全氟磺酸改性聚乙烯醇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PVAfPAN、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,交联剂酒石酸(Tat)用量以及原料液温度与浓度对PVA、PAN、PVA-PFSA、PAN复合膜分离件能的影响.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质量比为l/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81.1 g·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.     

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。     

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.     

PVA-TEOS/PAN复合膜渗透蒸发分离己内酰胺/水溶液

制备了以聚乙烯醇(PVA)与正硅酸乙酯(TEOS)交联膜为活性层,以超滤平板膜PAN为底膜的PVA-TEOS/PAN复合膜,并用于己内酰胺脱水.FT-IR和XRD谱图证实复合膜活性层中PVA与TEOS发生交联反应,形成了Si-O-C共价键,膜结晶度降低.用SEM和TGA分别对膜的形貌和热稳定性进行表征.考察了交联剂(T...     

三层结构PDMS/POS/PAN渗透汽化复合膜的制备及其分离性能

分别将四甲基二乙烯基二硅氧烷(DVTMS)和2,4,6,8-四甲基-2,4,6,8-四乙烯基环四硅氧烷(TMTV)与交联剂聚二甲基硅氧烷(PDMS)的B组分(B)聚合形成两种聚硅氧烷DB和TB,涂覆于聚丙烯腈(PAN)表面形成过渡层DB(TB)/PAN,涂覆PDMS分离层得3层结构的PDMS/DB(TB)/PAN渗透汽化复合膜,用于1%正丁醇水溶液的分离,表征了过渡层的结构,研究了硅氧烷/交联剂比和膜液中固形物含量对复合膜渗透汽化性能的影响.结果表明,在分离层和过渡层总厚度相同的情况下,涂覆DB和TB有效提高了膜的渗透汽化性能,最佳膜配方DVTMS:B=3:1(ω)及DB含量5%(ω)时,PDMS/DB/PAN膜的分离因子为40.96,渗透通量为628.40 g/(m2?h);TMTV:B=1:1(ω)及TB含量为3%(ω)时,PDMS/TB/PAN膜的分离因子为41.58,渗透通量为540.00 g/(m2?h).PDMS/DB/PAN膜和PDMS/TB/PAN膜的分离因子分别比相同分离层厚度的PDMS/PAN膜的分离因子提高8.5%和10.2%,渗透通量提高29.5%和11.3%.     

SiO_2-PEBAX/PAN膜渗透汽化分离吡啶

以聚醚共聚酰胺(PEBAX)为分离膜材料,聚内烯腈(PAN)超滤膜为支撑层,纳米气相二氧化硅(n-Si O2)颗粒为填充物,分别制备了PEBAX/PAN复合膜及n-Si O2-PEBAX/PAN填充型复合膜,旨在通过渗透汽化分离吡啶。采用扫描电镜(SEM)、X射线衍射(XRD)、傅里叶红外光谱(FT-IR)对复合膜进行表征,表明n-Si O2与聚合物只是物理混合。以吡啶/正庚烷混合物为模拟溶液,考察膜的溶胀及渗透汽化分离性能。溶胀实验结果表明:膜溶胀度随料液吡啶含量及温度的增加而增大。渗透汽化实验结果表明:n-Si O2填充量为10‰(wt)时总渗透通量最大,填充量为5‰(wt)时分离因子最大。总渗透通量和分离因子都随料液吡啶浓度增大而增加;渗透汽化操作温度升高,总渗透通量增大,而分离因子减小。当填充量为5‰(wt)、温度为30℃、以及料液吡啶含量为5000?g?g?1时,Pn5膜的总渗透通量为5.05 kg?m?2?h?1,分离因子为3.39。研究结果表明,Si O2-PEBAX/PAN复合膜对吡啶有较好的富集作用。     

PVA/ P（AA-Co-AN）/ PVA渗透汽化膜的研究

制备一种PVA/P(AA-Co-AN)/PVA复合膜用于甲醇水溶液的分离,膜的主体部分P(AA-Co-AN)由添加纳米S iO2粉末的丙烯酸(AA)和丙烯腈(AN)通过溶液共聚制得,两侧为交联聚乙烯醇(PVA)。考察了复合膜在高质量分数甲醇水溶液中的溶胀性能,探讨了浸泡液温度及浸泡液质量分数对溶胀度的影响,测试了复合膜的力学性能。考察了不同单体配比〔n(AA)∶n(AN)〕所制备的复合膜在不同质量分数甲醇水溶液,不同温度下的渗透汽化性能。结果显示,复合膜在高质量分数甲醇水溶液中具有良好的溶胀性能及渗透汽化性能;在n(AA)∶n(AN)=1∶1下所制备的复合膜,对高质量分数甲醇水溶液分离效果最佳,60℃时分离w(甲醇)=98%的水溶液,分离因子可达1 534,通量为583 g/(m2.h)。     

PVA/PAN共混膜渗透汽化分离醋酸-水溶液的研究

对自制聚乙烯醇(PVA)/聚丙烯腈(PAN)共混膜渗透汽化分离低浓度醋酸-水溶液体系的性能进行了研究。分别考察了操作温度、下游表压以及醋酸浓度对PVA/PAN共混膜渗透蒸发分离性能影响。结果表明,随着操作温度增大和醋酸浓度及下游压力的减小,膜的渗透通量增加,分离因子减小。在操作温度323 K、下游表压8 mm Hg的条件下,采用膜厚为45μm的PVA/PAN共混膜对90wt.%的醋酸-水体系进行渗透汽化分离,其渗透通量和分离因子分别达到3746 g·m-2·h-1和3.75。     

分离有机/有机混合物的PVA、CA系列膜及其渗透汽化性能研究(Ⅰ)膜材料与成膜工艺

依据溶度参数原则和分离甲基叔丁基醚(MTBE)/甲醇(MeOH)混合物的选择渗透性,选择了聚乙烯醇(PVA)为复合膜的分离层材料,聚丙烯腈(PAN)、醋酸纤维素(CA)系列为支撑层的膜材料.初步讨论了膜材料和复合膜结构对分离性能的影响,给出了用不同成膜工艺制备的膜性能,获得了可用于有机/有机体系分离的性能优良的PVA/PAN和PVA/CA复合膜,以及CTA中空纤维渗透汽化膜.     

新型聚乙烯醇/硅系杂化膜的制备及渗透性能

采用溶胶-凝胶法制备了聚乙烯醇（PVA）/γ-氨丙基三乙氧基硅氧烷（APTEOS）有机/无机杂化膜。用FTIR和XRD对杂化膜进行了表征。测定了膜在乙醇/水溶液中的溶胀行为。考察了杂化膜对85%（质量）的乙醇/水溶液的渗透蒸发分离性能。加入APTEOS降低了PVA的结晶度,有效控制了膜的溶胀,呈现出优良的分离性能。随着APTEOS含量的增加,杂化膜的选择性急剧增加,在5.0%（质量）时达到最大值;同时膜的渗透通量迅速增加。解决了PVA膜trade-off效应。     

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.     

Perfluorosulfonic acid—Tetraethoxysilane/polyacrylonitrile (PFSA‐TEOS/PAN) hollow fiber composite membranes prepared for pervaporation dehydration of ethyl acetate–water solutions

Preparation of organic‐inorganic composite membranes and their pervaporation (PV) permeation and separation characteristics for the aqueous solution of ethyl acetate were described. Polyacrylonitrile (PAN) hollow fiber ultrafiltration membrane as support membrane, the mixtures of perfluorosulfonic acid (PFSA) and tetraethoxysilane (TEOS) by the sol‐gel reaction as the coating solution, the PFSA‐TEOS/PAN hollow fiber composite membranes by the different annealing conditions were prepared. The swelling of PFSA in ethyl acetate aqueous solutions was inhibited with addition of TEOS. The PFSA‐TEOS/PAN composite membranes containing up to 30 wt % TEOS in coating solution exhibited high selectivity towards water, then the selectivity decreased and permeation flux increased with increasing the TEOS concentration more than 30 wt %. When the PFSA‐TEOS/PAN composite membranes were annealed, the separation factor increased with increasing annealing temperature and time. Higher annealing temperature and longer annealing time promoted the crosslinking reaction between PFSA and TEOS in PFSA‐TEOS/PAN composite membranes, leading to the enhanced selectivity towards water. For the PFSA/PAN and PFSA‐TEOS/PAN composite membrane with 5 and 30 wt % TEOS annealed at 90°C for 12 h, their PV performance of aqueous solution 98 wt % ethyl acetate were as follows: the separation factors were 30.8, 254 and 496, while their permeation flux were 1430, 513 and 205 g/m² h at 40°C, respectively. In addition, the PV performance of PFSA‐TEOS/PAN composite membranes was investigated at different feed solution temperature and concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

影响渗透汽化中空纤维复合膜分离性能的制备工艺研究

采用聚乙烯醇（ＰＶＡ）为分离层的模材料,以浸涂工艺把ＰＶＡ复合到聚砜（ＰＳ）或聚丙烯腈（ＰＡＮ）的中空纤维支撑层上,在长度为０．４ｍ的不锈钢管中组装若干根中空纤维复合膜测定对乙醇水溶液的渗透汽化（ＰＶ）分离性能。结果表明,ＰＶＡ／ＰＡＮ中空纤维复合膜的性能优于ＰＶＡ／ＰＳ,内径较大（１．３ｍｍ）的优于内径上（０．４ｍｍ）者,ＰＶＡ水溶液在中空纤维支撑层上的涂复次数对复合膜ＰＶ分离性能、以及ＰＶＡ／     

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。     

Comparative behavior of PVA/PAN and PVA/PES composite pervaporation membranes in the pervaporative dehydration of caprolactam

Flat‐sheet composite membranes were developed by the traditional phase inversion technique using poly;(vinyl alcohol) (PVA). PVA composite pervaporation (PV) membranes were prepared with crosslinked PVA selective layer and porous polyacrylonitrile (PAN) and polyether sulfone (PES) substrate layer material as supports for separating heat sensitivity substance ε‐caprolactam (CPL) from CPL/water mixtures. Glutaraldehyde was used as crosslinking agent. The effect of the composition of glutaraldehyde on membrane stability and structure were investigated. The operating parameters, such as feed concentration and operating temperature, remarkably affected PV performance of the composite membranes. The composite membranes with PVA casted on PAN (PVA/PAN) showed superior PV performance than that casted on PES (PVA/PES). This study has also shown that the type of porous support plays an important role in the PV performance. As a result, this work has presented the information needed of the behavior of PV membranes for dehydration applications of industrial caprolactam. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4005–4011, 2007     

Hybrid sol–gel membranes of polyacrylonitrile–tetraethoxysilane composites for gas permselectivity

Sol–gel reaction of tetraethoxysilane (TEOS) with fumed silica–polyacrylonitrile (PAN) membrane was carried out to prepare hybrid gas permeable membranes for oxygen and nitrogen separation. Various amounts of fumed silica microparticles with a few μm diameters were compounded in PAN–dimethylsulfoxide (DMSO) solution. After casting of the viscous compound solution on a flat sheet with 100 μm thickness, DMSO was evacuated under vacuum at 80°C. Then, the silica–PAN composite membranes were treated with TEOS for 1 day at 40°C in methanol. Air permeation was examined and compared in silica–PAN composite membranes with and without TEOS treatment. The latter hybrid membranes showed selective oxygen permeability, which depended on amounts of fumed silica in the membrane. The TEOS hybrid PAN membranes have a high ability of oxygen permselectivity for O₂/N₂ gas mixture with α(O₂/N₂) = 13–17, when the silica content was in the range of 13–20 wt %. This is attributed to siloxane network formation in hybrid silica–PAN composite membranes. Favorable siloxane network formation resulted in high oxygen permeability of the hybrid composite membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1752–1759, 2003     

Polymer membranes for separating organic mixtures

Polyvinyl alcohol (PVA), polyacrylonitrile (PAN), and cellulose ester were respectively chosen as the separation layer and the support in the composite membranes based on the concept of the solubility parameter and the permselectivities for separating ethanol/water mixture, isopropanol/water mixture, and caprolactam/water mixture. The effects of the membrane materials and the construction of the composite membrane on the separation performance were preliminary discussed. The separation performance of the membranes prepared by several making‐membrane techniques, i.e., the polymer solution making‐membrane technique, and the membrane treatment technique (heat treatment, organic solvent modification) were presented. The composite membranes of PVA/PAN and PVA/cellulose acetate, and cellulose triacetate hollow fiber membrane modified, which possess good performance in separating the organic systems, were developed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1160–1164, 2006     

聚乙烯醇-二氧化硅/聚丙烯腈杂化复合膜渗透蒸发分离己内酰胺/水溶液

制备了以聚乙烯醇(PVA)填充纳米SiO2改性膜为活性层,聚丙烯腈(PAN)超滤膜为底膜的PVA-SiO2/PAN杂化复合膜,并用于己内酰胺(CPL)脱水。用FTIR,SEM,XRD,TGA分别对膜进行了表征,并考察了膜中纳米SiO2粒子的质量分数、进料组分质量分数和温度对复合膜分离性能的影响。结果表明,引入纳米SiO2后,杂化膜的热稳定性明显提高。当膜中纳米SiO2质量分数为1.0%时,复合膜渗透蒸发分离性能最佳。60℃下此复合膜用于分离质量分数为40%的CPL溶液时,其总通量和分离因子分别达到2 177 g/(m2.h)和349。