聚乙烯醇／壳聚糖共混膜优先透醇性能的研究

聚乙烯醇／壳聚糖共混膜优先透醇性能的研究王新平，沈之荃，张富尧，林荣轩（浙江大学高分子系，化学系，杭州，３１００２７）关键词渗透蒸发，聚乙烯醇／壳聚糖共混物膜，乙醇水溶液本文首次报道利用亲水性的聚乙烯醇和壳聚糖制得具有很高的乙醇优先透过选择性的透醇型...     

有机物优先透过的聚二甲基硅氧烷渗透汽化膜的改性研究进展

有机物优先透过的渗透汽化过程(Organophilic Pervaporation,O-PV)是一种膜分离技术,可以有效脱除化学、制药、电子、石化、印刷、涂料、纺织等工业废水中含有的微量挥发性有机物(Volatile organic compounds,VOCs),如苯、甲苯、三氯乙烯、氯仿和苯酚等.膜(一般指高分子膜)是O-PV过程的核心,而用于O-PV的膜分离性能主要取决于膜材料所具有的内在分离性能.聚二甲基硅氧烷(Poly(dimethyl siloxane), PDMS )是目前为止应用最为广泛的O-PV膜材料.本文综述了有机物优先透过的PDMS渗透汽化膜的改性研究进展,并展望了其未来的发展方向和前景.     

渗透汽化优先透醇分离膜

20世纪70年代的能源危机促使了人们对可再生能源-发酵法制备乙醇与节能分离工艺的探求。渗透汽化膜分离技术作为一种新兴的膜分离技术,具有分离效率高、低能耗、易于和发酵装置耦合、易于与其它分离方法联用等显著优点,特别适用于乙醇/水等恒沸混合物体系的分离。本文简要介绍了渗透汽化优先透醇膜的研究背景,总结并分析了用于指导膜材料选择的理论,详细介绍了用于制备优先透醇膜的含硅聚合物、含氟聚合物、有机/无机复合膜材料以及其他聚合物等膜材料的的结构特点、改性方法及膜材料分子结构与渗透汽化性能间的关系,并对不同膜材料对乙醇/水的渗透汽化分离性能进行了总结比较,在此基础上总结了目前渗透汽化乙醇/水分离膜存在的问题,并对其未来的研究方向和发展前景进行了展望。     

高分子透过半透膜对溶液渗透压测定的影响

1.用实验证实有高分子透过半透膜时,π_(实验)=σ·π_(理论). 2.指出在透过过程中,溶质在溶液池和溶剂池内的物料平衡可能并不满足,大部分进入半透膜的高分子会停留在膜内. 3.在忽略溶质透过本身所引致的体积改变时,渗透压观察值 ?? k_s,k_p分别是半透膜对溶剂分子和高分子的透速常数. 4.高聚物试样中如无分子量极低的部分时,作者等建议可以在五至十倍于溶剂平衡所需时间的期间内观察渗透压是否随时间缓缓下降作为高分子有无透过半透膜的判据. 5.实验数据显示部分高分子透过半透膜的结果使所得??_n值偏高,A_2值偏低.     

离子交换树脂膜及其应用 Ⅰ.离子交换树脂膜

通常所谓膜就是指薄而柔软可折叠的一切天然物和人工制造的东西。根据它们在溶液里的性质可分为不透膜和半透膜二类。不透膜对于一切离子和分子都完全不能透过,这类性质的膜是很少存在。半透膜对于某些离子和分子可以透过而对于其他离子和分子完全不能或极少能透过,绝大部分的膜都是属于这类的,例如纤维素膜、羊皮纸、玻璃膜、硝化棉膜和许多动植物体内的器官表皮和细胞膜等,由于生理现象和这些膜的半透作用有密切关系,因此很早以前就对这些膜的半透性加以研究,并且应用到工业上和实验室里,例如电解净水,隔膜电解合成无机化合物等。     

聚偏氟乙烯-Nafion共混膜的制备及阻醇质子导电性能研究

直接甲醇燃料电池 (Ｄｉｒｅｃｔｍｅｔｈａｎｏｌｆｕｅｌｃｅｌｌ,ＭＤＦＣ)以高效、清洁和燃料储运方便等优点成为一类极具发展潜力的新型动力源 .但目前ＤＭＦＣ中普通使用的全氟磺酸膜 (如ＮａｆｉｏｎＴＭ 系列膜 )阻醇性能太差 ,导致大量甲醇从阳极穿过膜直接透到阴极 ,造成燃料的浪费和电池整体性能的下降 .据文献报道 ,即使甲醇浓度低到 1ｍｏｌ Ｌ ,也有近40 %的醇透过膜 .缺乏高性能的阻醇质子导电聚合物电解质膜是制约ＤＭＦＣ发展的瓶颈之一 .已有一些研究人员致力于新型膜材料的开发 ,如有人研制了聚苯并咪唑膜[1] 及各种掺杂…     

有机硅及其改性聚合物膜用于有机溶剂水溶液的渗透汽化分离

采用室温固化硅橡胶及其它三种改性硅氧烷聚合物制成渗透汽化膜,分离丙酮(A),丁酮(B)、乙醇(E)及异丙醇(P)等有机物的水溶液。结果表明,随着透过温度提高、透量成指数关系增大,但对分离系数影响甚小。透量大小顺序为A>B>E>P,分离系数大小顺序为A>B>P>E,当膜材料中(CH_3)_2SiO链节含量由70%上升到100%时,有机物的透量及分离系数同时增加。     

有机液优先透过渗透汽化膜

有机液优先透过膜作为渗透汽化膜及其相关过程的重要组成部分,近年来受到高度关注。综述了近年来有关其膜材质结构－分离特性,以及用于有机液／水分离研究的进展。     

聚1-三甲基硅基丙炔膜渗透汽化分离乙醇-水溶液的研究Ⅰ.PTMSP膜渗透汽化分离乙醇-水传质的基本特征

研究了聚１－三甲基硅基丙炔膜渗透汽化分离乙醇－水溶液传质的主要特点。发现膜对乙醇优先吸附、溶解，对水优先扩散。但因吸附液中水含量很低，总的结果表现为优先透醇。在３１３Ｋ，膜厚２０～２５μｍ，料液浓度１０ｗｔ％时，α＝１８．５，Ｊ＝０．９６９ｋｇ·ｍ－２·ｈ－１。透过膜的渗透液及其中的水和乙醇渗透汽化表观活化能分别为２８．８７、３１．３０和２７．６６ｋＪ／ｍｏｌ，并随料液浓度下降而增加。对实验数据进行非线性回归，建立了该膜传递乙醇的经验关联式：Ｊｅ＝－５．５６４Ｃ２Ｅ０＋１３．３４ＣＥ０－０．１５７３（ｋｇ·ｍ－２·ｈ－１），计算值与实验值相吻合。     

用于离子迁移率谱仪的快速热解析进样方法

热解析是用于离子迁移率谱仪(IMS)的液体和固体样品进样的重要手段,但在检测高沸点或易分解有机物时,存在易重新凝结或过热分解的问题.本研究建立了一种与IMS半透膜结合的热解析进样方法,设计了可快速加热的微型热解析装置,通过热子通电发热及热电偶测温实现对样品解析区域的升温控制,提高半透膜的进样效率.以低浓度三聚氰胺溶液为...     

A novel composite chitosan membrane for the separation of alcohol-water mixtures

A novel alcohol dehydration membrane with a three layer structure has been prepared. The top layer is a thin dense film of chitosan (CS), and the support layer is made of microporous polyacrylonitrile (PAN). Between the dense and microporous layer, there is an intermolecular cross-linking layer. This novel composite membrane has a high separation factor of more than 8000 and a good permeation rate of 0.26 kg/m² h for the pervaporation of 90 wt% ethanol aqueous solution at 60°C, 0.8 kg/m² h flux for a n-PrOH/water system and around 1 kg/m² h flux for an i-PrOH/water system using 80 wt% alcohol concentration at 60°C. The separation factor for both cases is more than 10⁵. The separation performance varies with feed composition, operating temperature and conditions of membrane preparation. The results show that the separation factor and flux of this membrane increase with raising the operating temperature. At the same time, the crosslinking layer improves durability of the composite membrane, and the pervaporation performance can be adjusted by changing the structure of the cross-linking layer. The cross section of the composite membrane has been examined by SEM.     

Pervaporation properties of novel alginate composite membranes for dehydration of organic solvents

A novel organic dehydration membrane consisting of aminated polyacrylontrile (PAN) microporous membrane as sublayer, alginate coating as top layer has been prepared and characterized by pervaporation experiment. The influence of hydrolysis and amination of the microporous support layer on selectivity and flux was studied and it was shown that amination of the sublayer improved pervaporation performance of the composite membrane greatly. The counter cation of alginate coatings as dense separating layer also influenced separation properties of the membrane, which was better for K⁺ than for Na⁺. This novel composite membrane with K⁺ as counter ion has a high separation factor of 1116 and a good permeation rate of 350 g/m² h for pervaporation of 90 wt.% ethanol aqueous solution at 70°C, higher separation factors and fluxes for n-PrOH/water, i-PrOH/water, acetone/water and dioxane/water systems. The results show that the separation factor and flux of this membrane increase with raising the operating temperature. At the same time, SEM micrographs show that the hydrolysis and amination of PAN microporous membrane change its pore structure. From the results it can be concluded that pore structure of the sublayer in addition to its chemical structure also make influence of separation properties of the composite membrane.     

具有界面交联结构藻酸钠复合膜的制备与性能

报道了一种具有界面交联结构的新型藻酸钠复合膜及其对醇水和其它有机物水体系的渗透汽化分离性能.该膜的活性层为藻酸钠,支撑层为氨化聚丙烯腈(PAN)多孔膜,在这两层之间存在着界面交联结构.研究了PAN多孔膜的水解时间、进行氨基化的二元胺种类及浓度对复合膜分离性能的影响,用己二胺进行氨基化所得到的复合膜的分离性能明显优于用乙二胺的结果.扫描电镜照片显示水解及氨基化改变了PAN超滤膜的孔结构,这也是影响新型复合膜性能的一个重要原因.     

一种新型亲水性有机-无机渗透蒸发分离膜——聚丙烯酰胺复合膜的制备

将纳米二氧化硅微孔膜用γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷处理,再通过自由基聚合接枝丙烯酰胺单体制备出一种新型的亲水性有机-无机复合膜.用TGA测定了单体在二氧化硅粉末上的接枝率;用SEM和AFM观察了接枝反应前后膜表面形态的变化;系统研究了接枝单体浓度对膜的渗透蒸发分离性能的影响.结果表明,这种膜用于醇水和丙烯酸水溶液的分离有很好的选择性和渗透性;在丙烯酰胺质量分数为3%的溶液中接枝的膜有较好的分离性;溶液浓度和操作温度对膜渗透性的影响非常特殊.     

醇／水混合液分离用聚乙烯醇复合膜的渗透汽化特性

制备了聚乙烯醇（ＰＶＡ）／聚丙烯睛（ＰＡＮ）渗透汽化复合膜，研究了交联剂用量、底膜结构、进料液组成、操作温度等因素对膜的渗透汽化性能的影响．发现ＰＶＡ／ＰＡＮ复合膜对水／醇混合液表现为水优先透过，进料液中乙醇浓度在６０～９９ｗｔ％的范围内，渗透通量Ｊｔ与温度之间符合Ａｒｒｈｅｎｉｕｓ关系，选择分离系数αＷ／Ｅ也随温度上升而增大．进料液为９５ｗｔ％的乙醇／水混合液时，７５℃下Ｊｔ高达３００～４５０ｇ／ｍ２ｈ，αＷ／Ｅ为８００～１１００．对异丙醇／水、异丁醇／水及甘油／水混合体系，复合膜显示出更为优秀的透过、分离性能．就膜的化学、物理结构与其渗透汽化性能间的关系进行了讨论．     

Pervaporation with chitosan membranes II. Blend membranes of chitosan and polyacrylic acid and comparison of homogeneous and composite membrane based on polyelectrolyte complexes of chitosan and polyacrylic acid for the separation of ethanol-water mixtures

Three different types of blend membranes based on chitosan and polyacrylic acid were prepared from homogeneous polymer solution and their performance on the pervaporation separation of water-ethanol mixtures was investigated. It was found that all membranes are highly water-selective. The temperature dependence of membrane permselectivity for the feed solutions of higher water content (>30 wt%) was unusual in that both permeability and separation factor increased with increase in temperature. This phenomenon might be explained from the aspect of activation energy and suggested that the sorption contribution to activation energy of permeation should not always be ignored when strong interaction occurs in the pervaporation membrane system.A comparison of pervaporation performance between composite and homogeneous membranes was also studied. Typical pervaporation results at 30°C for a 95 wt% ethanol aqueous solution were: for the homogeneous membrane, permeation flux = 33 g/m² h, separation factor = 2216; and for the composite membrane, permeation flux = 132 g/m² h, separation factor = 1008. A transport model consisting of dense layer and porous substrate in series was developed to describe the effect of porous substrate on pervaporation performance.     

Interfacially formed poly(N,N-dimethylaminoethyl methacrylate)/polysulfone composite membranes for CO2/N2 separation

Interfacially formed poly(N,N-dimethylaminoethyl methacrylate)/polysulfone (PDMAEMA/PSF) composite membranes were developed for CO₂/N₂ separation. A layer of PDMAEMA was deposited on a microporous PSF substrate by the solution coating technique, followed by crosslinking with p-xylylene dichloride (XDC) at the interface between the PDMAEMA solid layer and the crosslinking solution. The hydrophilicity and surface free energy of the membranes were analyzed by contact angle measurements with different probe liquids. The permselectivity of the membrane was shown to be affected by the PDMAEMA deposition time, interfacial crosslinking reaction time, and the PDMAEMA and XDC concentrations in the polymer coating solution and the crosslinking solution, respectively. The composite membrane showed a CO₂ permeance of 85 GPU and a CO₂/N₂ ideal separation factor of 50 at 23 °C and 0.41 MPa of CO₂ feed pressure.     

H2 separation using defect-free, inorganic composite membranes

Defect-free, microporous Al(2)O(3)/SAPO-34 zeolite composite membranes were prepared by coating hydrothermally grown zeolite membranes with microporous alumina using molecular layer deposition. These inorganic composite membranes are highly efficient for H(2) separation: their highest H(2)/N(2) mixture selectivity was 1040, in contrast with selectivities of 8 for SAPO-34 membranes. The composite membranes were selective for H(2) for temperatures up to at least 473 K and feed pressures up to at least 1.5 MPa; at 473 K and 1.5 MPa, the H(2)/N(2) separation selectivity was 750. The H(2)/CO(2) separation selectivity was lower than the H(2)/N(2) selectivity and decreased slightly with increasing pressure; the selectivity was 20 at 473 K and 1.5 MPa. The high H(2) selectivity resulted either because most of the pores in the Al(2)O(3) layer were slightly smaller than 0.36 nm (the kinetic diameter of N(2)) or because the Al(2)O(3) layer slightly narrowed the SAPO-34 pore entrance. These composite membranes may represent a new class of inorganic membranes for gas separation.     

Performance of Commercial and Laboratory Membranes for Recovering Bioethanol from Fermentation Broth by Thermopervaporation

A poly[1-(trimethylsilyl)-1-propyne] membrane was studied in a thermopervaporation process for ethanol recovery from fermentation media. Four commercial composite membranes based on polysiloxanes (Pervap 4060, Pervatech PDMS, PolyAn, and MDK-3) were studied for comparison. The dependences of the permeate flux, permeate concentration, separation factor, and pervaporation separation index on the temperature of the feed mixture (5 wt % ethanol in water) were obtained. The maximal values of the ethanol concentration in the permeate (35 wt %) and separation factor (10.2) were obtained for the poly[1-(trimethylsilyl)-1-propyne] membrane, whereas the PolyAn membrane provided the highest permeate flux (5.4 kg m^–2 h^–1). The ethanol/ water separation factor for the systems studied has a maximum at 60°С; this temperature of the feed mixture is optimum for recovering ethanol from aqueous media by thermopervaporation. The existing membranes based on polysiloxanes show low ethanol–water selectivity (less than 1). Poly[1-(trimethylsilyl)-1-propyne] membranes are the most promising for recovering bioethanol from fermentation mixtures by thermopervaporation, because they showed the highest selectivity to ethanol.     

SEPARATION OF PROPANE FROM PROPANE/NITROGEN MIXTURES USING PDMS COMPOSITE MEMBRANES BY VAPOUR PERMEATION

 This study deals with polydimethylsiloxane (PDMS)/polyvinylidene fluoride (PVDF) composite membranes for propane separation from propane/nitrogen mixtures, which is relevant to the recovery of propane in petroleum and chemical industry. The surface and cross-section morphology of PDMS/PVDF composite membranes was observed by scanning electron microscope (SEM). The surface morphology of PDMS/PVDF composite membranes is very dense. There are three layers, the thin dense top layer, finger-like porous middle layer and sponge-like under layer in the cross-section SEM image of PDMS/PVDF composite membranes. The effects of the types of cross-linking agents and pressure on the membrane permselectivity were investigated. The permeability of nitrogen was independent of feed pressure. However, the permeability of propane increased with the pressure increasing for all membranes. The membrane cured by a tri-functional crosslinker with attached vinyl groups had better performance than the tetra-functional one, in both selectivity and permeation flux. The total permeation flux is 1.769× 10^-2 cm³(STP)/(cm²·s) and the separation factor is 19.17 when the mole percent of propane in the gas mixture is 10 at the 0.2 MPa pressure difference and 25°C.