Synthesis and characterization of new highly selective polyaryloxyphosphazene-polysiloxane crosslinked copolymer films. Application to the extraction of organic compounds from water by pervaporation

A series of polyaryloxyphosphazene/polydimethylsiloxane (PABMP/PDMS) crosslinked copolymer films containing various PDMS contents were prepared by platinum-catalyzed hydrosilylation reaction. The physical morphology of these membranes was characterized by IR, DSC and transmission electron microscopy. Their transport properties were studied by pervaporation of saturated ethyl acetate aqueous solutions at 30°C. Each copolymer film led to preferential permeation of ethyl acetate. Moreover, selectivity and flux proved to be higher than a PABMP membrane, increasing with the PDMS content up to a 70 wt% value. At the maximum point, an aqueous solution of 7 wt% ethyl acetate was concentrated to 97 wt% with a normalized permeation flux of 25 kg/m².h.     

Recent advances in sodium alginate-based membranes for dehydration of aqueous ethanol through pervaporation

Sodium alginate (SA) is a progressive material for membrane fabrication. The technological development of SA-based membranes has made a significant contribution to the separation techniques, especially in aqueous organic solutions. The outstanding performance of SA is attributed to its outstanding structural flexibility and hydrophilicity. In view of structural characteristics, SA membranes have immense utilization in the pervaporation separation of organics. Among various organics, dehydration of aqueous ethanol is employed as a standard to check the success of pervaporation (PV) membrane. Because ethanol and water have comparable molecular sizes, thus difficult to extract water from aqueous ethanol mixtures than it is for other organics. A literature survey shows that wide-ranging data are available on the PV performance of SA and its modified membranes. In this context, the present review addresses the recent advances made in SA membranes for enhanced ethanol dehydration performance during the last decade. Available data since 2010 has been compiled for grafted, crosslinked, blend, mixed matrix, and composite hybrid sodium alginate membranes in terms of separation factor, permeation flux, and pervaporation separation index PSI. The data are assessed with reference to the effect of feed composition, membrane selectivity, flux, and swelling behavior.     

Permselectivity, solubility and diffusivity of propyl propionate/water mixtures in poly(ether block amide) membranes

This work is concerned with the separation of propyl propionate/water mixtures by pervaporation using PEBA membranes, which is relevant to aroma compound recovery from dilute aqueous solutions. The solubility and diffusivity pertinent to the permselectivity were investigated. The effects of feed concentration and the operating temperature on the separation performance were studied. Under the experimental conditions tested, the permeate concentration was much higher than the solubility limit, and upon phase separation substantially pure propyl propionate could be achieved. The diffusivity of propyl propionate through the membrane from its dilute aqueous solutions was affected by the solution concentration exponentially. It was shown that the permselectivity of the membrane for propyl propionate/water separation was mainly derived from its sorption selectivity due to the organophilicity of the membrane. The diffusivity of pure propyl propionate in the membrane was about 28 times higher than pure water diffusivity.     

Enhanced Pervaporation Performance of Multi-layer PDMS/PVDF Composite Membrane for Ethanol Recovery from Aqueous Solution

Multi-layer PDMS/PVDF composite membrane with an alternative PDMS/PVDF/non-woven-fiber/PVDF/PDMS configuration was prepared in this paper. The porous PVDF substrate was obtained by casting PVDF solution on both sides of non-woven fiber with immersion precipitation phase inversion method. Polydimethylsiloxane (PDMS) was then cured by phenyltrimethoxylsilane (PTMOS) and coated onto the surface of porous PVDF substrate one layer by the other to obtain multi-layer PDMS/PVDF composite membrane. The multi-layer composite membrane was used for ethanol recovery from aqueous solution by pervaporation, and exhibited enhanced separation performance compared with one side PDMS/PVDF composite membranes, especially in the low ethanol concentration range. The maximum separation factor of multi-layer PDMS/PVDF composite membrane was obtained at 60 °C, and the total flux increased exponentially along with the increase of temperature. The composite membrane gave the best pervaporation performance with a separation factor of 15, permeation rate of 450 g/m²h with a 5 wt.% ethanol concentration at 60 °C.     

主链含杯[4]芳烃的PBT-PDMS共聚酯的合成及其对水中微量苯的分离性能研究

合成了双官能化杯[4]芳烃衍生物,并通过共缩聚的方法制备了主链含杯[4]芳烃的聚对苯二甲酸丁二酯-聚二甲基硅氧烷(PBT-PDMS)共聚酯.利用1H-NMR,FTIR,SEC等手段表征了共聚物的组成及分子量.以此共聚物为膜材料,通过刮膜法制备了可用于渗透汽化的致密无孔分离膜,并用SEM表征了无孔膜的膜厚及截面结构.研究了温度和原始液浓度对渗透汽化的影响.该共聚物渗透气化膜分离水中微量苯的分离因子可达491,通量为58g/(m2h).     

Pervaporation performance of crosslinked polydimethylsiloxane membranes for deep desulfurization of FCC gasoline: I. Effect of different sulfur species

Crosslinked PDMS/PEI composite membranes were prepared, in which asymmetric 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 FTIR. The surface and section of PDMS/PEI composite membranes were investigated by scanning electron microscope (SEM). The infinite dilute activity and diffusion coefficients of thiophene, 2-methyl thiophene, 2,5-dimethyl thiophene, n-butyl mercaptan, n-butyl sulfide in crosslinked PDMS were measured in the temperature range of 80–100 °C by inverse gas chromatography. The solubility parameters of thiophene, 2-methyl thiophene, 2,5-dimethyl thiophene, n-butyl mercaptan, n-butyl sulfide were calculated by the group contribution method and the selectivity of PDMS composite membrane for different organic sulfur compounds was investigated. The composite membranes prepared in this work were employed in pervaporation separation of n-heptane and different sulfur forms mixtures. The theoretical results showed good agreement with the experimental results, and the order of partial permeate flux and selectivity for different organic sulfur compounds was: thiophene > 2-methylthiophene > 2,5-dimethylthiophene > n-butyl mercaptan > n-butyl sulfide, which should be significant for practical application.     

Sorption and pervaporation of dilute aqueous solutions of organic compounds through polymer membranes

Pervaporation of dilute aqueous binary mixtures of four organic compounds (benzene, chloroform, acetone and ethanol) through nitrile—butadiene and styrene—butadiene copolymers was investigated. A pervaporation device has been built, which allows measurement of the pervaporation flux and selectivity of a membrane as a function of the upstream composition of the feed and the downstream total pressure of the pervaporate. In order to relate pervaporation results to equilibrium properties of the membranes, the sorption of water and dilute aqueous solutions was mainly investigated. The pervaporation of dilute aqueous solutions of benzene and chloroform has been extensively studied, including the separation of traces of chloroform, and is modelled through a “sixcoefficients exponential model” [1]. This model is derived from a solution—diffusion analysis of the selective transfer, assuming an exponential dependence of both diffusivities on concentrations of both permeants. Semi-quantitative information about the potential interactions existing in the system solute i—solvent j—membrane and about the concentration profiles at steady-state may be derived from these coefficients.     

Recovery of pyridine from aqueous solution by membrane pervaporation

Three different membranes, based on poly(dimethylsiloxane) (PDMS), cation-exchange material and poly(vinyl alcohol) (PVA) respectively, were tudied for the separation of pyridine-water mixtures by pervaporation. The PDMS membrane was preferentially permeable to pyridine and the other two were selective towards water. Three membranes showed different permeation performance, allowing the application of the technique to the separation of feeds of different composition. The temperature profile of the permeability suggests that it is possible to carry out the operation at an elevated temperature in order to achieve high productivity. A combination of the three types of membranes was designed for the production of anhydrous pyridine from dilute pyridine aqueous solution by pervaporation.     

Multilayered poly(vinylidene fluoride) composite membranes with improved interfacial compatibility: correlating pervaporation performance with free volume properties

A spin-coating process integrated with an ozone-induced graft polymerization technique was applied in this study. The purpose was to improve the poor interfacial compatibility between a selective layer of poly(2-hydroxyethyl methacrylate) (PHEMA) and the surface of a poly(vinylidene fluoride) (PVDF) substrate. The composite membranes thus fabricated were tested for their pervaporation performance in dehydrating an ethyl acetate/water mixture. Furthermore, the composite membranes were characterized by field emission scanning electron microscopy (FE-SEM) for morphological change observation and by Fourier transform infrared spectroscopy equipped with attenuated total reflectance (ATR-FTIR) for surface chemical composition analysis. Effects of grafting density and spin-coating speed on pervaporation performance were examined. The composite membrane pervaporation performance was elucidated by means of free volume and depth profile data obtained with the use of a variable monoenergy slow positron beam (VMSPB). Results indicated that a smaller free volume was correlated with a higher pervaporation performance of a composite membrane consisting of a selective layer of spin-coated PHEMA on a PHEMA-grafted PVDF substrate (S-PHEMA/PHEMA-g-PVDF). The composite membrane depth profile illustrated that an S-PHEMA layer spin-coated at a higher revolutions per minute (rpm) was thinner and denser than that at a lower rpm.     

Effect of the permeants/polymer interactions on the pervaporative separation properties of the P(VDF-co-HFP) membrane

In this paper, the acetone-cast poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-co-HFP)) membranes were prepared by isothermally vacuum-dried at 60 °C and were employed in pervaporation of methyl acetate (MeAc) or ethyl acetate (EtAc) dissolved water solutions. DSC study on the swelling process indicated that two states of both MeAc and EtAc in their swollen P(VDF-co-HFP) membranes might exist which were the ‘bound state’ and ‘bulk state’. In addition, relative to the pure EtAc, the pure MeAc had stronger interaction with the P(VDF-co-HFP) membrane, making for its higher solubility in and lower diffusivity through the membrane. However, there is a competition between the organic permeants/water interactions and the organic permeants/polymer interactions when the P(VDF-co-HFP) membrane was tested for its pervaporative separating properties. With respect to MeAc in its water mixtures, EtAc in its water mixtures had higher solubility in the membrane instead because of its weaker interaction with water. As a result, better separating properties (higher permeate flux and separation factor) when the P(VDF-co-HFP) membrane was in pervaporation of the EtAc/water mixtures were obtained.     

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.     

PERVAPORATION OF ETHANOL/WATER MIXTURES WITH HIGH FLUX BY ZEOLITE-FILLED PDMS/PVDF COMPOSITE MEMBRANES

Thin-film zeolite-filled silicone/PVDF composite membranes were fabricated by incorporating zeolite particles into PDMS(poly(dimethylsiloxane)) membranes.The morphology of zeolite particles and zeolite filled silicone composite membranes were characterized by SEM.The zeolite-filled PDMS/PVDF composite membranes were applied for the pervaporation of ethanol/water mixtures and showed higher flux compared with that reported in literatures.The effect of zeolite loading and Si/Al ratio of zeolite particles on...     

Separation of aqueous organic mixtures by pervaporation and analysis by mass spectrometry or a coupled gas chromatograph—mass spectrometer

A method of analysis has been developed based on the use of selective membranes which gives the possibility of enriching, identifying and quickly analysing organic volatile compounds in dilute aqueous solution. The process used to separate water from organic products is pervaporation. p]One side of the selective membrane is in contact with the liquid mixture. The other side of the membrane, under vacuum, is directly connected with the ionization source of a mass spectrometer which analyses quantitatively and qualitatively the organic compounds in proportion as they pass through the membrane. p]A number of different pervaporation membranes were studied and the selectivity of the membranes to different aqueous mixtures has been measured. Four types of analytical applications are described.     

The Ultrafast and Continuous Fabrication of a Polydimethylsiloxane Membrane by Ultraviolet‐Induced Polymerization

The polydimethylsiloxane (PDMS) membrane commonly used for separation of biobutanol from fermentation broth fails to meet demand owing to its discontinuous and polluting thermal fabrication. Now, an UV‐induced polymerization strategy is proposed to realize the ultrafast and continuous fabrication of the PDMS membrane. UV‐crosslinking of synthesized methacrylate‐functionalized PDMS (MA‐PDMS) is complete within 30 s. The crosslinking rate is three orders of magnitude larger than the conventional thermal crosslinking. The MA‐PDMS membrane shows a versatile potential for liquid and gas separations, especially featuring an excellent pervaporation performance for n‐butanol. Filler aggregation, the major bottleneck for the development of high‐performance mixed matrix membranes (MMMs), is overcome, because the UV polymerization strategy demonstrates a freezing effect towards fillers in polymer, resulting in an extremely high‐loading silicalite‐1/MA‐PDMS MMM with uniform particle distribution.     

Pervaporation dehydration of isopropanol with chitosan membranes

Homogeneous and composite chitosan based membranes were prepared by the solution casting technique. The membranes were investigated for the pervaporation dehydration of isopropanol-water systems. The effects of feed concentration and temperature on the separation performance of the membranes were studied. In terms of the pervaporation separation index (PSI), the composite membrane was more productive than the homogeneous membrane for pervaporation of feed with high isopropanol content. It was observed that permeation increased and the separation factor decreased with the temperature. Modification of the homogeneous chitosan membrane by chemical crosslinking with hexamethylene diisocyanate improved the permselectivity but reduced the permeation rate of the membrane.     

Influence of sorption and diffusion of aroma compounds in silicone rubber on their extraction by pervaporation

Pervaporation was used to extract aroma compounds from dilute aqueous solutions. The use of a stirred cell allowed the reduction of the boundary layer effect which can be estimated using a mass transfer correlation. A resistance-in-series model was used to describe the flux of organic compounds through a silicone membrane. Calculation of the membrane resistance required the determination of the solubility and diffusion coefficients of the aroma substances in the polymer. These two characteristics were obtained by measuring the quantities of the aroma sorbed on the silicone at equilibrium and by studying the kinetics of sorption. At low concentration ranges, both characteristics were constant. They can be related to the hydrophobicity, the molar volume and the flux of the substances through the silicone membrane during pervaporation.     

Sorption Isotherms of Aromatic Compounds in Organophilic Polymer Membranes Used in Pervaporation

The sorption isotherms of seven aromatic compounds and some mixtures of them in soft-segment elastomeric polyether-polyamide block-copolymer (PEBA) have been measured at 25 and 50°C using UV-VIS spectroscopic and gas chromatographic analysis. The solubility in PEBA depends significantly on the molecular size of the aromatic compound. Sorption coefficients have been determined. The temperature dependence of the sorption coefficient has been used to determine also the sorption enthalpy of the aromatic compounds from the aqueous solution to the polymer phase. Ternary mixtures consisting of two aromatics in dilute aqueous solution have been investigated in order to study possible synergistic solubility effects. The sorption coefficients can be used for the prediction of the permeation rate across the nonporous PEBA membrane in the so-called pervaporation process. An example is presented.     

Preparation and characterization of a composite PDMS membrane on CA support

Polydimethylsiloxane (PDMS) is the most commonly used membrane material for the separation of condensable vapors from lighter gases. In this study, a composite PDMS membrane was prepared and its gas permeation properties were investigated at various upstream pressures. A microporous cellulose acetate (CA) support was initially prepared and characterized. Then, PDMS solution, containing crosslinker and catalyst, was cast over the support. Sorption and permeation of C₃H₈, CO₂, CH₄, and H₂ in the prepared composite membrane were measured. Using sorption and permeation data of gases, diffusion coefficients were calculated based on solution‐diffusion mechanism. Similar to other rubbery membranes, the prepared PDMS membrane advantageously exhibited less resistance to permeation of heavier gases, such as C₃H₈, compared to the lighter ones, such as CO₂, CH₄, and H₂. This result was attributed to the very high solubility of larger gas molecules in the hydrocarbon‐based PDMS membrane in spite of their lower diffusion coefficients relative to smaller molecules. Increasing feed pressure increased permeability, solubility, and diffusion coefficients of the heavier gases while decreased those of the lighter ones. At constant temperature (25°C), empirical linear relations were proposed for permeability, solubility, and diffusion coefficients as a function of transmembrane pressure. C₃H₈/gas solubility, diffusivity, and overall selectivities were found to increase with increasing feed pressure. Ideal selectivity values of 9, 30, and 82 for C₃H₈ over CO₂, CH₄, and H₂, respectively, at an upstream pressure of 8 atm, confirmed the outstanding separation performance of the prepared membrane. Copyright © 2009 John Wiley & Sons, Ltd.     

One-step fabrication of hydrophilic lignosulfonate-decorated reduced graphene oxide to enhance the pervaporation performance of calcium alginate membranes

In this study, a reduced graphene oxide (rGO)@sodium lignosulfonate (NaLS) composite material was fabtricated using a one-step method and then mixed with natural polysaccharide calcium alginate (CaAlg) to prepare the rGO@NaLS/CaAlg pervaporation membrane. The appearance and physical properties of the rGO@NaLS/CaAlg membrane were characterized by scanning electron microscopy and water contact angle. The swelling performance of the membrane and its dehydration performance to organic solvents were evaluated. The results indicate that the addition of rGO@NaLS can increase the hydrophilicity of the rGO@NaLS/CaAlg membrane and reduce its degree of swelling in the ethanol solution. The membrane incorporated with 6 wt% rGO@NaLS exhibits the best pervaporation performance, and ethanol can be purified to 99.8%.     

Deep desalination of water by evaporation through polymeric membranes

Transport properties and structural features of a number of already known and new types of polymeric membranes in desalination of aqueous salt solutions by membrane distillation and pervaporation were studied. The possibility of obtaining distilled water in a single stage by pervaporation from dilute or concentrated aqueous salt solutions was examined for the example of membranes fabricated from celluloses of varied origin (wood, cotton, bacterial).