硅橡胶复合膜渗透汽化分离硫/汽油混合物

Worldwide environment has resulted in a limit on the sulfur content of gasoline. It is urgent to investigate the desulfurization of gasoline. The polydimethylsiloxane (PDMS)/polyetherimide (PEI) composite membranes were prepared by casting a PDMS solution onto porous PEI substrates and characterized by scanning electron microscope (SEM). The membranes were used for sulfur removal from gasoline by pervaporation. The effects of feed temperature, sulfur content in the feed and PDMS layer thickness on membrane performance were investigated, and an activation energy of permeation was obtained. Experimental results indicated that higher feed temperature yielded higher total flux and lower sulfur enrichment factor. The total flux varied little with the increase of sulfur content in the feed, but the sulfur enrichment factor first increased with the amount of thiophene added into the gasoline, and then the variation was little. The increase of PDMS layer thickness resulted in a smaller flux but a larger sulfur enrichment factor. The result indicates that the PDMS/PEI composite membranes are promising for desulfurization by pervaporation.     

PDMS/陶瓷复合膜用于正丁醇-水体系的渗透汽化分离

Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from its aqueous solution using a polydimethylsiloxane (PDMS)/ceramic composite pervaporation membrane. The effects of operating temperature, feed concentration, feed flow rate and operating time on the membrane pervaporation per-formance were investigated. It was found that with the increase of temperature or butanol concentration in the feed, the total flux through the membrane increased while the separation factor decreased slightly. As the feed flow rate increased, the total flux increased gradually while the separation factor changed little. At 40 C and 1% (by mass) butanol in the feed, the total flux and separation factor of the membrane reached 457.4 g•m2•h1 and 26.1, respec-tively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.     

硅橡胶复合膜用于渗透蒸发的膜传质动力学(Ⅱ)膜内的扩散传质

The pervaporation of organics from dilute aqueous solution through a novel plate composite silicone rubber membrane was investigated. The measured and derived data indicated that the composite membrane possessed very high permeation flux and stable selectivity for dilute organic aqueous solution. Based upon the well- known resistance-in- series model, diffusive mass transfer behavior in membrane was investigated by calculation from the measured data with different skin layer thickness of membranes. The experimental results showed that the diffusive mass transfer coefficient conformed to Arrhenius correlation with temperature and was independent of the flow status. The diffusivities of the given alcohols in membrane had an order of magnitude 10 m-10·s-1 at a wider range of temperature, which is similar to those reported in literatures.     

硅橡胶膜的制备与表征

Pervaporation membrane with preferential permeation for organic compounds over water was prepared and characterized. Selection of membrane material and the effects of polydimethylsiloxane (PDMS), cross-linker,and catalyst concentrations on performances of pervaporation membrane at room temperature were discussed. In addition, the time of cross-linking, and the kinds of basic plate in the process of preparation were tested. The formulation of pervaporation membrane material was determined. Through the characterization of membrane byinfrared spectrometry(IR), scanning electron microscopy(SEM), transmission electron microscopy(TEM) and X-ray difftraction(XRD), it is proved that the structures and characters are suitable for the pervaporation process. Exveriments also demonstrate that the permeate flux and separation factor are suitable for the process.     

Preparation and Characterization of Silicone Rubber Membrane

Pervaporation membrane with preferential permeation for organic compounds over water was prepared and characterized. Selection of membrane material and the effects of polydimethylsiloxane (PDMS), cross-linker, and catalyst concentrations on performances of pervaporation membrane at room temperature were discussed. In addition, the time of cross-linking, and the kinds of basic plate in the process of preparation were tested. The formulation of pervaporation membrane material was determined. Through the characterization of membrane by infrared spectrometry(IR), scanning electron microscopy(SEM), transmission electron microscopy(TEM) and X-ray diffraction(XRD), it is proved that the structures and characters are suitable for the pervaporation process. Experiments also demonstrate that the permeate flux and separation factor are suitable for the process.     

ZSM-5填充PDMS复合膜渗透蒸发分离乙醛水溶液(英文)

Hydrophobic ZSM-5 zeolite filled polydimethylsiloxane(PDMS) composite membranes with Nylon micro-filtration membrane as the support layer were prepared to separate acetaldehyde from its aqueous solution.The composite membranes were characterized by Fourier transform infrared spectroscopy and X-ray diffraction.Their structural morphology and thermal stability were also examined.The swelling study showed that the composite membranes presented higher degree of swelling in aqueous solution of acetaldehyde than in pure water at 25 C,suggesting that the membranes have stronger sorption capacity in acetaldehyde solution.The effects of ZSM-5 filling content and acetaldehyde concentration on pervaporation performance of composite membranes were investigated.The permeation experiments at different temperatures showed that both selectivity and permeation flux of composite membranes increased with temperature.With 5%ZSM-5-PDMS/Nylon membrane at acetaldehyde mass concentration of 8% and 25℃,the separation factor of acetaldehyde/water achieved 35 and the permeation flux was 233.3 g·m-2·h-1.     

基于多场协同理论的渗透蒸发传质模型

Toprovide a theoretical basis for optimizing the pervaporation procedure, a mass transfer model for pervaporation for binary mixtures was developed basedon the multi-fields synergy theory. This model used the mechanism of sorption-diffusion-desorption and introduced a diffusion coefficient, which was dependent on the feed concentration and temperature. Regarding the strong coupling effect in the mass transfer, the concentration distribution in membrane was predicted using the Flory-Huggins thermodynamic theory. The batch experiments and other experiments with constant composition-were conducted-using a modified chitosan pervaporatioffmembrane to separate tert-butyl alcohol （TBA）-water mixtures. The parameters of the mass transfer model were obtained from the flux of the experiments with a constant composition and the activity coefficients available through phase equilibrium equation, using the Willson equation in the feed side and the Flory-Huggins thermodynamic theory within the membrane The simulation results of the experiments .are in good agreement with the results, of the experiments.     

Effect of silver-nanoparticles generated in poly(vinyl alcohol)membranes on ethanol dehydration via pervaporation

Pervaporation is an important membrane separation method of chemical engineering. In this work,silver-nanoparticles-poly(vinyl alcohol) nanocomposite membranes(AgNPs-PVA) are produced for the sake of improving its potentials for pervaporation of ethanol–water mixture so that the usual opposite trend between membrane selectivity and permeation can be reduced. The nanocomposite membranes are fabricated from an aqueous solution of poly(vinyl alcohol) with silver nanoparticles via the in-situ generation technique in the absence of any reducing agent. Successful generation of the nano size silver is measured by the UV–vis spectrum showing a single peak at 419 nm due to the plasmonic effect of silver nanoparticles. Our nanocomposite AgNPs-PVA membranes are characterized using scanning electron microscope(SEM), Fourier-transform infrared(FT-IR) spectroscopy, X-ray diffraction and thermogravimetric analysis(TGA). The pervaporation tests of our new AgNPs-PVA membranes show good results since at a higher temperature and higher ethanol concentration in the feed, the prepared membranes are highly permeable for the water having stable selectivity values and therefore our membranes show better performance compared to that of the other PVA-based nanocomposite membranes.     

NaA型分子筛膜用于医药工业异丙醇溶媒渗透汽化脱水(英文)

NaA zeolite membranes with 80 cm in length and 12.8 mm in outer diameter were prepared by our research group cooperating with Nanjing Jiusi Hi-Tech Co., China. The influence of dissolved inorganic salts and pH value in the feed of isopropanol (IPA) solution on NaA zeolite membranes was investigated. It was found that both factors exhibited strong influence on the stability of NaA zeolite membranes. A set of pretreatment steps such as pH adjustment and distillation of the IPA solution were proposed to improve stability for pervaporation dehydration. An industrial-scale pervaporation facility with 52 m2 membrane area was built to dehydrate IPA solution from industrial cephalosporin production. The facility was continuously operated at 368-378 K to dehydrate IPA solution from water mass content of 15%-20% to less than 2% with a feed flow rate of 400-500 L·h-1 and an average water flux of 1-1.5 kg·m-2·h-1. The successful application of this facility suggested a promising application of NaA zeolite mem-brane for IPA recovery from pharmaceutical production.     

乙醇/水及乙酸/水体系的渗透汽化分离

以乙醇/水及乙酸/水体系为研究对象,研究了渗透汽化过程中料液浓度、温度因素对分离效果的影响;结合乙醇、乙酸对聚二甲基硅氧烷(PDMS)膜的溶胀特性差别,分析并讨论了两者在渗透汽化过程中可能的分离机理. 研究表明,PDMS膜能够优先透醇,但乙酸分子的缔合物以及羧基与疏水PDMS膜高分子链的强相互作用降低了其在膜中的扩散速率,使低温时乙酸/水体系优先透水,只有当温度在60℃以上时才表现出优先透酸,且分离效果较差.     

RECOVERY OF ACETIC ACID OVER WATER BY PERVAPORATION WITH A COMBINATION OF HYDROPHOBIC IONIC LIQUIDS

The present work considers the application of an integrated pervaporation process to improve the pervaporation performance of acetic acid over water. This integrated pervaporation process was based on a plain PDMS membrane with a hydrophobic ionic liquid composed of a heterocyclic cation and [PF₆]^- anions. The hydrophobic ionic liquid was introduced as the third phase between the aqueous phase and the plain PDMS membrane for improving mass-transfer of acetic acid from its aqueous matrix to the PDMS membrane. The primary results indicated that the ionic liquid as an extractant prior to pervaporation was favorable for improving the permeate selectivity and the permeate flux of acetic acid compared with using only a plain PDMS membrane. This performance could be attributed to the acetic acid concentrated and the water molecules rejected by ionic liquid prior to pervaporation. Extraction of a real effluent containing acetic acid from an antibiotic pharmaceutical plant was carried out using the above integrated pervaporation, and the results imply that this integrated pervaporation process could be scaled up for recovering acetic acids over its water-rich effluents.     

RECOVERY OF ACETIC ACID OVER WATER BY PERVAPORATION WITH A COMBINATION OF HYDROPHOBIC IONIC LIQUIDS

The present work considers the application of an integrated pervaporation process to improve the pervaporation performance of acetic acid over water. This integrated pervaporation process was based on a plain PDMS membrane with a hydrophobic ionic liquid composed of a heterocyclic cation and [PF₆]^? anions. The hydrophobic ionic liquid was introduced as the third phase between the aqueous phase and the plain PDMS membrane for improving mass-transfer of acetic acid from its aqueous matrix to the PDMS membrane. The primary results indicated that the ionic liquid as an extractant prior to pervaporation was favorable for improving the permeate selectivity and the permeate flux of acetic acid compared with using only a plain PDMS membrane. This performance could be attributed to the acetic acid concentrated and the water molecules rejected by ionic liquid prior to pervaporation. Extraction of a real effluent containing acetic acid from an antibiotic pharmaceutical plant was carried out using the above integrated pervaporation, and the results imply that this integrated pervaporation process could be scaled up for recovering acetic acids over its water-rich effluents.     

Acetic acid/water separation by pervaporation with silica filled PDMS membrane

Silica‐filled polydimethylsiloxane (PDMS) composite membranes are prepared on a polytetrafluoroethylene support structure. The structure and the performance of the membranes are characterized by scanning electron microscope, Fourier transform infrared spectroscopy, X‐ray diffraction, and thermogravimetry. The pervaporation process for acetic/water separation is performed within the PDMS membranes. The vulcanization temperature was found to have a great influence on the separation performance of the membrane. The addition of silica can significantly improve the pervaporation flux and enhance the thermal stability of the membrane. With an increase in the feed temperature, selectivity decreases and permeation flux increases. Performed with a pure PDMS membrane vulcanized at 30°C, the separation factor at first will increase, then decrease when the feed flow rate was increased from 14 to 38 L · h^?1. The maximum separation factor is achieved when the feed flow rate is 26 L · h^?1. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Extraction of 1-butanol from aqueous solutions by pervaporation

The extraction of 1-butanol from fermentation broths by pervaporation offers potential for use in biotechnology. Various membrane materials have been screened for their suitability for this process. Polydimethylsiloxane (PDMS) membranes gave the best results in terms of flux and selectivity, with large variations depending on their nature and preparation. Selectivity was further increased by including either organophilic adorbents (cyclodextrins, zeolites), or oleyl alcohol in dense PDMS membranes. The predominance of driving force (i.e. activity gradient) on pervaporation extraction performances was shown by a comparative study on different binary aqueous solutions of alcohols. Water flux remained practically constant while the alcohol flux was linearly related to its feed concentration. The conclusions obtained with binary mixtures were consistent with those obtained with two model ternary solutions; the influence of salt on 1-butanol permeability was negligible, whereas ethanol had a strong effect.     

Pervaporation separation of aqueous organic mixtures through sulfated zirconia‐poly(vinyl alcohol) membrane

Sulfated zirconia‐poly(vinyl alcohol) membranes were prepared, and pervaporation performances for aqueous organic mixtures were investigated. These hydrophilic membranes were formed by crosslinking poly(vinyl alcohol) (PVA) with the solid acid of sulfated zirconia by an acid‐catalyzed reaction. The pervaporation performances were measured as a function of the content ratio of sulfated zirconia to PVA, which affected the degree of swelling for water and the crosslinking density of the membrane. The membrane selectivity in pervaporation of aqueous organic mixtures increased in order of acetic acid < ethanol < 2‐ethoxyethanol without sacrificing the permeation rate, depending on their feed compositions. The effects of feed temperature and concentration on the membrane performance were also significant. It was found that sulfated zirconia in the membrane preparation played an important role as a filler material as well as an effective crosslinking or insolubilization agent in improving and controlling the membrane performance, i.e., permeation rate and selectivity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1450–1455, 2001     

Separation of MTBE-Methanol Mixtures by Pervaporation

Abstract

Membranes made of a polymer blend of poly(acrylic acid) and poly(vinyl alcohol) were evaluated for the separation of methanol from methyl tert-butyl ether (MTBE) by pervaporation. The influence of the blend composition and the feed composition on the pervaporation performance were investigated. Methanol permeates preferentially through all tested blend membranes, and the selectivity increases with increasing poly(vinyl alcohol) content in the blends. However, a flux decrease is observed with increasing poly(vinyl alcohol) content. With increasing feed temperature the flux increases, and the selectivity remains constant. In addition, the influence of crosslinking on the permselectivity was investigated. The pervaporation flux decreases with increasing crosslinking density, but the selectivity is enhanced. This is due to a more rapid decrease in the component flux of MTBE compared to that of methanol.     

Sorption and permeation of acetic acid–water mixtures by pervaporation using copolymer membrane

Poly (acrylonitrile‐co‐methyl acrylate) copolymer designated as PANMA was used for making pervaporation membrane. This membrane was used for separation of acetic acid–water mixtures over the concentration range of 80–99.5 wt% acetic acid in water. Interaction parameters based on Flory–Huggins lattice model and engaged species induced clustering (ENSIC) model was used to explain swelling of the membranes. Coupling in sorption was explained in terms of activity coefficient of water and acid in feed and membrane using Flory–Huggins model and also by interpolating ENSIC parameters. Flow coupling in pervaporation was also determined from phenomenological deviation coefficients. Intrinsic membrane properties like partial permeability and membrane selectivity of the solvents were also determined. Diffusion coefficient and plasticization coefficient of the solvents were obtained using a modified solution–diffusion model. The copolymer membrane showed high flux and water selectivity for highly concentrated acid. Thus, at 30°C temperature 1–20 wt% water in feed was concentrated to 82–84 wt% water in permeate and for 0.95 wt% water in feed, the membrane showed thickness normalized flux and water selectivity of 1.71 kg m^?2 h^?1 mμ and 409, respectively. OLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

碳纳米管填充PDMS膜的渗透汽化性能

将碳纳米管（CNTs）填充到PDMS中制备出CNTs/PDMS杂化膜,并将其用于乙醇/水体系的分离,发现由多壁碳纳米管制备的膜分离性能优于单壁碳纳米管填充膜,在40℃下,进料乙醇浓度为5%（质量分数）时,膜的分离因子可由8.3提高到10.0,渗透通量为206.2 g·（m²·h）^-1;采用十二烷基三氯硅烷对多壁碳纳米管进行修饰,并对修饰前后碳纳米管的性能进行表征,研究表明修饰后碳纳米管表面形成疏水层,碳纳米管的疏水性增强;将修饰后的碳纳米管填充到PDMS中,可进一步提高杂化膜对乙醇的选择性,膜的分离因子可提高到11.3,渗透通量为130.9 g·（m²·h）^-1。     

The Effect of Process Parameters on the Pervaporation of Alcohols through Organophilic Membranes

Abstract

Several organophilic membranes were utilized to selectively permeate ethanol, n-butanol, and t-butanol from dilute aqueous mixtures using pervaporation (PV). Poly[1-(trimethylsilyl)-1-propyne] (PTMSP) membranes were utilized to investigate the effect of temperature, pressure, and start-up/transient time on the separation of aqueous ethanol mixtures. Results indicate optimal ethanol selectivity and flux at the lowest permeate-side pressure. Increased temperature significantly enhanced the productivity of PTMSP, but extended operation of the PTMSP membranes at high temperatures resulted in flux degradation. Two other hydrophobic membranes, poly(dimethyl siloxane) (PDMS) and a poly(methoxy siloxane) (PMS) composite, were used to separate n-butanol and t-butanol from dilute aqueous mixtures. The effect of feed concentration on the flux and selectivity was investigated. Both membranes were found to be more permeable to n-butanol than t-butanol. The PDMS membrane was found to be more effective than the PMS membrane in terms of flux and selectivity. The effect of membrane thickness on water permeation and on organic selectivity was also studied using the PDMS membrane.