐污染的疏水性油水分离膜提供了新思路。指出了疏水性膜用于油水分离的过程原理及应用现状：含油废水除油中,疏水性膜可实现O/W乳液的破乳、粗粒化油滴、滤除油滴及吸附油分子几方面的功能;含水油液除水中,膜被用来截留水滴,可直接得到净化的油品。最后,指出了其过程规模化应用前尚需解决的重要问题,特别是高度疏水/超亲油分离膜的制备、相关过程研究的深入及其规模化试验等方面需着力加强。     

Improved performance of the ultrafiltration membranes by simple modification with air plasma treatment and polymeric deposition

This study seeks to increase the antifouling properties of fluorinated polyvinylidene (PVDF) membranes through the synergistic application of plasma treatment and polymer deposition, employing polymerizations of polyvinylpyrrolidone (PVP) and polyethyleneimine (PEI). The results show remarkable success in modifications, presenting exceptional performance. Two distinct surface modification methods, plasma treatment and polymer deposition, were used to improve the antifouling properties and filtration performance of PVDF membranes. The plasma used was a discharge dielectric barrier using ambient air as gas, and hydrophilic polymers, PVP, and PEI. The results outlined changes in membrane roughness with a significant roughness reduction of up to 43% evident based on topographic and morphological analyses. Hydraulic permeability analysis revealed a substantial 35-fold increase, indicating a notable improvement in performance. All treated membranes exhibited higher water affinity and superior performance during 12-h ultrafiltration compared to their untreated counterparts. After chemical cleaning, water flux recovery exceeded 85% for all treated membranes, indicating the inherent antifouling properties of the surface.     

Surfactant modification of the surface energetics of hydrophobic polymers and protein adsorption

A low interfacial free energy between a polar surface and water is expected to lead to a smaller amount of protein adsorbed. However, nonpolar surfaces have high interfacial free energies with water. They can acquire lower interfacial free energies by modifying the polar and dispersion components of their surface free energy so that they approach those of water. The two-phase method, in which an aqueous solution of surfactant and chloroform constitute the two-phase system, can be used for the modification of the hydrophobic surface. The hydrophobic polymer is immersed for a short time in chloroform (which is a solvent for the polymer). This allows disentanglement of the surface chains. Subsequently, the polymer is pulled out through the solvent-water interface and further through the water phase. The monolayer of adsorbed surfactant present at the water-chloroform interface is thus transferred to the surface of the polymer. The hydrophobic chains of the surfactant and polymer entangle and the polar head groups orient towards the water phase. Protein adsorption experiments carried out with albumin and fibrinogen showed that the amounts of protein adsorbed on unmodified PMMA surfaces can be significantly higher than those on SDS- and Brij 35-modified surfaces. The sequence for adsorption is unmodified surface > SDS-modified surface > Brij 35-modified surface.     

Surface modification of poly(ether sulfone) ultrafiltration membranes by low‐temperature plasma‐induced graft polymerization

Low‐temperature helium plasma treatment followed by grafting of N‐vinyl‐2‐pyrrolidone (NVP) onto poly(ether sulfone) (PES) ultrafiltration (UF) membranes was used to modify commercial PES membranes. Helium plasma treatment alone and post‐NVP grafting substantially increased the surface hydrophilicity compared with the unmodified virgin PES membranes. The degree of modification was adjusted by plasma treatment time and polymerization conditions (temperature, NVP concentration, and graft density). The NVP‐grafted PES surfaces were characterized by Fourier transform infrared attenuated total reflection spectroscopy and electron spectroscopy for chemical analysis. Plasma treatment roughened the membrane as measured by atomic‐force microscopy. Also, using a filtration protocol to simulate protein fouling and cleaning potential, the surface modified membranes were notably less susceptible to BSA fouling than the virgin PES membrane or a commercial low‐protein binding PES membrane. In addition, the modified membranes were easier to clean and required little caustic to recover permeation flux. The absolute and relative permeation flux values were quite similar for the plasma‐treated and NVP‐grafted membranes and notably higher than the virgin membrane. The main difference being the expected long‐term instability of the plasma treated as compared with the NVP‐grafted membranes. These results provide a foundation for using low‐temperature plasma‐induced grafting on PES with a variety of other molecules, including other hydrophilic monomers besides NVP, charged or hydrophobic molecules, binding domains, and biologically active molecules such as enzymes and ribozymes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1699–1711, 1999     

A multicontinuum approach for the problem of filtration of oily water systems across thin flat membranes: I. The framework

A multicontinuum model is built to estimate the permeate flux of an oily water system across a thin flat membrane in cross filtration methodology is demonstrated. Several continua are constructed to represent droplet and pore‐size distribution of both the dispersed oil phase and the porous membrane, respectively. The possible permeation of the oil phase has been divided into three criteria. In the first criterion, oil droplets of a given size range may permeate through a given size range of the porous membrane, in the second criterion, oil droplets of another size range may be rejected through another pore size range, and in the third criterion, oil droplets may break apart leaving a tail inside the pore space, which will eventually permeate, and the rest will sweep off due to shear stress. These protocols identify the methodology of the proposed multicontinuum approach, which is introduced in this first part. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4604–4615, 2017     

自来水深度处理超滤膜的选择

试验设计、运行了聚砜中空纤维超滤(UF)膜,直接将未经预处理的某自来水管网输出水,处理成优质供水。结果表明,随着UF膜的切割分子量从0.6万增大到5万,产水量提高,对主要水质指标的去除率下降,净化水的水质优良,即使原水的水质突然恶化,UF膜能有效地将被严重污染的高浊度和色度的异常自来水转化成为符合饮用水水质指标的卫生洁净水。     

Ultrafiltration of industrial waste liquors from the manufacture of soy protein concentrates

Protein‐containing waste liquors from the manufacture of soy protein concentrates were processed by ultrafiltration to recover soluble protein using three different membranes (with molecular weight cut‐offs of 10, 30 and 50 kDa). Operating at 20 °C under reversible conditions, the experimental data of the normalized permeate flux (NPF) obtained at various transmembrane pressures were well described by a model reported in the literature. For each membrane and transmembrane pressure, the values of the parameters involved in the model were calculated. Operating at selected transmembrane pressures, protein rejections of 0.705, 0.747 and 0.637 were determined for the 10, 30 and 50 kDa membranes, respectively. Operation with the 10 kDa membrane at temperatures in the range 30–50 °C and operation with the 30 or 50 kDa membranes at 40 or 50 °C resulted in hysteresis. Copyright © 2006 Society of Chemical Industry     

Development of antimicrobial membranes via the surface tethering of chitosan

To render the surface of ultrafiltration membranes biocidal, cellulose membranes were modified with chitosan, a naturally occurring polycationic biocide. Through the use of chitosans of different molecular weights and membranes with different pore sizes, the alteration of the morphological structure of tethered chitosan layers was achieved. The importance of such structural differences in the antimicrobial activity of the prepared membranes against gram‐positive Staphylococcus aureus and gram‐negative Escherichia coli was studied. The antimicrobial efficiency improved with the use of chitosans with higher molecular weights and membranes with smaller pore sizes. This suggested that the surface location of the grafted chitosan chains was more preferential for a higher antimicrobial activity of the surface. Membranes modified with chitosan showed higher antimicrobial efficiency against gram‐positive S. aureus than against gram‐negative E. coli. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A multicontinuum approach for the problem of filtration of oily‐water systems across thin flat membranes: II. Validation and examples

In this second part, a validation exercise is conducted to investigate the accuracy of the multicontinuum approach in estimating the permeation capacity of membranes used for the filtration of oily‐water systems. Comparisons with the experimental works found in the literature reveals that the multicontinuum approach is quite accurate and show excellent match. Although the comparisons with the experimental data have been with respect to macroscopic integral variables, like the rejection capacity of membranes, the multicontinuum approach provides myriad information about the permeation process that have neither been presented nor even measured. Such detailed information has been highlighted in two examples. Details about which of the oil continua is going to be rejected or permeated through which porous membrane continuum are obtained. Furthermore, the flux of each oil continuum through every porous membrane continua is likewise obtained. These informations are then lumped to calculate the rejection capacity of membranes. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1095–1105, 2018     

Charged membranes for ultrafiltration treatment of synthetic waste water containing peptone

Continuous ultrafiltration of synthetic waste water containing peptone was carried out by using positively and negatively charged polyacrylonitrile membranes. The filtration experiments were operated in cross-flow mode under 10 kPa of applied pressure. The filtration properties of the charged membranes were compared with those of uncharged polyacrylonitrile ultrafiltration membranes having similar molecular sieve characteristics and membrane structure to the charged ultrafiltration membranes. During the continuous filtration, the filtration rate decreased and the operation pressure increased because of the formation of a peptone gel layer on the membrane surface. It was found that, for the positively charged membrane, the decrease in the filtration rate of the charged membranes was smaller than that of the uncharged membrane. In addition, the positively charged membrane maintained the initial operation pressure during the filtration. The reduction of fouling in the positively charged membrane was discussed by analyzing the gel components on the membrane surface.     

Separation of oil/water emulsions using nano MgO anchored hybrid ultrafiltration membranes for environmental abatement

This work focuses on utilizing the dual role of sulfonated polyphenyl sulfone (SPPSU) as both an anchoring agent and an interlayer modifying agent in the preparation of nano MgO/SPPSU/PPSU membranes for oil removal from water. These asymmetric membranes were prepared using the phase inversion technique. The dispersed nano MgO was observed in the membrane matrix as seen by scanning electron microscope and energy dispersive X‐ray analysis. The reduction in contact angle value establishes the increases in hydrophilicity. An increase in SPPSU (wt %) loosens the nano MgO/SPPSU/PPSU membrane packing as exhibited by the increase of d‐spacing by X‐ray diffraction analysis. The antifouling properties were tested using humic acid, as a model foulant. Further, in castor oil/water emulsion separation, it was found that the membrane with 25 wt % anchored moiety SPPSU/nano MgO produced a greater flux recovery ratio of 94.9% (±0.3) without compromising the oil rejection of 99% (±0.4) and better oleophobic surfaces for oil. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42848.     

An improved method for surface modification of porous water purification membranes

The surfaces of polysulfone and polyethersulfone ultrafiltration membranes were coated with polydopamine, yielding hydrophilic membranes that, under constant transmembrane pressure fouling conditions, have previously shown enhanced flux relative to unmodified membranes. When evaluated under constant permeate flux fouling, however, modified membranes exhibited higher transmembrane pressures than their unmodified analogs. This increased transmembrane pressure in the coated membranes was ascribed to the decrease in membrane permeance resulting from applying the polydopamine coating. The membrane permeance could be tuned by varying polydopamine deposition time and, even at the shortest deposition times studied here, a few minutes, a substantial increase in membrane hydrophilicity could be achieved. Therefore, polydopamine was deposited on a membrane of relatively high permeance until the pure water permeance of the modified membrane matched that of a membrane having lower native permeance, permitting a comparison of the fouling performance of a modified and unmodified membrane with the same pure water permeance. This approach was repeated, using a single, high permeance membrane as the base membrane for modification, to produce a family of modified membranes having the same initial pure water permeances as lower permeance, unmodified membranes. When unmodified and modified membranes of the same initial permeance were compared at constant flux fouling conditions, the modified membranes consistently exhibited lower transmembrane pressures and similar organic rejections to the unmodified membranes. Because many porous water purification membranes are operated at constant flux in industrial settings, an interesting methodology for membrane surface modification may be to surface-modify a membrane of high permeance until the desired permeance is achieved, rather than by surface modification of a membrane that natively has the desired water transport characteristics, since the surface modification procedures almost invariably lead to lower pure water permeance.     

A review of nanoparticle-enhanced membrane distillation membranes: membrane synthesis and applications in water treatment

Membrane distillation (MD) is a thermally driven process that uses low-grade energy to operate and has been extensively explored as an alternative cost-effective and efficient water treatment process compared to conventional membrane processes. MD membranes are synthesized from hydrophobic polymers, e.g. polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) or polypropylene (PP), using various methods including phase inversion and electrospinning techniques. Recent literature on MD membranes clearly shows their important role in surface water/wastewater treatment and seawater desalination. Modification of MD membranes with nanoscale materials significantly improves their performance, preventing wetting and fouling. This review presents a critical assessment of the progress on the use of nanomaterials for the modification of MD membranes. The techniques commonly used to synthesize MD membranes, the modifications that have been adopted for the incorporation of nanomaterials onto membranes, and the unique properties these nanomaterials impart on the membranes are discussed. The use of modified membranes in different MD configurations and their application in groundwater, surface water, wastewater, brackish water and seawater treatment is reviewed. Finally, cost implications, commercial viability, environmental sustainability, and future prospects of MD are also discussed to elucidate promising approaches for a future and successful implementation of MD at an industrial scale. © 2019 Society of Chemical Industry     

Optimization of the elastic modulus for polymeric nanocomposite membranes

The mechanical properties of polymeric membranes are critical factors for a successful and durable application in water treatment technologies. Fabricating membranes with optimal mechanical properties require delicate balancing between material, additives, processing conditions, porosity, and many other variables. Several variables to be optimized demands detailed experimental and computational investigations. The design of experiments (DOEs) technique using a validated framework with a computational model for the prediction of the elastic behavior can lower the number of conducted experiments for optimal membrane fabrication conditions. In this study, optimization of the elastic modulus of polymeric membranes is performed using DOE with computational modeling and validated with experiments. The optimum storage modulus of polymeric nano-filled membranes is determined at an operating temperature of 35°C. DOE is employed with a three-factor–three-level problem. The Taguchi DOE is utilized to obtain the experiments scheme, followed by the prediction of the storage modulus and fabrication of the polymeric nano-filled membrane with the optimum modulus. Predicted results demonstrate that the modulus of polyether sulfone (PES) reinforced with 0.3 wt.% halloysite nanotubes (HNTs) is the optimum combination. The fabricated PES/0.3 wt.% HNT membrane is in good agreement with the predicted modulus with a percentage error of 3%.     

Effect of the ethylene content of poly(ethylene-co-vinyl alcohol) on the formation of microporous membranes via thermally induced phase separation

Porous poly(ethylene-co-vinyl alcohol) (EVOH) membranes were prepared via thermally induced phase separation. The effect of the EVOH ethylene content on the membrane morphology and solute rejection property was investigated. For EVOHs with ethylene contents of 27–44 mol %, polymer crystallization (solid–liquid phase separation) occurred, and the membrane morphology was the particulate structure. However, the liquid–liquid phase separation occurred before crystallization for EVOH with a 60 mol % ethylene content. Cellular pores were formed in this membrane. For the particulate membranes, higher solute rejection and lower water permeance were obtained for EVOH with a lower ethylene content. The membrane formed by the liquid–liquid phase separation showed a sharper solute rejection change with a change in the solute radius than the particulate membranes did. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2583–2589, 2001     

亲水/疏水复合膜强化膜蒸馏深度处理工业废水的研究进展

工业废水中通常含有多种疏水性有机污染物及表面活性剂,传统疏水微孔膜用于膜蒸馏处理工业废水的过程中,这些污染物容易沉积在膜表面引发膜污染和膜润湿,导致膜蒸馏过程的低效甚至失败。亲水/疏水复合膜是一种表层亲水而底层疏水的非对称膜材料,可通过在膜表面形成水合层减缓污染物的吸附累积,同时保留疏水基底膜对污染物的高截留率,用于膜蒸馏过程可有效强化其处理复杂工业废水的效果。本文概述了构筑亲水/疏水复合膜的仿生学原理与表面润湿理论,介绍了复合膜常用的制备方法,重点分析了多种亲水材料改性制备的复合膜用于膜蒸馏深度处理工业废水的强化效果及强化机制,认为复合膜表面形成的亲水层可有效抑制工业废水中疏水性污染物与膜表面的疏水-疏水相互作用,减轻膜污染及膜润湿倾向,提高污染物截留效率,而氧化石墨烯等亲水物质可加速水分子通过,提升膜蒸馏产水通量。最后指出未来亲水/疏水复合膜的发展可以通过建立污染物在复合膜中的传递模型,进一步探究复合膜对工业废水处理过程的强化机制,通过优化调控复合膜结构,提升复合膜对工业废水中多种污染物的截留率和抗污染性能,实现膜蒸馏抗污染性、截留率和产水通量的同步提升,并通过开展中试研究验证复合膜用于工业废水深度处理的经济性和长期稳定性。     

Preparation of poly(vinyl chloride) (PVC) ultrafiltration membranes from PVC/additive/solvent and application of UF membranes as substrate for fabrication of reverse osmosis membranes

Ultrafiltration (UF) membranes were prepared from poly(vinyl chloride) (PVC) as main polymer, poly(vinyl pyrrolidone) (PVP) as additive, and 1‐methyl‐2‐pyrrolidone (NMP) as solvent using Design Expert software for designing the experiments. The membranes were characterized by SEM, contact angle measurement, and atomic force microscopy. The performance of UF membranes was evaluated by pure water flux (PWF) and blue indigo dye particle rejection. In addition, the molecular weight cutoff of UF membranes was determined by poly(ethylene glycol) (PEG) rejection. The UF membranes were used as substrates for fabrication of polyamide thin film composite (TFC) reverse osmosis (RO) membranes. The results showed that the model had high reliability for prediction of PWF of UF membranes. Also, increment in PVC concentration caused reduction of PWF. Moreover, at constant PVC concentration and if the concentrations of PVC was lower than 10 wt %, the PWF reduced by increasing the concentration of PVP. However, at PVC concentration higher than 11 wt %, increment in PVP concentration showed increment and reduction of PWF. The PEG rejection results showed that the prepared membranes had UF membranes properties. Finally, the NaCl rejection tests of RO membranes by PVC as substrates indicated that the performance of RO membranes were lower than commercial membranes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46267.