新型PVA/PA复合膜的微结构及其成膜条件

将不同材料分别用作复合膜的分离层和支撑体,是制备优良选择渗透性分离膜的重要方法之一.采用浇铸工艺将具有亲水性和高分离因子的聚乙烯醇(PVA)涂覆在高度透水性的反渗透(RO)聚酰胺(PA)膜表面,制备成渗透汽化(PV)分离有机物水混合物的PVA/PA复合膜.扫描电子显微镜(SEM)和原子力显微镜(AFM)以及红外光谱分析表明,PVA-PA层结构为一体化,膜表面光滑、致密,分离层上的微囊高度下降到4 nm左右.可以认为膜的优异传质性能取决于良好微结构包括PVA的化学交联和膜的结构形貌.铸膜液中PVA和交联剂的浓度以及热处理条件对复合膜分离性能的影响是明显的.这一新型的复合膜在环境温度下PV分离异丙醇(IPA)/水混合物的渗透通量(J)接近100 g·m-2·h-1,渗透物中的水含量(CP-H2O)大于99.5%.     

PA/PVA/PA多层交替复合分离膜的制备与表征

以工业应用的反渗透(RO)聚酰胺(PA)复合膜为支撑膜,通过组合浸涂法和界面缩聚(IP)法的两步成膜工艺,制备了分离层为交替复合的聚酰胺/聚乙烯醇/聚酰胺(PA/PVA/PA)多层复合膜(MLCM).用扫描电子显微镜(SEM)和原子力显微镜(AFM)分析了PA/PVA/PA MLCM的结构特征.结果表明,浸涂和IP的工艺条件是影响MLCM的分离性能以及微结构的主要因素.优化工艺制成的PA/PVA/PA MLCM,在实验温度20℃和下游真空度小于1000 Pa时,渗透汽化(PV)分离异丙醇(IPA)浓度为87.8%的水混合物,渗透通量(J)为60～80 g·m~(-2)·h~(-1),渗透物中水含量(CC_(p-H_2O))达99%以上.不同材料制成的多层交替复合的分离层具有显著的微结构形态和独特的双重选择性分离功能,其纳米-亚微米级厚度的多层结构强化了复合膜的水渗透性.     

改性复膜对微水异丙醇的渗透汽化脱水

介绍了用缩甲醛改性的PVA/PAN复合膜的制备方法,并用于质量分数低于5%的微水异丙醇体系的渗透汽化(PV)深度脱水研究,考察了操作温度、料液浓度与操作压力等因素对分离性能的影响。渗透通量J与分离系数α均随温度的升高而增大,而随料液异丙醇浓度的升高J减小而α增大,在72℃、1.6 kPa膜后压力下,该膜对含异丙醇质量分数为98%的体系,仍有α=316,J=262 g/(m.h)的分离效能,显示了较好的工业应用前景。     

壳聚糖-海藻酸钠/聚丙烯腈聚离子复合膜渗透汽化分离乙酸乙酯水溶液

制备了壳聚糖-海藻酸钠/聚丙烯腈（CS-SA/PAN）聚离子复合膜,将此膜用于渗透汽化分离乙酸乙酯水溶液.用红外光谱（FT-IR）表征CS、SA、CS/SA均质膜.研究CS-SA/PAN聚离子复合膜的溶胀性、料液浓度和SA质量分数、操作温度对乙酸乙酯水溶液脱水效果的影响.实验表明：CS/SA聚离子均质膜在乙酸乙酯水溶液中的溶胀度随溶液中水质量分数的增加而增大,随SA的质量分数增加而减小,40℃、SA质量分数为2.0%时,CS/SA聚离子均质膜在乙酸乙酯质量分数为97%的水溶液中溶胀度可达51%.随着SA质量分数的增加,CS-SA/PAN聚离子复合膜的渗透通量减小,分离因子增大,40℃、SA质量分数为2.0%时,分离乙酸乙酯质量分数为97%的水溶液,CS-SA/PAN聚离子复合膜渗透通量可达348g/（m^2.h）,分离因子为7245.随着料液中水含量的增加和料液温度的升高,膜渗透通量增大,分离系数减小,渗透通量与料液温度的关系能较好地吻合Arrhenius方程.     

聚丙烯酸-聚乙烯醇共混膜分离甲醇-碳酸二甲酯共沸体系

采用涂敷法制备了聚丙烯酸(PAA)-聚乙烯醇(PVA)共混膜,将其用于渗透汽化法分离甲醇(MeOH)-碳酸二甲酯(DMC)共沸物,考察了共混比例、热处理条件对甲醇分离性能的影响. 渗透汽化实验结果表明,随着热处理时间延长或热处理温度提高,分离因子先升高后降低,而渗透通量则逐渐减小;随着共混膜中PAA/PVA比例增加,分离因子先升高后降低,而渗透通量先减小后增大;当PAA/PVA质量比为7/3、热处理时间为60 min、热处理温度为150℃时,选择性最佳,在料液组成为70%(w) MeOH-30%(w) DMC及70℃的操作温度下,甲醇的分离因子为9.5(透过侧MeOH浓度为95.5%, w),渗透通量为360 g/(m2×h).     

NaA/PAN复合膜渗透汽化分离DMF/H_2O溶液的性能研究

采用流延法制备大面积的NaA/PAN分子筛复合膜,并用于渗透汽化分离二甲基甲酰胺/水(DMF/H2O)溶液。考察了料液组成、进料量和操作温度对膜分离性能的影响。实验结果表明:渗透通量随着温度的升高而增大,在DMF质量分数为20%,操作温度为24℃,料液量为1.5 m3/h,膜后侧压力为500 Pa的条件下,NaA/PAN膜的渗透通量达到1.84 kg/(m2·h),分离因子为11.5。     

全氟磺酸改性聚乙烯酵渗透汽化膜分离乙酸乙酯-水溶液

以聚乙烯醇（PVA）为原材料,全氟磺酸（PFSA）为共混改性材料,以聚丙烯腈（PAN）中空纤维超滤膜为底膜制备了PVA／PAN、PVA-PFSA／PAN复合膜,并用于乙酸乙酯脱水。考察了共混涂膜液中PVA／PFSA配比,交联剂洒石酸（Tac）用量以及原料液温度与浓度对PVA／PAN、PVA-PFSA／PAN复合膜分离性能的影响。实验结果表明,Tac交联的PVA／PAN、PVA-PFSA／PAN复合膜均对水具有较好的分离选择性。共混涂膜液中PVA／PFSA质量比为1／1、Tac／PVA质结比为1／5时所制备的PVA-PFSA/PAN复合膜渗透汽化分离性能最佳。40℃下此复合膜用于分离98％（wt）的乙酸乙酯水溶液时,其渗透通量和分离因予分别为81.1g·m^-2·h^-1和1890。同样条件下,与交联PVA／PAN复合膜相比,交联PVA-PFSA／PAN复合膜的渗透通量显著提高。     

多层聚酰胺复合膜的制备及其特性

聚酰胺（PA）具有特定的反渗透（RO）淡化海水和渗透汽化（PV）分离有机物混合物的优良性能。本研究采用水相含单体间苯二胺（m-PDA）和有机相含单体均苯三甲酰氯（TMC）体系,通过多次界面缩聚（IPC）工艺,制成了以RO用的PA复合膜作为多孔支撑膜的多层PA（ML-PA）复合膜。分别用原子力显微镜（AFM）和扫描电子显微镜（SEM）观察了ML-PA膜的微结构。ML-PA膜的厚度、PA高分子微囊聚集的致密程度、平均面粗糙度,都随着IPC反应次数的增加而显著提高。改变制备工艺参数,例如水相中单体和有机相中交联剂的浓度、IPC反应的温度和时间、以及IPC反应的次数,可以得到不同分离性能的ML-PA复合膜。当在m-PDA浓度为2．0％的水溶液中浸渍20min,然后在TMC浓度为0．5％的正己烷溶液中浸渍20s,IPC反应5次,每次反应温度均为40℃,获得的ML-PA复合膜在室温（25℃）下PV分离浓度为88．2％的异丙醇（IPA）水混合物时,渗透通量接近30．0g／m^2·h,渗透物中的水含量大于99．0％。     

聚醚共聚酰胺复合膜制备及其在渗透汽化膜法脱盐中的应用研究

以亲水性聚醚共聚酰胺PEBA为分离层膜材料,采用浸渍涂覆法制备了具有较薄致密皮层的PEBA复合膜,并对其渗透汽化膜法脱盐性能进行了研究。在操作条件下,PEBA复合膜可获得5.6～51.3 L/（m2/h）的渗透液流量,盐截留率可达99%以上。随着原料液氯化钠质量浓度（0～70 g/L）的增大,渗透液流量减小,氯化钠截留率基本保持不变;随着操作温度的升高（30～70℃）,渗透液流量呈指数增大,渗透液流量和温度的关系满足阿伦尼乌斯方程,通过拟合计算得到纯水的表观活化能为26.8 kJ/mol,原料液中加入盐后,水的表观活化能略微升高,在27.5～29.8 kJ/mol。     

聚乙烯醇复合膜用于水—乙醇液体混合物分离的渗透性能研究

本文研究了水-乙醇液体混合物在PVA/PS复合膜中的渗透性能,讨论了料液浓度、温度对透过性能的影响;并用电镜观察了复合膜的形态结构。结果表明此膜的性能与PVA均质膜变化规律相似。     

Preparation of PFSA‐PVA/PSf hollow fiber membrane for IPA/H2O pervaporation process

Using Na⁺ form of perfluorosulfonic acid (PFSA) and poly(vinyl alcohol) (PVA) as coating materials, polysulfone (PSf) hollow fiber ultrafiltration membrane as a substrate membrane, PFSA‐PVA/PSf hollow fiber composite membrane was fabricated by dip‐coating method. The membranes were post‐treated by two methods of heat treatment and by both heat treatment and chemical crosslinking. Maleic anhydride (MAC) aqueous solution was used as chemical crosslinking agent using 0.5 wt % H₂SO₄ as a catalyst. PFSA‐PVA/PSf hollow fiber composite membranes were used for the pervaporation (PV) separation of isopropanol (IPA)/H₂O mixture. Based on the experimental results, PFSA‐PVA/PSf hollow fiber composite membrane is suitable for the PV dehydration of IPA/H₂O solution. With the increment of heat treatment temperature, the separation factor increased and the total permeation flux decreased. The addition of PVA in PFSA‐PVA coating solution was favorable for the improvement of the separation factor of the composite membranes post‐treated by heat treatment. Compared with the membranes by heat treatment, the separation factors of the composite membranes post‐treated by both heat treatment and chemical crosslinking were evidently improved and reached to be about 520 for 95/5 IPA/water. The membranes post‐treated by heat had some cracks which disappeared after chemical crosslinking for a proper time. Effects of feed temperature on PV performance had some differences for the membranes with different composition of coating layer. The composite membranes with the higher mass fraction of PVA in PFSA‐PVA coating solution were more sensitive to temperature. It was concluded that the proper preparation conditions for the composite membranes were as follows: firstly, heated at 160°C for 1 h, then chemical crosslinking at 40°C for 3 h in 4% MAC aqueous solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Modified poly(vinyl alcohol)/chitosan blended membranes for isopropanol dehydration via pervaporation: Synthesis optimization and modeling by response surface methodology

Box–Behnken (BB) design of response surface methodology (RSM) was effectively applied to optimize fabrication conditions of modified poly(vinyl alcohol) (PVA) and chitosan (CS) blended pervaporation (PV) membranes. The PVA/CS membranes were crosslinked either by chemical reaction with glutaraldehyde (GA) or by heat‐treating at different temperatures. The main objectives were to determine the optimal levels of fabricating parameters and also to investigate interactions among the variables. CS content in the blended membranes, concentration of crosslinking agent and heat‐treating temperature were the fabrication parameters, the main effects and interaction effects of which on membrane structure and PV performance toward isopropanol (IPA)/water dehydration were investigated, and for which regression models were established. The modified PVA/CS blended membranes were characterized by means of scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) as well as X‐ray diffraction (XRD). It was found that the CS content is the most significant factor influencing flux and separation factor among the three studied variables and the experimental results are in excellent accordance with predicted values from the developed RSM regression models. The RSM results indicated that under preparation conditions of 80 wt % CS in the blended membrane, 0.58 wt % GA concentration, and 77 °C heat‐treating temperature, the maximum separation factor of 5222.8 and the normalized flux of 9.407 kg µm/m²h can be acquired with feed content of 85 wt % IPA at 25 °C, showing that the prepared membrane is highly efficient for PV dehydration of IPA. The models were satisfactorily validated against experimental data. Furthermore, the optimum membrane presents excellent separation performance at different feed compositions and temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44587.     

Dehydration of isopropanol by PVA-APTEOS/TEOS nanocomposite membranes

In the present work, dehydration of isopropanol was investigated by novel organic-inorganic nanocomposite membranes which were prepared through sol-gel reaction of polyvinyl alcohol (PVA) with γ-aminopropyl-triethoxysilane (APTEOS) and tetraethoxysilane (TEOS). The PVA chains were crosslinked by mixing silane coupling agents. This reaction between polymer chains and silanols agents could control degree of swelling of the nanocomposite membranes in aqueous isopropanol (IPA) solutions. The membranes were characterized by SEM and ATIR. Effects of APTEOS content in the membranes, feed concentration and temperature on pervaporation (PV) performance were investigated. It was found out that separation factor and permeation flux increase with increasing APTEOS content in the membranes. Arrhenius-type relationship was used for describing the temperature dependence of permeation flux. It was also found out that separation factor decreases with increasing temperature.     

Pervaporation properties of polyvinyl alcohol/ceramic composite membrane for separation of ethyl acetate/ethanol/water ternary mixtures

In further purification of ethyl acetate (EAC) process, azeotropic distillation or extractive distillation is usually applied. High energy consumption limits the economic profit of the process. In this study, pervaporation separation of EAC/ethanol (EA)/water ternary mixtures using the ceramic-supported polyvinyl alcohol (PVA) composite membrane was investigated to substitute the azeotropic distillation or extractive distillation. Swelling experiments were performed to evaluate the sorption characteristic of the membrane. Flory-Huggins theory was applied to study the interaction between the membrane and the penetrant. The UNIFAC model was adopted to investigate the variation of the penetrant activity in the membrane. The effects of operation temperature, feed water content and feed flow rate on the PV performance of the membrane were systematically investigated. The composite membrane exhibited high PV performance with the total flux of 2.1 kg·m⁻²·h⁻¹ and 94.9 wt% permeate concentration of water (operation condition: feed composition 82.6 wt% EAC, 8.4 wt% EA, 9 wt% water, feed temperature 60 °C, feed flow rate 252 mL· min⁻¹). The PV performance of the membrane varied slightly over a continuous PV experiment period of 110 h. Our results demonstrated that the PVA/ceramic membrane was a potential candidate for the purification of EAC/EA/water ternary mixtures.     

Pervaporation separation of water–isopropanol mixture using carboxymethylated poly(vinyl alcohol) composite membranes

The pervaporation separation of water–isopropanol mixtures was carried out using carboxymethylated poly(vinyl alcohol) (CMPVA) composite membranes. Carboxymethylated PVA (CMPVA) was synthesized by reacting PVA with various concentrations of monochloroacetic acid. Substitution efficiency of the CMPVA ranged from 12–32%. The cross‐sectional structure of the composite membrane for pervaporation was confirmed by scanning electron microscopy (SEM) exhibiting a 20‐μm active skin layer. Glass transition temperature of the CMPVA was in the range of 74–84°C, and decreased with increasing substitution efficiency. Degree of swelling and permeation flux for water–isopropanol in pervaporation increased with the substitution degree of carboxymethylation. CMPVA composite membrane, having 16% substitution efficiency, showed the following pervaporation performance; permeation flux of 831 g/m² h and separation factor of 362 measured at 80°C and 85 wt % feed isopropanol concentration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 241–249, 1999     

Pervaporation dehydration of ethyl acetate aqueous solution using the doubly modified polyvinyl alcohol (PVA) composite membrane

Polyvinyl alcohol–tetraethoxysilane–perfluorosulfonic acid (PVA–TEOS–PFSA) hybrid membrane was prepared by sol–gel method through PVA being modified doubly by PFSA and TEOS. With polyacrylonitrile (PAN) ultrafiltration membrane as a substrate membrane, PVA–TEOS–PFSA/PAN composite membrane was fabricated by dip-coating method for pervaporation (PV) dehydration of ethyl acetate (EAc) aqueous solution. The hybrid membrane was characterized by swelling degree, static contact angle, Fourier transform infrared spectra and scanning electron microscope. Effects of PFSA and TEOS contents in coating solution on PV performance of composite membrane were investigated, respectively. With increasing PFSA content, the permeation flux of composite membrane increased, while the separation factor decreased. Just the opposite, the increase of TEOS content resulted in the decrease in permeation flux and the increase in separation factor. In addition, the PV performances of composite membranes were also investigated at different feed temperatures and water concentrations in feed, respectively. The PVA–TEOS–PFSA/PAN composite membrane, which was prepared from coating with PVA/PFSA mass ratio of 80/20 and TEOS content of 20 wt%, exhibited the permeation flux of 347.9 g m^?2 h^?1 and the separation factor of 2218 for PV dehydration of 2 wt% water of EAc solution at 40 °C.     

Enhancement of pervaporation performance of composite membranes through in situ generation of silver nanoparticles in poly(vinyl alcohol) matrix

Composite membranes were prepared from an aqueous solution of poly(vinyl alcohol) (PVA) and silver sulphate. The silver nanoparticles were generated in situ before crosslinking PVA matrix by reduction of silver ions using sodium borohydride. Physico‐chemical properties of the resulting composite membranes were studied using Fourier transform infrared spectroscopy (FTIR), UV–vis spectroscopy (UV–vis), thermogravimetric analysis (TGA), Wide‐angle X‐ray diffraction (WAXD), scanning electron microscopy (SEM), and universal testing machine (UTM). The UV–vis spectrum shows a single peak at 410 nm due to surface plasmon absorption of silver nanoparticles. This surely specified that silver nanoparticles are generated in PVA matrix. The membranes were under go pervaporation (PV) for separation of water from isopropanol at different temperatures. The results indicated that hydrophilicity and amorphous nature of the membranes were increased with increasing silver nanoparticles in PVA matrix. The swelling and separation performance of the membranes were studied. Both permeation flux and separation factor were increased with increasing silver nanoparticles in PVA matrix. The results showed that the membrane containing 2.5 mass% of Ag salt exhibited excellent PV performance. The values of total flux and flux of water are almost closed to each other, indicating that membranes could be effectively used to break the azeotropic point of water‐isopropanol. The long‐term test was performed at room temperature and ascertained that membranes were durable up to 30 days for the dehydration of IPA. On the basis of the estimate Arrhenius activation energy values, the efficiency of the membranes was discussed. The calculated ΔH_s values are negative for all the membranes, indicating that Longmuir's mode of sorption is predominant. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41248.     

γ-(2,3环氧丙氧)丙基三甲氧基硅烷改性壳聚糖渗透蒸发杂化膜的制备及乙醇脱水性能研究

通过γ-缩水甘油醚氧丙基三甲氧基硅(KH-560)对壳聚糖进行交联改性制备乙醇脱水渗透蒸发杂化膜.实验结果表明偶联剂的加入能有效提高壳聚糖膜的分离效果,随着偶联剂含量的增加,杂化膜的对水的选择性先增加后下降,在2％(质量分数)时有最好的选择性.膜的分离因子随着进料温度的增大而降低,随着乙醇浓度的增大而增大;通量随着进料温度的增大而增大,随着乙醇浓度增大而减小.硅烷偶联剂/壳聚糖杂化膜呈现出良好的渗透蒸发分离性能,当进料乙醇浓度为95％(质量分数),温度为35℃时,通量和分离因子分别为134g/(h·m2)和97214.