界面聚合法制备聚哌嗪酰胺复合纳滤膜

以聚醚砜超滤膜为基膜,哌嗪(PIP)为水相单体,均苯三甲酰氯(TMC)为有机相单体,采用界面聚合法制备了复合纳滤膜,扫描电镜、表层的红外分析结果表明在基膜表面聚合了一层聚酰胺膜,膜性能测定结果表明膜表面荷负电,对不同无机盐的截留率为Na2SO4MgSO4MgCl2NaCl。界面聚合条件对膜性能的影响表明,最佳聚合条件为:PIP浓度0.5%～2%,TMC浓度0.15wt%～0.75wt%,聚合时间≥1min,热处理温度60℃～80℃,时间15 min左右。     

单体结构对聚酰胺类复合膜分离性能的影响

采用间苯二甲酰氯、均苯三甲酰氯、均苯四甲酰氯分别与间苯二胺、乙二胺、哌嗪在耐高温杂萘联苯聚醚砜酮(PPESK)超滤膜表面进行界面聚合,制备了7种具有不同功能层结构的新型超薄复合膜.采用红外、X射线衍射、原子力显微镜等测试手段对复合膜结构进行表征,测试了7种复合膜对0·2%的Na2SO4水溶液,0·2%NaCl水溶液的分离性能,分析了单体结构与复合膜分离性能的关系.     

聚酰胺纳滤膜对黄连中生物碱的截留性能

以盐酸小檗碱为模型分子,考察循环时间、操作压力、料液浓度和离子强度等因素对聚酰胺纳滤膜截留盐酸小檗碱性能的影响。实验表明:聚酰胺纳滤膜对盐酸小檗碱的截留率80min后基本稳定;随着操作压力的增加,膜通量和截留率都增大;随着料液浓度的增加,聚酰胺纳滤膜通量下降,对盐酸小檗碱的截留率先增大后下降;随着溶液中离子强度的增加,膜通量和截留率都减小。在黄连提取液中生物碱含量为0.025g/L、操作压力为0.4MPa条件下,聚酰胺纳滤膜5min可使黄连提取液中生物碱浓缩6.27倍。     

盐湖提锂纳滤膜研究进展

锂是我国发展新能源等产业的关键资源,进口依赖度大。盐湖提锂是应对锂短缺问题的重要途径,然而盐湖中高浓度的伴生镁离子给高效提锂带来挑战。纳滤膜可通过孔径筛分和电荷排斥效应的协同,有效分离镁锂离子,在盐湖提锂中扮演着重要的角色。本文从纳滤膜结构(孔径、电荷、厚度)调控出发,介绍了新单体设计、表面改性、共混掺杂、底膜改性等膜结构调控策略,阐述了膜结构与镁锂分离性能的构效关系,总结了不同制膜方法在镁锂分离过程中的优劣,展望了新型镁锂分离纳滤膜的研究方向。     

高分子量芳香共聚酰胺的合成

系统地对对苯二甲酰氯、对苯二胺和４，４′－二氨基二苯醚三元共缩聚体系低温溶液聚合的多种影响因素进行了研究，得到对数比浓粘度为５．８～７．０ｄｌ／ｇ的芳香共聚酰胺。实验结果表明：反应时间、反应温度、二酰氯与二胺的摩尔比、酸吸收剂吡啶用量、助溶盐氯化锂用量、４，４′－二氨基二苯醚用量以及单体浓度对共缩聚物的对数比浓粘度都有较大影响。     

氮气等离子体改性壳聚糖-聚丙烯腈复合纳滤膜

以氮气低温等离子体对壳聚糖-聚丙烯腈复合纳滤膜进行表面改性。用接触角、扫描电镜、扫描探针显微镜、X射线光电子能谱观察膜表面的亲水性和形貌特征,分析膜表面化学组成;以γ-氨基丁酸为分离对象表征膜的纳滤性能。结果表明:经50 W、20 Pa的氮气等离子体作用2 min,壳聚糖膜表面的亲水性大幅改善,其接触角由102.0°下降至44.3°,平整度明显提升;膜表面中的C—C、C—O和酰胺基团均减少,而胺基和羰基相应增加;在pH=6.15的水溶液中对w=1.0%的γ-氨基丁酸进行纳滤,液体通量由原来的1.12 L/(m~2·h)提高至1.75 L/(m~2·h),且对氨基酸的截留率从28%提升至83%。     

动电法研究聚酰胺类纳滤膜界面电现象

以DK膜为研究对象,以透过式流动电位测试系统为分析手段,采用动电法研究聚酰胺类纳滤膜的界面电现象。根据Helmholtz-Smoluchowski方程和Gouy-Chapman模型系统地考察了电解质溶液浓度和离子种类、价态等因素对膜ζ电位和电荷密度的影响。研究发现,在一定浓度范围内,DK型纳滤膜的电荷密度与电解质溶液浓度之间符合Freundlich吸附等温式,其中对于Na2SO4溶液:ln|σ|(mC/m2)=2.436 0.505lnC(mol/m3);对于MgSO4溶液:ln|σ|(mC/m2)=-0.539 1.412lnC(mol/m3);对于KCl溶液:ln|σ|(mC/m2)=-0.140 0.280lnC(mol/m3);对于CaCl2溶液:ln|σ|(mC/m2)=-2.287 1.105lnC(mol/m3)。结果表明,电解质溶液中阴离子的特性吸附是聚酰胺类纳滤膜荷电现象产生的主要原因。     

三甲基苯二胺芳香聚酰胺的结构与性能

利用ＩＲ，ＷＡＸＤ，ＤＳＣ及ＴＧ等表征了多取代芳香族聚酞胺的结构与性能。     

聚氯乙烯/醋酸纤维素合金纳滤膜材料的研制及其界面性能表征

以聚氯乙烯(PVC)、醋酸纤维素(CA)为膜基材,四氢呋喃为溶剂,蒸馏水为沉淀剂,采用溶液共混法制备出PVC／CA合金纳滤膜材料作为高效液相色谱(HPLC)柱填料。由HPLC实验给出的参考溶质的保留时间计算膜-液界面的溶质平衡分配系数K和界面水层体积Ks,探讨合金化前后聚氯乙烯膜材料界面性能及亲水性的变化,并测定了PVC／CA合金的极性(av)和非极性(am)参数。     

PES中空纤维复合纳滤膜的制备

采用界面聚合法制备聚醚砜（PES）中空纤维复合纳滤（NF）膜,讨论了制备条件对PES中空纤维复合NF膜性能的影响。实验结果表明,聚合反应时间、均苯三甲酰氯浓度、哌嗪浓度和酸吸收剂三乙胺浓度对复合NF膜性能有显著影响,同时二次反应能够提高复合NF膜的截留率,对2g／L的Na2SO4截留率可达到99．2％。     

Effect of aqueous and organic solutions on the performance of polyamide thin‐film‐composite nanofiltration membranes

Polyamide/polyacrylonitrile thin‐film‐composite (TFC) nanofiltration (NF) membranes for the separation of oleic acid dissolved in organic solvents (methanol and acetone) were interfacially prepared by the reaction of trimesoyl chloride in an organic phase with an aqueous phase containing piperazine and m‐phenylene diamine. The interfacial reaction was confirmed by an investigation of the attenuated total reflection infrared spectrum. The surface morphology of the polyamide TFC membranes was examined with scanning electron microscopy. The hydrophilic properties of the membrane surfaces were conjectured on the basis of the ζ potential and contact angle. The effects of the monomer concentrations of the monomer blends (aliphatic and aromatic diamines) and drying times on various aspects of membrane performance, such as the solvents (water, alcohols, ketones, and hexane), permeation rates, and organic solute [poly(ethylene glycol) 200 and oleic acid] rejection rates, were investigated. All the membranes showed good solvent resistance. The polar solvent flux for water and methanol was higher than that for a nonpolar solvent (hexane). The membranes gave good rejection rates of oleic acid dissolved in methanol and acetone. The NF membranes were compared with various commercial membranes. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2151–2163, 2002     

Influence of the polyacyl chloride structure on the reverse osmosis performance,surface properties and chlorine stability of the thin-film composite polyamide membranes

This paper aims to study the structure–property relationship and make several reasonable suggestions for tailoring special separation performance and surface properties of thin-film composite polyamide membranes. In the experiments, composite membranes of different thin films with small structural differences were prepared through interfacial polymerization of trimesoyl chloride (TMC), 5-isocyanato-isophthaloyl chloride (ICIC), and 5-chloroformyloxy-isophthaloyl chloride (CFIC) with m-phenylenediamine (MPD) separately, after which their reverse osmosis performances were evaluated by permeation experiment with salt aqueous solution, and film properties were characterized by AFM, SEM, XPS, ATR-IR, contact angle and streaming potential measurements. Chlorine stability was also studied through the evaluation of membrane performance before and after hypochlorite exposure. The results show that the polyacyl chloride structure strongly influences the reverse osmosis performance, surface properties and chlorine stability of the composite membranes; that the introduction of isocyanato group into polyacyl chloride improves the hydrophilicity, water permeability and surface smoothness of the thin-film composite membrane, and increases the absolute value of zeta potential at both low and high pH, but reduces the chlorine stability; and that the introduction of chloroformyloxy group increases the salt rejection rate and the surface roughness of the composite membrane, but lowers the water permeability.     

Interfacially polymerized thin film composite membranes on microporous polypropylene supports for solvent-resistant nanofiltration

Interfacial polymerization (IP) is a powerful technique for fabrication of thin film composite (TFC) membranes. The polymers used most often as support are polysulfone (PS) or polyethersulfone (PES). These supports have limited stability in organic solvents. In this work, microporous polypropylene (PP) flat film and hollow fiber membranes were used as a support to fabricate TFC membranes for nanofiltration by the IP technique. Porous polypropylene membranes can provide substantial chemical, pH, and solvent resistance and are therefore suitable as supports for fabricating TFC membranes functioning as solvent-stable nanofiltration membranes. The surface and the pore interior of polypropylene flat sheet and hollow fiber membranes were hydrophilized first by pre-wetting with acetone followed by oxidation with chromic acid solution. A standard procedure to successfully coat the hydrophilized flat film and hollow fiber membranes was developed next. The monomeric system chosen for IP was poly(ethyleneimine) and isophthaloyl dichloride. The TFC hollow fiber membranes were characterized by nanofiltration of safranin O (MW 351) and brilliant blue R (MW 826) dyes in methanol. Rejection values of 88% and 43% were achieved for brilliant blue R and safranin O, respectively at a transmembrane pressure of 413 kPa in the TFC hollow fiber membranes. Pressure dependences of the solvent flux and solute rejection of the TFC membranes were studied using the modified flat sheet membranes up to a pressure of 965–1241 kPa. Solvent flux increased linearly with an increase in the transmembrane pressure. Solute rejection also increased with an increase in the transmembrane pressure. All modified membranes were also characterized using scanning electron microscopy. Extended-term solvent stability of the fabricated membranes was studied in toluene; the membranes demonstrated substantial solvent stability in toluene.     

Interlaboratory studies of highly permeable thin‐film composite polyamide nanofiltration membrane

The aim of this paper is to survey interlaboratory studies of performance data to produce highly permeable thin‐film composite (TFC) polyamide nanofiltration (NF) membrane in the form of flat sheet at bench scale. TFC polyamide NF membranes were fabricated via interfacial polymerization of 1,3‐phenylenediamine and trimesoyl chloride on porous polyethersulfone (PES) membrane. The NF membranes were characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), and cross‐flow filtration. The AFM and SEM analyses indicated that a rough and dense film was formed on the PES support membrane. The permeability and NaCl rejection of the NF membrane prepared at the presence of camphor sulfonic acid as pH regulator and triethylamine as accelerator in the aqueous solution were 21 l m^?2 h^?1 and 70%, respectively. In order to estimate the repeatability and reproducibility standard deviations, the development of an interlaboratory study was conducted by measurements of permeation flux and salt rejection of the synthesized membranes. Repeatability standard deviation of the permeation flux data for the membrane based on optimum formulation was 1.99, and reproducibility standard deviation was 3.55. Also based on this trend, repeatability standard deviation of the salt rejection data was 1.57, and reproducibility standard deviation was 4.11. The American Society for Testing and Materials standard E691‐05 was used for data validation of the repeatability and reproducibility standard deviations and consistency statistics. Copyright © 2011 John Wiley & Sons, Ltd.     

Silver nanoparticles immobilized on thin film composite polyamide membrane: characterization,nanofiltration, antifouling properties

Microbial biofouling is one of the major obstacles for reaching the ultimate goal of realizing a high permeability over a prolonged period of nanofiltration operation. In this study, the hybrid nanocomposite membranes consisting of silver (Ag) nanoparticles with antibiofouling capability on microorganism and polyamide (PA) were prepared by in situ interfacial polymerization and characterized by X‐ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM). The hybrid membranes were shown to possess the dramatic antibiofouling effect on Pseudomonas. In addition, Ag nanocomposite membranes had little influence on the performances of the membrane such as on water flux and salt rejection. SEM analysis results showed that all Pseudomonas were dead on the PA/Ag nanocomposite membrane, indicating the effectiveness of silver nanoparticles. This investigation offers a strong potential for possible use as a new type of antibiofouling membrane. Copyright © 2007 John Wiley & Sons, Ltd.     

High flux nanofiltration membranes based on interfacially polymerized polyamide barrier layer on polyacrylonitrile nanofibrous scaffolds

Electrospun polyacrylonitrile (PAN) nanofibrous scaffold was used as a mid-layer support in a new kind of high flux thin film nanofibrous composite (TFNC) membranes for nanofiltration (NF) applications. The top barrier layer was produced by interfacial polymerization of polyamides containing different ratios of piperazine and bipiperidine. The filtration performance (i.e., permeate flux and rejection) of TFNC membranes based on electrospun PAN nanofibrous scaffold was compared with those of conventional thin film composite (TFC) membranes consisting of (1) a commercial PAN ultrafiltration (UF) support with the same barrier layer coating and (2) two kinds of commercial NF membranes (i.e., NF90 and NF270 from Dow Filmtec). The nanofiltration test was carried out by using a divalent salt solution (MgSO₄, 2000 ppm) and a cross-flow filtration cell. The results indicated that TFNC membranes exhibited over 2.4 times more permeate flux than TFC membranes with the same chemical compositions, while maintaining the same rejection rate (ca. 98%). In addition, the permeate flux of hand-cast TFNC membranes was about 38% higher than commercial NF270 membrane with the similar rejection rate.     

Nanofiltration membranes based on poly(vinylidene fluoride‐co‐chlorotrifluoroethylene)‐graft‐poly(styrene sulfonic acid)

Graft copolymers comprising poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) backbone and poly(styrene sulfonic acid) side chains, i.e. P(VDF‐co‐CTFE)‐g‐PSSA were synthesized using atom transfer radical polymerization (ATRP) for composite nanofiltration (NF) membranes. Direct initiation of the secondary chlorinated site of CTFE units facilitates grafting of PSSA, as revealed by FT‐IR spectroscopy. The successful “grafting from” method and the microphase‐separated structure of the graft copolymer were confirmed by transmission electron microscopy (TEM). Wide angle X‐ray scattering (WAXS) also showed the decrease in the crystallinity of P(VDF‐co‐CTFE) upon graft copolymerization. Composite NF membranes were prepared from P(VDF‐co‐CTFE)‐g‐PSSA as a top layer coated onto P(VDF‐co‐CTFE) ultrafiltration support membrane. Both the rejections and the flux of composite membranes increased with increasing PSSA concentration due to the increase in SO₃H groups and membrane hydrophilicity, as supported by contact angle measurement. The rejections of NF membranes containing 47 wt% of PSSA were 83% for Na₂SO₄ and 28% for NaCl, and the solution flux were 18 and 32 L/m² hr, respectively, at 0.3 MPa pressure. Copyright © 2008 John Wiley & Sons, Ltd.     

Study on the thin-film composite nanofiltration membrane for the removal of sulfate from concentrated salt aqueous: Preparation and performance

Thin-film composite (TFC) nanofiltration (NF) membrane was prepared through the interfacial polymerization between piperazine (PIP) and trimesoyl chloride (TMC) on the polysulphone support membrane. The chemical structure of membrane surface was studied by attenuated total reflectance infrared (ATR-IR) and X-ray photoelectronic spectroscopy (XPS). Parametric studies were conducted by varying reaction time, curing temperature, curing time and additives in PIP solution for obtaining the optimum polymerization conditions. Systematic performance studies were conducted with different feed solutions, feed concentrations, feed pHs, operating temperatures and pressures. Continuous and comparative tests were also conducted to determine the performance stability and separation efficiency of the thin-film composite NF membrane prepared. High performance thin-film composite NF membrane for the selective sulfate removal from concentrated sodium chloride aqueous with the water permeability coefficient of 75 L/(m² h MPa) could be prepared under specific conditions. Experimental results on concentrated mixed solution of NaCl and Na₂SO₄ demonstrated that the NF membrane developed could be successfully used for the removal of sodium sulfate from the concentrated brine of chloralkali industry with high permeate flux, selectivity and performance stability.