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。     

Preparation and characterization of PVA-g-GO/PVA/PAN composite membrane for pervaporation desalination

Graphene oxide (GO) has extensive applications in membrane-based separations, but its dispersion in the membrane has always been a problem due to the presence of π–π interactions in GO nanosheets. In this study, a grafting reaction was designed by using poly (vinyl alcohol) (PVA) for GO grafting modification and poly (vinyl alcohol)-g-graphene oxide (PVA-g-GO) nanocomposites were synthesized. The grafting material to GO was the same as the basic separation polymer material. PVA-g-GO showed better dispersibility and hydrophilicity than GO, and a series of composite membranes were prepared using a polyacrylonitrile (PAN) ultrafiltration (UF) membrane as a substrate. PVA-g-GO nanocomposites and membranes were characterized by using X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), water contact angle, scanning electron microscopy (SEM), etc. The addition of PVA-g-GO improved both the separation performance and anti-swelling property of the composite membrane, and the PVA-g-GO/PVA/PAN composite membrane loaded with 2 wt.% PVA-g-GO obtained a high flux of 4.46 kg/m² · h and a high rejection of 99.99% when dehydrating 3.5 wt.% NaCl solution at 30°C by pervaporation.     

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     

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     

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／     

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%.     

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.     

Preparation and characterization of CMCS/PVA blend membranes and its sorption and pervaporation performance (I)

Novel pervaporation (PV) membranes for ethanol dehydration were prepared by blend poly(vinyl alcohol) (PVA) and carboxymethyl chitosan (CMCS), followed by the crosslinking reaction with glutaraldehyde; the structure and miscibility of the blend membranes were characterized by Fourier transform infrared, X‐ray diffraction, and differential scanning calorimetry; the results indicated that the blends were miscible. The effect of feed concentration, operation temperature, crosslinking agent content, etc. on sorption performance and PV performance of the blend membrane is investigated. The membrane of CMCS/PVA blend ratio of 8 : 2 exhibited a high separation factor of 2959 with a reasonably high water flux value of 0.14 kg m^?2h^?1 at the azeotropic feed composition (95 wt % of ethanol) at a temperature of 45°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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 and characterization of PVA/SA composite nanofiltration membranes

Nanofiltration (NF) composite membranes based on poly(vinyl alcohol) (PVA) and sodium alginate (SA) were prepared by coating PVA/SA (95/5 in wt %) mixture solutions on microporous polysulfone (PSF) supports. For the formation of a defect free thin active layer on a support, the PSF support was multi‐coated with a dilute PVA/SA blend solution. The PVA/SA active layer formed was crosslinked at room temperature by using an acetone solution containing glutaraldehyde as a crosslinking agent. The prepared composite membranes were characterized with a scanning electron microscopy (SEM), a Fourier transform infrared spectroscopy (FTIR), an electrokinetic analyzer (EKA) and permeation tests: The thicknesses of the active layers were about 0.25 μm and 0.01 μm depending on the preparation conditions. The crosslinking reaction of the active layers were completed in less than three minutes via the formation of acetal linkage. The surface of the PVA/SA composite membrane was found to be anionic. The permeation properties of the composite membrane were as follows: 1.3 m³/m² day of flux and > 95% of rejection at 200 psi for 1000 ppm PEG600 solution. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 347–354, 2000     

表面偏析法制备用于乙醇渗透蒸发脱水的整体PVA-PES复合膜(英文)

A facile surface segregation method was utilized to fabricate poly(vinyl alcohol)-polyethersulfone (PVA-PES) composite membranes. PVA and PES were first dissolved in dimethyl sulfoxide (DMSO), then casted on a glass plate and immersed in a coagulation bath. During the phase inversion process in coagulation bath, PVA spontaneously segregated to the polymer solution/coagulation bath interface. The enriched PVA on the surface was further crosslinked by glutaraldehyde. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive spectrometer (EDS) confirmed the integral and asymmetric membrane structure with a dense PVA-enriched surface and a porous PES-enriched support, as well as the surface enrichment of PVA. The coverage fraction of the membrane surface by PVA reached up to 86.8% when the PVA content in the membrane recipe was 16.7% (by mass). The water contact angle decreased with the increase of PVA content. The effect of co-agulation bath type on membrane structure was analyzed. The membrane pervaporation performance was evaluated by varying the PVA content, the annealing temperature, feed concentration and operation temperature. The mem-brane exhibited a fairly good ethanol dehydration capacity and long-term operational stability.     

Study of pervaporation for dehydration of caprolactam through PVA/nano silica composite membranes

We investigated nano silica/PVA composite membranes to propose an improved caprolactam pervaporation (PV) dehydration process. The membranes were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and contact angle measurement. Compared with the pure PVA membranes, the nano silica/PVA composite membranes showed different surface morphologies with enhanced hydrophilicity because of their unique formation. To evaluate PV performance and mechanism, we assessed the permeation flux, separation factor, diffusivity/sorptivity selectivity, and activation energy of the composite membranes. The evaluated results indicate that the nano silica/PVA composite membranes induced a breakthrough in the dehydration of a caprolactam-water mixture with a maximum flux of 3.8 kg m^? 2 h^? 1 and an acceptable separation factor of 150.     

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.     

陶瓷支撑的有机复合膜及其在渗透汽化中的应用(英文)

Pervaporation(PV),as an environmental friendly and energy-saving separation technology,has been received increasing attention in recent years.This article reviews the preparation and application of macroporous ceramic-supported polymer composite pervaporation membranes.The separation materials of polymer/ceramic composite membranes presented here include hydrophobic polydimethylsiloxane(PDMS) and hydrophilic poly(vinyl alcohol)(PVA),chitosan(CS) and polyelectrolytes.The effects of ceramic support treatment,polymer solution properties,interfacial adhesion and incorporating or blending modification on the membrane structure and PV performance are discussed.Two in-situ characterization methods developed for polymer/ceramic composite membranes are also covered in the discussion.The applications of these composite membranes in pervaporation process are summarized as well,which contain the bio-fuels recovery,gasoline desulfuration and PV coupled proc-ess using PDMS/ceramic composite membrane,and dehydration of alcohols and esters using ceramic-supported PVA or PVA-CS composite membrane.Finally,a brief conclusion remark on polymer/ceramic composite mem-branes is given and possible future research is outlined.     

明胶涂覆于亲水化改性的支撑层上以提高复合膜的结构稳定性和渗透蒸发性能简

The interfacial compatibility of composite membrane is an important factor to its structural stability, andseparation performance. In this study, poly （ether sulfone） （PES） support layer was first hydrophilically modified with poly（vinyl alcohol） （PVA） via surface segregation during the phase inversion process. Gelatin （GE） was then cast on the PVA-modified PES support layer as the active layer followed by crosslinking to fabricate composite membranes for ethanol dehydration. The enrichment of PVA on the surface of support layer improved interfacial compatibility of the as-prepared GE/PVA-PES composite membrane. The water contact angle measurement and X-ray photoelectron spectroscopy （XPS） data confirmed the surface segregation of PVA with a surface coverage density of -80%. T-peel test showed that the maxima/force to separate the support layer and the active layer was enhanced by 3 times compared with the GE/PES membrane. The effects of PVA content in the support layer, crosslinking of GE active layer and operating parameters on the pervaporative dehydration performance were investigated. The operational stability of the composite membrane was tested by immersing the membrane in ethanol aqueous solution for a period of time. Stable pervaporation performance for dehydration of 90% ethanol solution was obtained for GE/PVA-PES membrane with a separation factor of -60 and a permeation flux of -1910 g.m^-2.h1 without peeling over 28 days immersion.     

Effects of CNTs Content on Physicochemical and Pervaporation Separation Properties of PVA Membranes

In this study, the morphological and separation characteristics of PVA membranes incorporated with functionalized CNTs are reported. CNTs was extensively characterized using TGA, FESEM, and TEM. The physicochemical properties of PVA-CNTs membranes were characterized using FESEM, tensile test, DSC, and XRD. DSC measurements showed an increase in melting and glass transition temperature, implying enhancement of polymer chains compacting. XRD analysis confirmed the results of DSC and showed that CNTs can promote crystallinity of the PVA membranes. In addition, tensile measurements revealed that incorporating CNTs into the PVA membranes improves their mechanical properties. The synthesized nanocomposite membranes were then evaluated in pervaporation (PV) dehydration of isopropanol (IPA). The separation results showed that incorporating CNTs into the PVA membranes significantly increases water selectivity of the PVA membranes. This can be attributed to the fact that incorporating CNTs compacts and rigidifies PVA matrix and decreases its free volume. Furthermore, permeation of water molecules through the nanocomposite membranes decrease as a result of the polymer chains rigidification. Effects of feed composition and temperature on PVA-CNTs nanocomposite membranes were investigated. Besides, effects of CNTs content on permeation properties and activation energies of PVA membranes were evaluated.     

Dehydration of tetrahydrofuran by pervaporation using crosslinked PVA/PEI blend membranes

Dense blend membranes were prepared by blending hydrophilic polymers poly(vinyl alcohol) (PVA) and poly(ethyleneimine) (PEI), which were then crosslinked by glutaraldehyde (GA) in a mixture of solvents under the catalysis of hydrochloric acid (HCl) for the dehydration of tetrahydrofuran (THF) by pervaporation. The effect of experimental parameters such as feed water concentration, permeate pressure, and membrane thicknesses on permeate parameters, i.e., flux and selectivity were determined with feed water concentration less than 40 wt %. The membranes were found to have good potential for breaking the azeotrope of 94 wt % THF with a flux of 1.072 and 0.376 kg/m² h for plane PVA/PEI and crosslinked PVA/PEI blend membrane, which exhibited high selectivity of 156 and 579 respectively. Selectivity was found to improve with decreasing feed water concentration and increasing membrane thickness, whereas flux decreased correspondingly. High permeate pressure causes a reduction in both flux and selectivity. These effects were clearly elucidated with the aid of the known relationship among plasticization effect, degree of swelling, permeate pressure, and feed water concentration. These blend membranes were also subjected to sorption studies to evaluate the extent of interaction and degree of swelling in pure as well as binary feed mixtures. Further ion exchange capacity studies were carried out for all the crosslinked and uncrosslinked membranes to determine the total number of interacting groups present in the membranes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1152–1161, 2006     

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.     

新型PVA/PA复合膜的运行工艺对渗透汽化性能的影响

研究了聚乙烯醇（PVA）/聚酰胺（PA）复合膜渗透汽化（PV）分离异丙醇（IPA）/水混合物时运行工艺的影响,模拟了渗透通量（J）预测方程。结果表明,PVA/PA复合膜在料液中w（IPA）%在0～95%范围内或在25℃～100℃的操作温度范围获得的渗透液中IPA含量[w′（IPA）]都小于1%,J随料液中w（IPA）%的下降或操作温度的提高而增加。分离性能预测方程的拟合结果与试验数据有良好一致性。在室温条件下,经过90 d的间歇运行或经过120 d的长期贮存后,PVA/PA复合膜的分离性能稳定,在IPA/水混合物的共沸温度80.4℃运行时的J为73.1 g/m^2·h,渗透液中的水含量[w′（H2O）]都大于99.5%,展示了其在食品、生物、制药和化学等工业中将具有良好的应用前景。     

己内酰胺/氯化镁复配增塑聚乙烯醇的性能研究

采用己内酰胺/氯化镁为复配增塑剂,通过流延法制备出了增塑改性的聚乙烯醇(PVA)膜。采用DSC、TGA、XRD分析和力学性能与熔体流动性能测试的方法考察了己内酰胺/氯化镁复配增塑剂对PVA性能的影响。结果表明:氯化镁与己内酰胺复配具有良好的协同增塑效应,其对PVA的增塑效果优于单独使用己内酰胺;复配增塑剂能够有效破坏PVA分子间的氢键,降低PVA的结晶度;加入复配增塑剂后,PVA的熔点降低,热稳定性提高,熔体流动性有所改善,拉伸强度降低,断裂伸长率上升。