聚哌嗪酰胺-SiO_2/聚砜中空纤维纳滤膜的制备及表征

以聚砜(PSf)为基膜,哌嗪(PIP)为水相单体、均苯三甲酰氯(TMC)为油相单体,采用界面聚合的方法制备了聚哌嗪酰胺-SiO_2/PSf中空纤维纳滤膜,通过在水相或者油相中添加SiO_2纳米粒子,使膜在维持较高截留率的情况下提高膜通量,讨论了界面聚合时间、SiO_2在水相或油相中的含量对膜性能的影响。结果表明,当水相PIP的质量浓度为10 g/L、SiO_2、PIP的质量比为0.05,油相TMC的质量浓度为1.5 g/L、界面聚合时间10 s,并在60℃下热处理15 min时,所得纳滤膜具有良好的分离性能,对于无机盐的截留率大小为Na_2SO_4MgSO_4NaClMgCl_2,表明纳滤膜表面带负电;对活性艳蓝溶液的截留率可达90%以上。     

聚哌嗪酰胺复合纳滤膜的制备及表征

用哌嗪(PIP)溶液为水相反应单体,均苯三甲酰氯(TMC)正庚烷溶液为有机相反应单体,通过界面聚合法制备聚哌嗪酰胺中空纤维复合纳滤膜,研究了水相单体和有机相单体浓度对纳滤膜的影响及基膜预处理、对复合纳滤膜进行后处理对复合纳滤膜分离性能的影响,采用扫描电镜(SEM)和原子力显微镜(AMF)对制备的纳滤膜进行表征,所制备的聚酰胺复合纳滤膜在操作压力0.6 MPa下,对质量浓度2 000 mg/L的MgSO4溶液的脱除率为90%以上。     

基于树状分子聚酰胺-胺(PAMAM)的复合纳滤膜制备及性能研究

以聚砜超滤膜为支撑膜,通过聚酰胺-胺(PAMAM,G0)与均苯三甲酰氯(TMC)的界面聚合反应制备复合纳滤膜。首先优化了界面聚合过程,并通过场发射扫描电子显微镜(FESEM)进行了膜的表面形貌分析,最后考察了纳滤膜对Na2SO4、不同分子量聚乙二醇及小分子有机物的分离性能。结果表明:较优的纳滤膜制备条件为:PAMAM浓度0.25%(wt),TMC浓度0.3%(wt),界面聚合时间90 s,热处理温度60℃。FESEM分析表明经界面聚合反应后,超滤膜表面形成了一层致密的活性层。随着操作压力的增加及Na2SO4浓度的降低,膜对盐的截留率均不断增大。复合纳滤膜可有效截留盐,且其截留分子量(MWCO)处于600~1000 g mol 1。     

间苯二甲胺为单体制备耐氯复合纳滤膜及其性能

以间苯二甲胺(mXDA)为胺类单体与均苯三甲酰氯(TMC)反应,制备了1种耐氯复合纳滤膜,对其表面组成、结构进行了表征,并通过改变缓冲体系、调节界面反应条件,对该纳滤膜的性能进行优化。结果表明,界面聚合反应后在底膜上成功制备了聚酰胺层。在水相单体m XDA、油相单体TMC的质量分数分别为0.1%、0.075%,反应时间30 s、热处理时间10 min的优化条件下,复合纳滤膜对Na_2SO_4的截留率达94.5%,通量56.4 L/(m~2·h)。而且该膜在活性氯的质量浓度为5 g/L时浸泡1 h仍能保持完整的功能层结构,在截留率基本保持不变的情况下水通量提升33%。     

原位界面聚合制备PVDF复合纳滤膜的研究

为改善聚偏氟乙烯(PVDF)复合纳滤膜性能，以掺入单体哌嗪(PIP)的铸膜液制备基膜，通过原位界面聚合快速制备复合纳滤膜，简化了制备程序。ATR-FTIR分析结果表明，基膜上成功生成聚酰胺(PA)层，SEM观察到PA层表面具有典型结节结构。得到的复合纳滤膜对Na₂SO₄截留率为95.59%,渗透通量为12.37 L/(m²·h·bar),远高于传统界面聚合制备的PVDF复合纳滤膜。72 h的持续测试结果表明该复合纳滤膜具有良好的长期稳定性。     

纳米碳管改性聚哌嗪酰胺复合纳滤膜的制备

采用混酸(H2SO4/HNO3=3/1(V/V))处理多壁碳纳米管(MWNTs)制备了羧基化碳管(Carboxylated MWNTs),并与哌嗪(PIP)反应,制备了胺化的多壁纳米碳管(Amine functionalized MWNTs)。以聚砜(PSf)超滤膜为基膜,以均苯三甲酰氯(TMC)为油相单体和胺化的多壁纳米碳管与哌嗪(PIP)为水相单体,采用界面聚合法制得多壁碳纳米管改性聚哌嗪酰胺复合纳滤膜。采用傅里叶红外光谱(FT-IR)、拉曼光谱(RAM)、X射线光电子能谱(XPS)和扫描电子显微镜(SEM)和静态接触角表征了改性前后碳纳米管和复合膜的结构,结果表明哌嗪成功氨化改性了碳纳米管,基膜表面复合了一层聚哌嗪酰胺膜。重点考察了碳管在水相中添加量、TMC浓度、聚合时间对复合膜性能的影响,结果显示,在有机相单体浓度为1 g?L?1,水相单体浓度为2 g?L?1,水相中多壁碳纳米管的浓度为0.1 g?L?1,反应时间为45 s,复合膜的纯水通量为85.6 L?m?2?h?1,Na2SO4的截留率达到98%,对不同盐溶液的截留效果分别为:Na2SO4MgSO4MgCl2NaCl。水相中碳纳米管的加入,能有效改善膜的分离性能。     

新型高通量复合纳滤膜的制备及其性能研究

以聚乙烯亚胺(PEI)和单宁酸(TA)为水相单体、均苯三甲酰氯(TMC)为油相单体,通过界面聚合制备了复合纳滤膜,并对膜性能进行了表征和评价测试。结果表明,水相溶液TA、PEI的质量分数分别为0.3%、0.2%,水相pH为12,油相溶液TMC的质量浓度为0.2 g/L,反应时间为1 min,在60℃下烘干成膜为优化制备条件。此复合膜在温度为25℃、压力为0.5 MPa下得到的对4种无机盐截留顺序为Na_2SO_4MgSO_4MgCl_2NaCl,水通量MgCl_2NaClNa_2SO_4MgSO_4。该纳滤膜具有良好的SO_4~(2-)和Cl~-的分离效果。同时,该纳滤膜具有良好的耐污染性能,对腐殖酸和牛血清蛋白的24 h抗污染测试,水通量仍达到初始水通量的84.2%以上。     

基于单宁酸-壳聚糖复合胶体粒子的复合纳滤膜及其脱盐性能

以聚丙烯腈(PAN)超滤膜作为载体,以单宁酸(TA)-壳聚糖(CS)复合胶体粒子作为水相溶液,均苯三甲酰氯(TMC)的正已烷溶液作为有机相单体,通过界面聚合法成功制备了一种高通量、高截留的复合纳滤膜。对纳滤膜的表面形貌及性能进行分析,研究单体质量分数及界面聚合时间对纳滤膜性能的影响,用4种无机盐来考察膜的盐截留性能。结果表明,在纳滤膜表面成功聚合了复合薄层,并具有良好的亲水性。复合纳滤膜对Na_2SO_4的截留率达到97%,水通量达27.2 L/(m~2·h),可作为一种性能优异的纳滤膜用于无机盐的去除。     

氯化聚氯乙烯复合纳滤膜的制备及其在模拟RB5染料废水处理中的应用

以氯化聚氯乙烯（CPVC）超滤膜为基膜,采用单宁酸（TA）和哌嗪（PIP）在CPVC膜表面共沉积后与交联剂均苯三甲酰氯（TMC）进行界面聚合得到PA/TA/CPVC复合纳滤膜,采用扫描电镜（SEM）、原子力显微镜（AFM）、红外光谱及接触角对PA/TA/CPVC复合纳滤膜进行了表征,并探讨了干燥时间、TA/PIP浓度比、TA+PIP总浓度、TMC浓度对PA/TA/CPVC复合纳滤膜微观结构与性能的影响。结果表明,TA/PIP浓度比最佳为7/3,TA/PIP层的最佳干燥时间为20min,PA/TA/CPVC复合纳滤膜的纯水通量随着TA+PIP总浓度的增加和TMC浓度的增加而减少,对PEG1000的截留率均在90%以上。PA/TA/CPVC复合纳滤膜纯水通量最大值为4.5L/(m² · h · bar),此时PEG1000的截留率达到95.8%。对模拟RB5染料废水的最大通量为4.3L/(m² · h · bar),此时RB5的截留率为95.4%,对模拟RB5染料废水的稳定性较好。     

聚酰胺复合纳滤膜的制备与表征

以间苯二甲胺(m-XDA)和均苯三甲酰氯(TMC)分别为水相和油相反应单体,通过界面聚合制备聚酰胺复合纳滤膜.研究了界面聚合反应中水相单体浓度、水相pH值、油相单体浓度、反应时间、后处理温度及时间等因素对所制备的复合膜分离性能的影响.用红外光谱(FT-IR)和扫描电子显微镜(SEM)对所制备的膜进行结构和形态表征.所制备的聚酰胺复合纳滤膜在操作压力1.4MPa下,对1000mg·L-1的硫酸钠溶液的脱盐率为82.98%,通量为28.48L·m-2·h-1.     

TMC/TMPIP纳滤超薄复合膜的制备

基于哌嗪(PIP)与均苯三甲酰氯(TMC)界面聚合制备纳滤膜的原理,设计并合成了具有支化结构的三亚胺功能基团水相单体--均苯三甲酰哌嗪(TMPIP)盐酸盐,并与TMC界面聚合制得分子结构与TMC/PIP相同的TMC/TMPIP超薄纳滤复合膜。采用傅里叶红外光谱(FTIR)和扫描电镜(SEM)表征了复合膜皮层的化学结构和表面形貌,结果表明在聚砜底膜表面形成了膜厚为100 nm左右的TMC/TMPIP超薄皮层。通过与TMC/PIP复合膜对PEG 200水溶液的分离性能相比较发现,TMC/TMPIP复合膜因其高度的网络化结构和超薄皮层,因而具有更高的截留率和水通量。考察了TMC/TMPIP复合膜对水中不同盐的截留性能,其截留率顺序与TMC/PIP复合膜相同,而通量和截留率均优于后者。     

Fabrication of anti-fouling polyamide nanofiltration membrane by incorporating streptomycin as a novel co-monomer

Polyamide (PA) thin-film composite (TFC) nanofiltration (NF) membrane has extremely broad application prospects in separation of monovalent/divalent inorganic salts mixed solution. However, membrane fouling is the main obstacle to the application of PA, TFC and NF membrane. Streptomycin (SM) is a hydrophilic antibiotic containing a large number of hydroxyl and amino groups. In this work, the NF membrane was prepared via interfacial polymerization (IP) between trimesoyl chloride (TMC) in the organicphaseand SM/piperazine (PIP) mixture in theaqueousphase. The NF membrane structure and performance were characterized in detail. The results showed that SM successfully participated in the IP. The negative charge and hydrophilicity of membrane surface were improved. The prepared membrane exhibited good anti-adhesion and anti-bacterial performance. Additionally, when the SM concentration was 2%, the prepared membrane exhibited the optimal permselectivity. The water permeance was 89.4 L·m^-2·h^-1·MPa^-1. The rejection of NaCl and Na₂SO₄ were 17.17% and 97.84%, respectively. The NaCl/Na₂SO₄ separation factor of the SM2-PIP/TMC membrane in 1000 mg·L^-1 NaCl and 1000 mg·L^-1 Na₂SO₄ mixed solution was 40, which was 3.3 times that of PIP/TMC membrane. It indicated that SM2-PIP/TMC demonstrated excellent monovalent/divalent salts separation performance. This work provided an easy and effective approach to preparing anti-fouling NF membrane while possessing superior monovalent/divalent salts separation performance.     

热处理条件对PVA/PAN和PPVA/PAN渗透汽化复合膜分离性能的影响

制备了以聚乙烯醇（PVA）、磷酸酯化聚乙烯醇（PPVA）和活性分离层的PVA／PAN、PPVA／PAN渗透汽化复合膜并用于乙醇－水恒沸混合物的分离。考察了热处理条件对复合膜分离性能及吸附性能的影响。结果表明,复合膜的分离性能主要是由热处理温度决定的,并且,PPVA／PAN复合膜比PVA／PAN复合膜具有更好的分离性能。确定了最佳的热处理条件,对于PVA／PAN复合膜：在403K下,热处理时间不小于4h,对于PPAV／PAN复合膜：在423K下,热处理时间不小于2h。     

Preparation, morphology and performance evaluation of polyvinylalcohol (PVA)/polyethersulfone (PES) composite nanofiltration membranes for pulp and paper wastewater treatment

In this study, thin film composite PVA/PES nanofiltration membranes were fabricated for the treatment of pulp and paper industrial wastewater. Phase separation induced by immersion precipitation was used to prepare the PES support membrane. PVA/PES composite nanofiltration membranes were prepared by dipping the support PES membrane in the PVA and cross-linking solutions at different conditions. Maleic acid (MA) was used as cross-linking agent. PVA and MA have concentrations of 0.5?C2 and 0.05?C1 wt%, respectively. Morphological studies were carried out by means of scanning electron microscopy (SEM) as well as atomic force microscopy (AFM) techniques. In addition, the hydrophilicity of membranes was examined by contact angle measurements. Permeability and ability of PVA/PES composite nanofiltration membranes to reduce COD of the wastewater were evaluated by a cross flow filtration system. SEM images indicated that the PVA layer was uniformly formed on the PES support membrane. AFM images showed that the surface roughness, porosity and pore sizes of PES support membrane were reduced after formation of PVA layer on the support surface. Moreover, the hydrophilicity of the membranes was significantly increased. Experimental results demonstrated that the PVA/PES composite nanofiltration membranes were able to reduce the COD of wastewater. Optimum conditions for preparation of PVA/PES composite membrane are consisted of PVA concentration: 1 wt%, MA concentration: 0.5 wt%, cross-linking time: 3?min and curing time: 3?min.     

Preparation and characterization of high‐selectivity hollow fiber composite nanofiltration membrane by two‐way coating technique

A novel coating technique, named as two‐way coating (TWC), was explored to prepare hollow fiber composite (HFC) nanofiltration (NF) membrane through interfacial polymerization from piperazine (PIP) and trimesoyl chloride (TMC) on the lumen side of hollow fiber polysulfone ultrafiltration membrane with an effective membrane area of 0.4 m². The optimum preparation conditions were systematically investigated and obtained as follows: PIP 0.023 mol/L, TMC 0.0057 mol/L, air blowing rate 2.7 m/s for 30 min after aqueous coating, aqueous coating pressure 0.1 MPa, organic solution flowing rate 0.32 m/s, and heat treating time 3 min. The resultant HFC membrane showed a high selectivity of divalent ion and monovalent ion. Salt rejections of MgSO₄ and NaCl were 98.13 and 18.6% with the permeate flux of 32.6 and 40.2 L m^?2 h^?1 at 0.7 MPa, respectively. Field emission scanning electron microscopy images indicated that composite membrane prepared by TWC technique had a uniform active layer from the upper end to the bottom of the hollow fiber. And the salt rejection and permeate flux showed almost no difference between different membrane sections. Stability results suggested that good reproducibility could be obtained by TWC technique for the preparation of high‐performance HFC NF membrane. The resultant NF membrane showed a high removal rate of chemical oxygen demand and chroma of landfill leachate which were approximately 100%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41187.     

Performance enhancement of nanofiltration membranes via surface modification with a novel acylation reagent

Acyl chloride monomers have been serving as the dominant acylation reagent for preparing thin-film composite (TFC) nanofiltration (NF) membranes over the past few decades. Herein, a novel acylation reagent (trimellitic anhydride, TMA) was exploited in conjunction with trimesoyl chloride (TMC) to undergo interfacial polymerization with piperazine (PIP) on the polysulfone substrate membranes. The introduction of TMA enabled the deeper diffusion of PIP monomers into the organic phase, resulting in the creation of novel circular-shaped protuberances on the top surface of the polyamide layer and the significant increase in the effective membrane area. Besides, abundant in-situ carboxylic groups were generated in the polyamide layer, conducive to both the surface hydrophilicity and negative charge density. Consequently, with an addition of 0.03 wt% TMA, pure water flux reached up to 15.3 L m⁻² hour⁻¹ bar⁻¹, almost 2.2 times that of the pristine membrane, and high rejection of Na₂SO₄ (97.3%) was maintained, evincing the superior desalination performance of the TMA-modified membranes. The interaction mechanism between TMA, TMC, and PIP was described in detail. Furthermore, the TMA-modified membranes exhibited a stable separation performance over the long-running process.     

有机溶剂纳滤膜的润湿性对渗透和分离性能的影响

有机溶剂纳滤是一种绿色、高效、节能的新型膜分离技术，在回收和处理有机溶剂中具有广泛的应用前景。本文采用浸渍法分别将聚合物聚二甲基硅氧烷（PDMS）、嵌段聚醚酰胺（PEBAX2533）和聚乙烯醇（PVA）与聚砜（PS）超滤基膜复合，制备了3种不同润湿性的聚合物耐溶剂纳滤膜，研究了PDMS/PS、PEBAX/PS和PVA/PS复合膜对甲醇、乙醇、异丙醇、正己烷、正庚烷的渗透性能，考察了3种聚合物膜对伊文思蓝/甲醇溶液的有机溶剂纳滤性能。结果表明，有机溶剂在不同润湿性复合膜的渗透和传递性能与溶剂本身的溶度参数、分子量、黏度和极性等有很密切的相关性，溶剂的分子量、黏度、分子动力学直径越小，在同一极性复合膜中渗透通量越大；对伊文思蓝/甲醇溶液的有机溶剂纳滤分离表明，PDMS/PS和PEBAX/PS复合膜的截留率均可达90%以上，通量分别为 58.0L/(m²·h·MPa)和72.2L/(m²·h·MPa)；PVA/PS复合膜的截留率为85.1%左右，通量为57.5L/(m²·h·MPa)。     

纳米聚苯胺改性聚哌嗪酰胺纳滤膜的制备

以导电态纳米聚苯胺(PANI)为添加剂, 哌嗪和均苯三甲酰氯(TMC)为反应单体, 通过界面聚合反应在聚砜超滤膜上形成复合层制备纳滤膜。采用扫描电子显微镜(SEM)和原子力显微镜(AFM)等对复合膜的性能和结构分别进行了测试和表征。SEM照片证实PANI含量低时, 可以在复合膜上分布得比较均匀;AFM图像看出膜表面粗糙度的增加;膜性能的测试结果证实了添加PANI的复合膜水通量得到了提高, 同时脱盐率也有变化。最优实验条件下, 膜对Na₂SO₄、MgSO₄、MgCl₂和NaCl的截留率分别为99.4%、98.5%、85.4%和59.2%。试验结果表明, 加入PANI能够提高膜的水通量, 并提升了膜的脱盐性能。     

氧化石墨烯/碱式硫酸铝掺杂聚醚砜/聚酰胺复合纳滤膜的制备及其性能

先由氧化石墨烯（GO）、硫酸铝和尿素通过水热法制得氧化石墨烯/碱式硫酸铝（GO-BAS）复合物,继与哌嗪（PIP）溶液共混作为水相;均苯三甲酰氯（TMC）溶于正己烷作为有机相;采用界面聚合法使两相单体在聚醚砜（PES）基膜表面形成聚酰胺（PA）功能层,制得氧化石墨烯/碱式硫酸铝复合物掺杂的聚醚砜/聚酰胺（PES-PA-GO-BAS）复合纳滤平板膜,并在较低的工作压力（0.3 MPa）下对其进行性能研究。其对无机盐溶液的截留率依次为：Na₂SO₄（91.08%） > MgSO₄（83.42%） > MgCl₂（68.97%） > NaCl（17.62%）;纯水通量可达24.19 L·m^-2·h^-1,较之聚酰胺纳滤膜提高了近60%,且具备良好的稳定性和耐碱性。