聚二甲基硅氧烷渗透汽化膜的研究进展

聚二甲基硅氧烷(PDMS)作为一种疏水的橡胶态聚合物材料,可用于渗透汽化技术领域,其对有机物的脱除具有明显的优势,近年来得到了广泛的关注。介绍了PDMS膜的特点,总结了国内外运用不同材料作为支撑层制备PDMS渗透汽化复合膜的研究进展以及应用情况,指出了PDMS渗透汽化膜存在的问题及其发展方向。     

渗透汽化分离精油中挥发性芳香化合物的研究进展

精油及其挥发性组分在化妆品、食品和药品工业、农业及食品保鲜等领域有着广泛的应用潜力。目前挥发性精油的分离主要采用的是分段蒸馏技术,该技术存在成本高、能耗大且容易造成精油组分破坏等缺陷,因此其应用受到了极大的限制。渗透汽化（pervaporation,PV）是一种用于液体混合物分离的新型膜分离技术,具有高效节能、环境友好和容易操作等优点,特别是能够实现热敏性物质的高效单级分离,因此在挥发性精油的分离和挥发性芳香化合物组分精制等方面具有巨大的应用潜力。本文系统总结了渗透汽化技术在挥发性精油分离领域的最新进展,综述了用于分离挥发性精油的渗透汽化膜材料、分离工艺及其应用现状,并对渗透汽化用于大规模分离挥发性精油过程中面临的挑战进行了讨论。     

芳烃优先透过的渗透汽化复合膜的制备及分离性能研究

采用紫外光接枝填充聚合技术,以非对称聚丙烯腈(PAN)超滤膜为底膜,聚乙二醇甲醚甲基丙烯酸酯(MePEO300MA)为大分子单体,制备了芳烃优先透过的渗透汽化复合膜。考察了单体浓度和紫外光照射反应时间对复合膜甲苯/正庚烷渗透汽化分离性能的影响,并对复合膜降低石脑油芳烃含量,优化乙烯裂解原料进行了初步探索。研究结果表明,复合膜对甲苯质量分数为20%的甲苯/正庚烷混合物(80℃)的分离系数达到5.6,渗透通量为2.47 kg/(m2.h);当切割比为20%时,石脑油的芳烃质量分数由7.52%降至4.11%,降低了45%,初步说明渗透汽化复合膜在降低石脑油的芳烃含量,优化乙烯裂解原料方面的应用前景。     

"充填型"复合膜脱除水中微量有机氯化物的研究

利用等离子体照射引发接枝聚合方式制备了具有"充填型"结构的复合膜,在渗透汽化膜分离过程中研究了其从水中脱除微量有机氯化物的分离性能.该复合膜由两种材料组成;耐溶剂性能优良的高密度聚乙烯多孔基膜和接枝聚合后充填于基膜微孔中的聚丙烯酸甲酯,后者形成渗透汽化过程的分离选择性.使用FT-IR光谱图证实基膜接枝后表面存在羰基,表明形成接枝聚合的复合膜.在室温下进行渗透汽化实验,能够有效脱除水中微量的二氯甲烷、三氯甲烷和三氯乙烯,其中脱除二氯甲烷的渗透汽化分离因子超过2000,渗透通量达到120 g·(m2·h)- 1.     

渗透汽化处理石化有机废水技术研究进展

针对有机废水的治理现状,介绍了一种新型膜分离技术-渗透汽化技术.首先,总结了它在石化有机废水处理领域的应用现状,主要集中在挥发性有机物废水处理和高盐有机废水处理2个方面;其次,提出了渗透汽化应用过程中存在的主要问题,即膜通量和膜的分离系数偏低,它是渗透汽化技术工业应用的主要障碍;最后,展望了渗透汽化在石化废水处理领域的具体发展方向,并预测了渗透汽化在废水处理领域的发展前景.     

中空纤维渗透汽化膜分离研究现状与展望

本文综述了中空纤维渗透汽化膜分离的研究进展,包括中空纤维支撑膜的制备、复合膜的制备方法、中空纤维渗透汽化膜的工业应用和中空纤维渗透汽化膜传质特性等几个方面,对这个方面所存在的问题以及今后发展方向进行了展望.     

PSF支撑层结构对PDMS复合膜渗透汽化性能的影响

以4种不同结构的聚砜(PSF)作为支撑层,制备PDMS/PSF渗透汽化复合膜,考察其用于乙醇/水体系的分离性能,以研究支撑层结构对渗透汽化复合膜分离性能的影响。采用SEM和EDX分析复合膜表层结构,结果表明,支撑层结构几乎不影响复合膜的选择性,但对膜通量有较大影响,特别是支撑层的表面结构对复合膜性能的影响比断面结构更明显。     

催化剂对酯化反应渗透汽化膜稳定性的影响

比较了酯化反应耦合渗透汽化膜反应器中不同的催化剂体系及其含量对ＰＰＶＡ／ＰＡＮ复合膜稳定性的影响。试验结果表明,固体超强酸催化剂体系对复合膜的稳定性没有影响。活性层酯化度为３．３％及６．２％的复合膜具有良好的稳定性。能够适合于酯化反应耦合渗透汽化过程研究及应用。     

模拟的发酵液组分对聚二甲基硅氧烷/陶瓷复合膜渗透汽化性能的影响

对所制备的聚二甲基硅氧烷（PDMS）/陶瓷复合膜进行了渗透汽化性能表征。通过在乙醇-水混合体系中添加不同的模拟发酵液组分;如葡萄糖（多羟基醛）、甘油（多元醇）、丁二酸（有机酸）、KCl（无机盐）;考察了各组分对复合膜渗透汽化性能的影响。研究发现：在333 K下;在乙醇浓度为65 g·L-1的混合物中添加不同浓度的第三组分;有机添加物对膜的渗透汽化性能没有明显影响;而无机盐的加入使膜的分离因子稍有提高。所制备的PDMS/陶瓷复合膜;在上述渗透汽化过程中表现出良好的稳定性和对乙醇的优先选择性;渗透通量和分离因子（醇/水）分别在4.5～4.7 kg·m^-2·h^-1、8.3～10.3之间。     

PTFE对PDMS复合膜在低浓度有机物水溶液中渗透汽化性能的影响

制备了聚四氟乙烯（PTFE）超细粉体填充聚二甲基硅氧烷（PDMS）复合膜,通过扫描电子显微镜、傅里叶变换红外光谱仪、热失重分析仪等测试仪器对复合膜进行了表征,利用低浓度有机物（乙醇、丙酮、正丙醇）水溶液体系进行渗透汽化,并由单组分溶解实验计算了有机物（乙醇、丙酮、正丙醇）在复合膜中的溶解度。结果表明,PTFE含量由0增加至10 %（质量分数,下同）时, 复合膜的表面积及热稳定性得到了提高,有机物乙醇、丙酮、正丙醇在复合膜中的溶解度分别由0.0923、0.1589和0.2691 g/g提高至0.0991、0.1678和0.2773 g/g;加入PTFE后提高了复合膜的渗透汽化性能。     

水溶液中挥发性有机化合物渗透蒸发分离技术

介绍了水溶液中挥发性有机化合物 (VOCs)的各种分离方法 ,重点分析了渗透蒸发分离技术经济优势。阐释了渗透蒸发膜的选择标准、渗透蒸发过程的传质机理 ,以及原料液浓度、原料液温度、原料液流量、渗透侧压力、添加剂和膜组件型式等因素对渗透蒸发过程分离效率的影响 ,并简要预测了渗透蒸发过程的发展趋势与动态。     

Pervaporative dehydration of diethylene glycol through a hollow fiber membrane

In this study, the pervaporative dehydration of diethylene glycol (DEG) through a commercial hollow fiber membrane was investigated at various feed temperatures in the range of 333–363 K with feeds containing 0.5–2.0 wt % water. Unlike the usual pervaporative dehydration process in which water is less volatile than the organic solvent, the feed mixture used in this study contained the organic component DEG, which is less volatile than water, resulting in unique permeation behaviors. The permeation behaviors of the individual components were investigated as functions of the feed temperature and feed composition. In particular, the effect of the low vapor pressure characteristics of DEG was investigated. Semi‐empirical equations for predicting the individual component fluxes and separation factor were quantified directly from actual dehydration pervaporation of DEG. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polysiloxaneimide membranes for removal of VOCs from water by pervaporation

For the separation of volatile organic compounds (VOCs) from water by pervaporation, three polysiloxaneimide (PSI) membranes were prepared by polycondensation of three aromatic dianhydrides of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), and pyromellitic dianhydride (PMDA) with a siloxane‐containing diamine. The PSI membranes were characterized using ¹H‐NMR, ATR/IR, DSC, XRD, and a Rame‐Hart goniometer for contact angles. The degrees of sorption and sorption selectivity of the PSI membranes for pure organic compounds and organic aqueous solutions were investigated. The pervaporation properties of the PSI membrane were investigated in connection with the nature of organic aqueous solutions. The effects of feed concentration, feed temperature, permeate pressure, and membrane thickness on pervaporation performance were also investigated. The PSI membranes prepared have high pervaporation selectivity and permeation flux towards hydrophobic organic compounds. The PSI membranes with 150‐μm thickness exhibit a high pervaporation selectivity of 6000–9000 and a high permeation flux of 0.031–0.047 kg/m² h for 0.05 wt % of the toluene/water mixture. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2691–2702, 2000     

Pervaporation removal of volatile organic compounds from aqueous solutions using the highly permeable PIM‐1 membrane

Wastewater containing volatile organic compounds (VOCs) is generated in various industrial processes and is seriously harmful to the natural environment and human health. Its treatment has become extremely important due to increasing environment concerns. Here, a high permeable membrane for fast and high‐efficient VOCs removal from aqueous solutions by pervaporation is reported. The as‐prepared PIM‐1 membrane allows ultrafast permeation of VOCs and exhibits excellent VOCs selectivity, particularly for ethyl acetate, dimethyl ether, and acetonitrile. Typically, the PIM‐1 membrane exhibits an ultrahigh flux and separation factor of 39.5 kg μm m^?2 h^?1 and 189, respectively, in the pervaporation of 1.0 mol% aqueous ethyl acetate solution. Furthermore, the solubility‐diffusion mechanism is revealed in the pervaporation of 10 kinds of 1.0 mol% VOCs solutions. It is found that the pervaporation performance is affected directly by physicochemical properties of VOCs. Moreover, effects of feed composition and temperature on the pervaporation are studied in details. © 2015 American Institute of Chemical Engineers AIChE J, 62: 842–851, 2016     

Sorption and diffusion of volatile organic compounds in fluoroalkyl methacrylate‐grafted PDMS membrane

Pervaporation is known as an excellent method for the purification of contaminated water, the extraction of aroma compounds, etc., and has been widely studied. The prediction of permeation is important for treatment, extraction, and quantitative analysis. To predict permeation, a solution–diffusion mechanism is proposed. The octanol–water partition coefficient (Pow) has been generally used in expressing hydrophobicity. The hydrophobicity, Pow, is closely related to the solubility of organic compounds. Also, the molecular volume is closely related to the diffusion of organic compounds. In this study, we improved polydimethylsiloxane (PDMS) membranes by plasma grafting of fluoroalkyl methacrylates (FALMA) to enhance the affinity of PDMS to volatile organic compounds (VOCs). Furthermore, we investigated the pervaporation through the plasma‐grafted PDMS membrane and the PDMS membrane and the solution–diffusion mechanism of various VOCs. The permselectivity of tetrachloroethylene (PCE) and toluene determined by the sorption and the diffusion characteristics permeating in the membrane was high. Because the molecular volume of the VOCs is greated than that of water and the permeates quickly penetrate in rubbery membranes like PDMS, permselectivity was not affected by the diffussivity. Solubility significantly affected the permselectibity during pervaporation through a hydrophobic rubbery membrane. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 773–783, 2000     

优先透过有机物渗透汽化膜研究进展

近年来膜分离技术被广泛应用于有机物的分离回收。渗透汽化能有效地分离共沸混合物、近沸混合物、异构体和热敏性化合物等有机物。渗透汽化以成本低、条件温和、设备简单、无污染等优点在有机物分离回收领域有着巨大优势，可广泛的应用于工业生产。该文以优先透过有机物为主旨，首先分析了材料对膜结构和特点的影响。其次综述了制备方法和改性方法对膜性能的影响。重点讨论了膜在有机混合物分离回收领域的应用。最后，对目前渗透汽化技术所存在的问题做出了总结，对未来的研究方向和研究思路进行了展望。未来优先透过有机物渗透汽化膜的研究应借助新的计算工具，侧重于材料选择、制备方法和改性方法的改进，如探索具有多功能化学基团和具有明确层次结构的多孔填料的聚合物材料等，使优先透过有机物渗透汽化膜具有更加广阔的应用前景。     

CONCENTRATION POLARIZATION ANALYSIS AT THE ENTRANCE REGION OF A FLAT SHEET PERVAPORATION MODULE FOR VOC REMOVAL

Concentration polarization is a phenomenon that is inherent in all membrane separation processes, which is difficult if not impossible to measure experimentally. Concentration polarization in a pervaporation module causes flux decline and is therefore an important issue in predicting the performance of the membrane unit for evaluation and optimization. Short-form (small L/D ratio) membrane configurations, commonly used for membrane evaluations or certain material separations, compound the complexity of process modeling that addresses concentration polarization since a substantial portion of the membrane flow channel would be considered as an “entrance region” based on the flow profile that is not fully developed. This article employed the classic boundary layer theory, combined with mass transfer phenomena in a pervaporation process that is used in volatile organic compound (VOC) removal from contaminated water sources, to theoretically analyze the concentration polarization severity in the entrance region of a flat sheet membrane module.     

Chemical modification of poly(substituted-acetylene). IV. Pervaporation of organic liquid/water mixture through poly(1-phenyl-1-propyne)/polydimethylsiloxane graft copolymer membrane

Poly(1-phenyl-1-propyne)/polydimethysiloxane (PPP/PDMS) graft copolymer membranes having various PDMS content were prepared by solvent casting method, and the permeation characteristics at pervaporation were examined upon the aqueous solutions containing organic liquids such as alcohols, acetone, dioxane, acetonitrile, pyridine, and DMF. At pervaporation of ethanol/water mixture, preferential permeation of ethanol was observed for all the copolymer membranes, although PPP membrane showed water permselectivity. The permselectivity of the copolymer membrane also depended on operation temperature, but was independent on the thickness of the membrane. Furthermore, an excellent permselectivity of organic liquids was observed at the pervaporation of several organic liquid/water mixtures except in the case of DMF/water mixture. Observed high selectivity is thought to be due to the depression of the membrane swelling and the high solubility of the liquids into the membrane.     

浅析渗透汽化膜脱水及其应用

渗透汽化作为一种节能、低能耗、绿色环保的新型膜分离技术,正受到世界范围内越来越广泛的关注和研究。文中简述了渗透汽化膜技术的基本原理、工艺流程和传质模型,介绍了影响分离效果的因素及特点;分析渗透汽化技术在有机溶剂脱水、水中脱除有机物以、有机物/有机物的分离以及化学反应中的工业应用情况,并进行经济性分析,最后展望了该技术的应用前景。     

Effect of Residual Solvent on Physicochemical Properties of Poly(Phenylene Isophtalamide) Membrane

The influence of a plasticizer in the form of the residual solvent dimethylacetamide on pervaporation and sorption properties of membranes based on poly(phenylene isophtalamide) (PA) was investigated. To analyze the influence of the plasticizer on membrane transport properties, pervaporation of binary water–ethyl acetate mixtures was studied. The method of sorption calorimetry was used to investigate water sorption properties of the studied membranes and PA powder. Moreover, to characterize the PA membranes, contact angle measurements and thermogravimetric analysis (TGA) were applied. It is shown that the presence of a residual organic solvent significantly changes the sorption and transport characteristics of the membranes. The residual organic solvent increases the amount of water absorbed by the polymer membrane. In pervaporation of water/ethyl acetate mixtures, the presence of the residual solvent dimethylacetamide makes the membrane more permeable but less selective for water separation.