Regulatable pervaporation performance of Zn-MOFs/polydimethylsiloxane mixed matrix pervaporation membranes

Pervaporation (PV) is an emerging separation technique for liquid mixture. Mixed matrix membranes (MMMs) often demonstrate trade-off relationship between separation factor and flux. In this study, by changing the organic linkers (2-methyl imidazolate, imidazole-2-carboxaldehyde, 2-ethyl imidazolate), ZIF-8, ZIF-90 and MAF-6 were prepared and filled in polydimethylsiloxane (PDMS) membranes for dealcoholization of 5% (mass) n-butanol solution, and the membranes properties and pervaporation performances were adjusted. Compared with the pure PDMS membrane, the addition of ZIF-8 resulted in a 9% increase in flux (1136 g·m^-2·h^-1) and a 22.5% increase in separation factor (28.3), displaying anti-trade-off effect. For the MAF-6/PDMS MMMs (2.0% mass loading), the pervaporation separation index (PSI) and separation factor were 32347 g·m^-2·h^-1 and 58.6 respectively (increased by 34% and 154% in contrast with that of the pure PDMS membrane), and the corresponding permeation flux was 552 g·m^-2·h^-1, presenting great potential in the removal butanol from water. It was deduced that the large aperture size combined with moderate hydrophobicity of metal-organic frameworks (MOFs) favor the concurrent increase in permeability and selectivity.     

Preparation of polydimethylsiloxane/polystyrene interpenetrating polymer network membranes and permeation of aqueous ethanol solutions through the membranes by pervaporation

Polydimethylsiloxane (PDMS)/polystyrene (PSt) interpenetrating polymer network (IPN) membranes were prepared by the bulk copolymerization of styrene and divinylbenzene in the PDMS networks. The interpenetration of PDMS and PSt resulted in the improvement of mechanical properties of PDMS. Transmission electron microscope (TEM) observation demonstrated that the PDMS/PSt IPN membranes have microphase-separated structures consisting of a continuous PDMS phase and a discontinuous PSt phase. When an aqueous ethanol solution was permeated through the PDMS/PSt IPN membranes by pervaporation, the PDMS/PSt IPN membranes exhibited ethanol permselectivity, regardless of the PDMS content. The effects of their microphase-separated structures on the permeability and selectivity for aqueous ethanol solutions are discussed experimentally and theoretically. © 1996 John Wiley & Sons, Inc.     

聚二甲基硅氧烷的改性技术及其渗透汽化性能的影响因素

介绍了聚二甲基硅氧烷(PDMS)的改性技术,总结了不同改性方法在渗透汽化中的应用,分析了影响PDMs膜渗透汽化性能的影响因素,指出了PDMs膜存在的问题及其发展方向.     

全硅沸石/聚二甲基硅氧烷渗透汽化膜制备及分离性能

考察了全硅沸石/聚二甲基硅氧烷(PDMS)渗透汽化均质膜制膜液中国液比(质量比)对渗透汽化膜性能的影响,利用均匀设计优化方法对交联时间、交联温度、全硅沸石填充鼍和PDMS中b胶量等对膜分离因子的影响进行了研究,制备了对丁醇分离性能较高的渗透汽化均质膜.50℃下,分离原料液质量分数为1.6%的丙酮-丁醇-乙醇-水溶液时,...     

Study of crosslinking density in polydimethylsiloxane networks by DSC

A calorimetric study for estimating crosslinking densities of polydimethylsiloxane (PDMS) networks is presented. It involves the experimental determination of the heat capacities of the polymer with (C) and without (C) crosslinking. The theoretical basis of the method is described as well as the procedure used for the determination of the C_ps. The crosslinking densities of PDMS networks, determined by absorbency (swelling) measurments, using the Flory-Rehner equation, and by the method described here, are compared. The PDMS, obtained by the anionic synthesis of octamethylcyclotetrasiloxane, was analyzed by gel permeation chromatography and infrared spectroscopy. Separate samples of the polymer were further crosslinked at different network densities. The C_ps and the thermal stabilities were determined by DSC and TGA, respectively. The results indicate that the crosslinking density ratios of the polymer networks calculated by the relation ΔC/C are in reasonable agreement with those obtained from absorbency measurements. The crosslinking density can also be obtained from heat capacity measurments if the density of the network is known at the temperature that ΔC_p is obtained. © 1995 John Wiley & Sons, Inc.     

TS‐1 molecular sieves filled polydimethylsiloxane membranes for ethanol/water separation via pervaporation

TS‐1 molecular sieves were synthesized and characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, and UV–Vis spectroscopy. Results showed that the morphology, crystallinity, and purity of TS‐1 were closely related to the Ti/Si ratio, crystallization time, crystallization temperature, and calcination time. The TS‐1 particles were incorporated into polydimethylsiloxane to form mixed matrix membranes (MMMs), and these MMMs were first used to separate ethanol/water mixtures via pervaporation. The MMMs with 50 wt% TS‐1 (Ti/Si ratio of 0.02) loading showed the highest separation factor of 14.1 for 5 wt% ethanol feed concentration at 50°C. POLYM. ENG. SCI., 56:583–589, 2016. © 2016 Society of Plastics Engineers     

Tunable physicochemical properties of PVA nanocomposite membranes for enhanced pervaporation performance

This study reveals the effect of hydrophilic bentonite nanoclay on the pervaporation separation of azeotropic composition of water and 1,4‐dioxane. The permselectivity of the membrane increased with filler concentration and was selective toward water at minimum filler loading. The intrinsic properties such as membrane permeance and selectivity increased with the concentration of hydrophilic bentonite nanoclay and crosslinked poly(vinyl alcohol) (PVA) with 2 wt% nanoclay membranes showed intrinsic selectivity 443 (532% increment than that of pristine membranes) with water permeance 4,675 gas permeation unit which is significantly higher compared to earlier literature. X‐ray diffraction and Transmission electron microscopy showed the well exfoliated and distributed nanoclay structure in the crosslinked PVA matrix. Interaction of PVA with nanoclay and the hydrophilic character of the membranes were characterized by Fourier transform infrared spectra and contact angle analysis, respectively. Interestingly, in this work the membranes exhibited simultaneous increment in both permeation flux and selectivity with filler loading, rather than the usual inverse trend of flux and selectivity. A predictive model of pervaporation was used to explain the pervaporation behavior and it showed good agreement with experimental results for overall pervaporation performance, preferential sorption of water, and hydrophilic‐hydrophobic nature of the membranes. POLYM. ENG. SCI., 58:849–858, 2018. © 2017 Society of Plastics Engineers     

Modified ZSM‐5/polydimethylsiloxane mixed matrix membranes for ethanol/water separation via pervaporation

In this article, chlorosilane‐modified ZSM‐5 particles were incorporated into polydimethylsiloxane (PDMS) to form mixed matrix membranes (MMMs) for ethanol/water mixture separation via pervaporation (PV). The membranes were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, and mechanical performance testing. The maximum loading and dispersion of ZSM‐5 into PDMS were improved by chlorosilane modification. To evaluate the PV performance, the MMMs were used to separate an aqueous ethanol solution. The effect of zeolite loading and operational conditions on PV performance was investigated in detail. The separation factor of the composite membranes filled with modified ZSM‐5 increased considerably versus unmodified membrane, while the total flux decreased to some degree. Of all the chlorosilane‐modified membranes, dodecyltrichlorosilane modified ZSM‐5 filled PDMS showed the best separation factor of 15.8 for ethanol. POLYM. COMPOS., 37:1282–1291, 2016. © 2014 Society of Plastics Engineers     

偶联剂对纳米二氧化硅/PDMS复合膜渗透汽化性能影响的研究

用3种硅烷偶联剂3-氨丙基三乙氧基硅烷(AMES)、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(MEMS)、十六烷基三甲氧基硅烷(HEMS)分别对纳米二氧化硅粒子进行改性,利用制备的改性粒子与PDMS制备了一系列平板复合渗透汽化分离膜,用于乙醇/水溶液分离.实验结果表明:复合膜的渗透汽化性能得到显著的提高.3种改性粒子在提高渗透通量方面:HEMS＞MEMS＞ AMES;在提高分离因子方面,MEMS与AMES对复合膜的影响十分接近,而HEMS远小于前两者.当MEMS改性二氧化硅的质量分数为4％时,在40℃质量分数为10％的乙醇/水溶液中,复合膜的分离因子达到最高值11.17,渗透通量为216.1g/(m2 ·h).     

新型侧链型聚酰亚胺膜的制备及其渗透汽化分离性能

针对苯/环己烷混合物体系的特点,采用两种新型侧链二胺3,5-二氨基苯甲酸苯酯(PDA)和3,5-二氨基苯甲酸-4-三氟甲基苯酯(FPDA),制备了一系列由不同二酐与二胺单体如4,4'-二氨基二苯醚(ODA)和3,5-二氨基苯甲酸(DABA)聚合而成的用于渗透汽化分离苯/环己烷的聚酰亚胺膜,对其结构和各项性质进行了表征,并对膜材料的微观结构与宏观分离性能之间的关系进行了较为深入的研究。随着侧链二胺的引入,聚酰亚胺膜的分离效率随之持续增大,分离能力得以改善。渗透汽化实验结果表明,以6FDA为二酐单体的两类聚酰亚胺膜具有较优异的分离性能。乙二醇交联的6FDA-FPDA/ODA/DABA(1:7:2)膜综合渗透汽化分离性能最优。在50℃时,对于含苯50 %(质量)的苯/环己烷混合物,其渗透通量为9.84 kg·μm·m^-2·h^-1,分离因子达6.1。     

Pervaporation performance of polydimethylsiloxane membranes for separation of benzene/cyclohexane mixtures

Crosslinked polydimethylsiloxane/polyetherimide (PDMS/PEI) composite membranes were prepared, in which asymmetric microporous PEI membrane prepared with phase inversion method was acted as the microporous supporting layer in the flat‐plate composite membrane. The different function composition of the PDMS/PEI composite membranes were characterized by reflection Fourier transform infrared (FTIR) spectroscopy. The surface and section of PDMS/PEI composite membranes were investigated by scanning electron microscope (SEM). The composite membranes prepared in this work were employed in pervaporation separation of benzene/cyclohexane mixtures. Effects of feed temperature, feed composition, concentration of crosslinking agent on the separation efficiency of benzene/cyclohexane mixtures were investigated experimentally. In addition, the swelling rate and stableness of composite membrane during long time operation were studied, which should be significant for practical application. The results demonstrated that the pervaporation method could be very effective for separation of the benzene/cyclohexane mixtures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Sorption behavior and preliminary pervaporation results of cross-linked polyvinylalcohol and polydimethylsiloxane membranes prepared for the separation of water-ethylacetate mixtures

Since pervaporation process is the coupling of solution and diffusion mechanisms, a sorption study was carried out with membranes prepared by cross-linking polyvinylalcohol (PVA) and polidimethylsiloxane (PDMS). Tartaric acid (Tac) was used as the cross-linking agent for PVA, and a commercial cross-linking agent was used for PDMS. Sorption experiments were carried out at 30-50°C temperature range in pure water and ethyl acetate using the films prepared. The PVA and PDMS films prepared preferentially sorb water and ethylacetate, respectively. A pervaporation study at 30°C was carried out for pure ethylacetate and pure water, and mixtures of ethylacetate containing 2 and 2.5 wt% water using 100 w m thick PVA membrane. The results indicate that the PVA membrane prepared is extremely selective for water.     

Separation of aqueous phenol through polyurethane membranes by pervaporation

The separation of a phenol-water mixture using a polyurethane membrane by a pervaporation method was investigated. Polyurethane was selected as a membrane material because its affinity for phenol was considered to be high. Polyurethane was prepared by the polyaddition of 1,6-diisocyanatohexane and polytetramethyleneglycol. The polyurethane layer was sandwiched with a porous polypropylene membrane (Celgard® 2500). Pervaporation measurement was carried out under vacuum on the permeate side, and the permeate vapor was collected with a liquid nitrogen trap. The phenol concentration in the permeate solution increased from 0 to 65 wt % with increasing feed concentration of phenol from 0 to 7 wt %. The total flux also increased up to 930 g m^-2 h^-1 with increasing phenol partial flux. In the sorption measurement at 60°C, the concentration of phenol in the membrane was 68 wt %, which was higher than that of the permeate solution. Therefore, it was considered that the phenol selectivity was based on high solubility in the polyurethane membranes. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:469–479, 1997     

Pervaporation via silicon-based membranes: Correlation and prediction of performance in pervaporation and gas permeation

Pervaporation (PV) is a membrane technology that holds great promise for industrial applications. To better understand the PV mechanism, PV dehydrations of various types of organic solvents (methanol, ethanol, iso-propanol, tert-butanol, and acetone) were performed on five types of organosilica and two types of silicon carbide-based membranes, all with different pore sizes. Water permeance was dependent on the types of organic aqueous solutions, which suggested that organic solvents penetrated the pores and hindered the permeation of water. In addition, water permeance of various types of membranes in PV was well correlated with hydrogen permeance in single-gas permeation. Furthermore, a clear correlation was obtained between the permeance ratio in PV and that in single-gas permeation, which was confirmed via the modified-gas translation model. These correlations make it possible to use single-gas permeation properties to predict PV performance.     

Crosslinked chitosan membranes: characterization and study of dimethylhydrazine dehydration by pervaporation

Crosslinked chitosan membranes were synthesized using glutaraldehyde and characterized by infra‐red (IR) and wide‐angle X‐ray diffraction (WAXD) spectroscopic methods. The membranes were applied for the pervaporation‐based dehydration of the highly hazardous and hypergolic unsymmetrical dimethylhydrazine liquid propellant. The characterization techniques were an efficient tool in identifying polymer–liquid interaction sites and the separation mechanisms involved. The crosslinked polymer was found to have good potential for the separation of the aqueous azeotrope of the propellant (20 wt%) and its enrichment to >90% purity. An equilibrium sorption study examined the preferential affinity of the membrane amongst the two penetrating liquids. The pervaporation performance of the membrane was evaluated by varying the experimental parameters of feed composition, membrane thickness and permeate pressure, and found to be promising. © 2001 Society of Chemical Industry     

支撑层对硅橡胶复合膜渗透汽化分离性能的影响

引言 为了扩大渗透汽化技术的应用领域,科研工作者需要进一步增强渗透汽化膜的分离性能.从工业化的观点而言,用于实际应用的渗透汽化膜大多是复合膜,它由选择层(或分离层)和支撑层组成.一般认为,选择层决定着复合膜的选择性和通量,支撑层起支撑和机械稳定作用.Nijhuis[1]在从甲苯-水体系中分离甲苯的过程中对均质膜和以聚砜为支撑层的复合膜的分离性能进行了比较;Sturken[2]分别用聚醚酰亚胺和聚偏氟乙烯为支撑层的硅橡胶膜从二氯乙烷-水体系中提取二氯乙烷,他们得到了相同的结论:支撑层的影响可以忽略.然而Scholz[3],Heinzelmann[4],Rautenbach[5],Borges[6],Vankelecom[7],Farooq[8],Lipnizki[9]等均在各自研究中发现,由于基膜和分离层的物理化学性质以及制膜方法等众多因素的存在使得支撑层在一定程度上影响复合膜的分离性能;Feng[10]对均质硅橡胶膜和有微孔支撑层的硅橡胶复合膜的分离性能进行了比较,发现均质硅橡胶膜优先透过异丙醇,而有微孔亲水性支撑层的硅橡胶复合膜则优先透过水,这表明在一定的情况下,支撑层甚至起主导作用并能够决定复合膜的分离性能.因此,通过系统研究以不同多孔材料为支撑层的复合膜对有机物-水溶液的分离性能的影响,能够找到最优的复合膜支撑层,从而能够提高复合膜的分离性能.然而,至今关于支撑层对渗透汽化膜分离性能影响的系统研究仍相当少.     

Enhancing the separation performance by introducing bioadhesive bonding layer in composite pervaporation membranes for ethanol dehydration

A high performance composite membrane was prepared under the inspiration of bioadhesion principles for pervaporative dehydration of ethanol. Chitosan (CS) and polyacrylonitrile (PAN) ultrafiltration me...     

无机盐对聚二甲基硅氧烷/陶瓷复合膜渗透汽化性能的影响

将渗透汽化应用于醇/水体系的分离,具有诸多显著的优势。然而,目前的研究大都基于二元体系,而实际的应用体系是多元的,还包含少量无机盐和糖类等,它们的存在对膜的性能具有一定的影响。本文研究了NaCl、KCl和MgCl2 3种无机盐的加入对聚二甲基硅氧烷 （PDMS）/陶瓷复合膜渗透汽化性能的影响。结果表明,在313 K,无机盐的加入使复合膜的分离因子和通量均有所提高。其中二价盐MgCl2对渗透汽化性能的影响最为显著,分离因子最大提高到醇/水体系的2.8倍。而一价盐NaCl和KCl的加入,使分离因子分别提高为醇/水体系的2.5倍和2.4倍。同时借助于Setschenow扩展方程计算了乙醇活度,对实验结果进行了初步的解释。     

Hydrophilic membranes for pervaporation: An analytical review

An analytical review has been attempted on the issues encountered in selecting polymers for hydrophilic pervaporation (PV) membranes. It is well known that permselectivity is determined by selective sorption and by selective diffusion. Selective sorption is governed by the presence of the active centers in the polymer which are capable of specific interactions with water. The analysis of the influences of the type of interactions of water-active centers of the polymer on the membrane performances are presented. Selective diffusion is governed by the rigidity and the regularity of the polymer structure and also by the constructure of the polymer's interspace. There is a net of bonds and crosslinks in the polymer due to existence of inter- and intramolecular interactions in it. This net is responsible for the stability of the mass transfer properties of the polymer to the feed water. The influences of the degree of swelling and frequencies of the crosslinks in the polymer are analysed. The main role of the selective diffusion in the selective permeation is demonstrated. The possibility of the existence of two different channels (hydrophilic and hydrophobic) for the permeation of water and organics is discussed, and it has been concluded that there are two different channels for friable polymers which have fragments with not so strong inter- and intra-molecular interactions. But in the polymers with strong inter- and intra-molecular interactions and a narrow net of these bonds (e.g., polyelectrolyte complexes), the hydrophobic channels are strongly collapsed. They can be opened only by water at its high feed concentrations. It was concluded that one of the most prospective ways to create highly permeative and highly selective materials for dehydration of organics by PV is using polyelectrolyte complexes (especially for the separation of water with organic molecules, which have more than three carbon atoms in total).