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.     

分子筛膜-精馏耦合用于费托合成水相副产物混合醇回收的工艺流程模拟

费托合成油水相副产物混合醇的回收多采用萃取精馏的分离方法,此方法需要配置7个精馏塔和5路循环回路。通过分析发现,流程冗长的关键因素在于混合醇中除甲醇外各个组分均与水产生共沸,而分子筛膜渗透汽化技术不受汽液平衡的限制,因此可以利用分子筛膜渗透汽化技术将混合醇中的水分先脱除,然后再利用精馏技术对混合醇各组分进行分离。本文完成了精馏-膜分离耦合工艺分离混合醇的全流程模拟,并与传统的萃取精馏工艺流程进行对比。精馏-膜分离耦合工艺大幅简化了原有萃取精馏工艺流程,整体能耗降低30%。并根据此流程在陕西延长石油（集团）有限公司建成了国内第一套膜分离-精馏耦合工艺的1000t/a低碳混合醇回收和分离的工业示范装置。     

生物乙醇提浓工艺中渗透蒸发膜材料的研究进展

渗透蒸发膜分离技术具有分离效率高、低能耗、易于和发酵装置耦合等优势,在生物乙醇的分离、提浓工艺中得到广泛应用。结合国内外生物乙醇的研究现状,综述了渗透蒸发膜分离技术的研究进展,并对渗透蒸发膜分离技术的核心材料--膜材料的制备与应用进行详细介绍,展望了生物乙醇的渗透蒸发膜分离技术的发展前景。     

Hybrid membrane and conventional processes comparison for isoamyl acetate production

Four process alternatives for the production of isoamyl acetate, by the liquid phase esterification of acetic acid with isoamyl alcohol, were evaluated by simulation in terms of product purity, energy integration and economics. The analysis involves a transition from conventional (two structures that use acetic acid or alcohol in excess) to hybrid membrane process (two distillation–pervaporation hybrid systems). Acetate recovery is identified as a crucial factor to minimize energy costs in all considered processes. For conventional processes, the amount of energy required for separation, at low acetate recovery levels, is considerably lower if acetic acid is used in excess. For the hybrid processes, there is an optimum value of acetate recovery that minimizes the total required heat duty and membrane area. Hybrid distillation–pervaporation process allows obtaining the specified product purity with lower energy requirements and more economical tradeoffs than the considered conventional processes. The economic optimum design maximizes energy savings and minimizes total annualized costs. After optimization and energy integration, the best process alternative includes, in a hybrid system, one packed bed reactor, two pervaporation units and a distillation column.     

Influence of operation parameters on the separation of mixtures by pervaporation and vapor permeation with inorganic membranes. Part 1: Dehydration of solvents

The separation performance of two different commercially available tubular inorganic membranes was studied for solvent dehydration. The separation layers consisted of A-type zeolite and microporous silica. The membrane characteristics were determined as function of operating conditions such as feed composition, temperature, and permeate pressure in pervaporation and vapor permeation. Among different membranes of the same batch, flux and selectivity were reproducible within 10%. The partial flux of water as the preferentially permeating component increases linearly with the water vapor pressure difference between feed and permeate and depends only marginally (viscosity influence) upon the properties of the organic component. The flux of the organic (retained) component is low and can best be described by assuming a substance and membrane specific permeance (flux over partial pressure difference) that is independent of composition. At very low water concentration in the feed one would expect a strong increase in permeability of the retained component through non-zeolite pores and larger silica pores as predicted by pure component measurements. However, this effect was not observed in mixtures within the concentration range studied here. A temperature rise improves flux rates exponentially while selectivity remains high. Thus, higher module cost in comparison to polymeric membranes can be compensated by reduced membrane area if a higher operating temperature can be chosen. Flux and selectivity decline as a function of permeate pressure with decreasing driving force. In vapor permeation with inorganic membranes superheating of the vaporous feed improves their performance while for polymeric materials a steep flux decline is observed. High flux and selectivity are obtained in the separation of water from alcohols. The normalized flux values of the A-type zeolite membrane are roughly 10 kg/m² h bar with a mixture selectivity of 2000 for methanol, 4000 for ethanol and 8000 for n-butanol. The average permeance of the amorphous silica membrane lies above 12 kg/m² h bar with mixture selectivity of 50 for methanol, 500 for ethanol and 2000 for n-butanol. The separation mechanism is mainly based on adsorption and diffusion enhanced by shape selectivity and size exclusion in some cases. The transport characteristics could be described with a simple transport model based on normalized permeate fluxes. With regard to the operation stability of the membranes, no deterioration of the performance was observed for the A-type zeolite in solvent dehydration or in separation of water from reaction mixtures. The silica membrane showed an initial conditioning effect involving a rearrangement of Si-OH groups with an increase in selectivity and decrease in flux of about 30%. After a few hours the performance stabilized and remained constant during further operation.     

Selective removal of acetone and butan-1-ol from water with supported ionic liquid–polydimethylsiloxane membrane by pervaporation

The use of ionic liquid–polymer in supported ultrafiltration membrane in vacuum pervaporation has been verified. The ultrafiltration membranes were impregnated by two ionic liquids (1-ethenyl-3-ethyl-imidazolium hexafluorophosphate and tetrapropylammonium tetracyano-borate) and polydimethylsiloxane. These new and very stable supported ionic liquid–polymer membranes were used for separation of ternary mixtures butan-1-ol–acetone–water by vacuum pervaporation. In comparison with polydimethylsiloxane membranes, the average enrichment factor of butan-1-ol increased in both cases. This higher selectivity shows a good potential for improving pervaporation separation process.     

Induced Hydrophilicity of the Nanoclay on the Pervaporation Performance of Cross-Linked Poly(vinyl alcohol) Nanocomposite Membranes

In the present study, a novel poly(vinyl alcohol) membrane system was developed by a systematic approach for the pervaporation separation of water–isopropanol azeotropic mixtures. Poly(vinyl alcohol) with 5 vol% cross-linked membranes showed water permeance of 4166 gpu with intrinsic selectivity 47. To further enhance the separation efficiency a hydrophilic nanofiller, bentonite nanoclay, is reinforced with cross-linked poly(vinyl alcohol) (5 vol% glutraldehyde) membranes. The water permeance of the membranes increased to 8232 gpu, which is 100% more than that of cross-linked membranes. Membrane selectivity and the overall pervaporation performance also showed about 63 and 157% increment, respectively.     

Pervaporation of ethanol-water mixtures through poly(vinyl alcohol-g-acrylic acid) membranes prepared by use of Fenton's reagent in grafting

Ionic crosslinking of the ferric ions and the carboxylic groups in the poly(vinyl alcohol-g-acrylic acid) (poly(VA-g-AA)) membranes improves the size screening effect in the pervaporation of ethanol-water separation. In the grafting polymerization of acrylic acid monomer onto poly(vinyl alcohol) (PVA), ferric ions are remained in the polymer membranes as the Fenton's reagent(Fe²⁺-H₂O₂) is used to initiate the reaction. Completely reversed trends in terms of the degree of swelling, the pervaporation selectivity, and the flux of permeates are obtained depending on that the ferric ions are present or absent in the membranes. The degree of swelling decreases, the pervaporation selectivity increases, and the flux decreases as the grafting percentage increases for the membranes containing ferric ions. The degree of swelling and the flux of permeates increase but the pervaporation selectivity is reduced as the grafting percentage increases for the membranes which were washed with acid to remove ferric ions.     

Development of a Mixed-Matrix Membrane for Pervaporation

Abstract

In the production of pure alcohol, pervaporation is developing into an important technology. In this study, in order to improve the performance of the pervaporation process, a mixed-matrix polymer-zeolite membrane is developed. In the preparation of these membranes, cellulose acetate as base polymer, acetone or DMF as solvent, and 13X or 4A zeolites as fillers were used. To test the performance of homogeneous and mixed-matrix membranes, a laboratory-scale pervaporation setup was constructed. The effect of the following experimental parameters on the selectivity and flux were experimentally studied to determine the optimum values of operating conditions and to understand the separation mechanism in the indicated ranges: feed concentration, 70–90 wt%; feed temperature, 30–70°C; feed flow rate, 32–76 L/h. It was observed that the addition of zeolite to the membrane matrix improves the flux value twofold with respect to its homogeneous membranes with some loss in their selectivity. For example, for a feed concentration of 74 wt% EtOH at 50°C and 1 mmHg, the flux value for the unfilled membrane is 0.6 L/m²·h, and for a 30% zeolite-filled membrane, the flux is increased to 1.33. For these cases, the selectivities are 7.76 and 5.0 for the unfilled and filled membranes, respectively. TEM micrographs of the mixed-matrix membranes show a homogeneous distribution of zeolite particles which produce a cavelike porous structure in the matrix. The combined effect of this modified morphology and zeolite selectivity is the possible reason for the observed pervaporation performances of mixed-matrix membranes.     

Separation of water–alcohol mixtures by pervaporation through asymmetric nylon 4 membrane

The dehydration of aqueous alcohol solutions through asymmetric nylon 4 membranes were investigated using pervaporation processes. The formation of asymmetric pervaporation membranes are discussed in terms of the content of the nonsolvent in the casting solution, polymer concentration, and compositions of the coagulation medium. The effects of the feed composition, feed temperature, and molar volume of the alcohols on the pervaporation performances of the asymmetric membranes are discussed. A separation factor of 4.72 and a permeation rate of 0.78 kg/m² h for the asymmetric membrane were obtained. Compared to the conventional homogeneous nylon 4 membrane, the asymmetric membrane can effectively overcome the pervaporation performances of the nylon 4 membrane for separation of water–alcohol mixtures. © 1994 John Wiley & Sons, Inc.     

Pervaporation of 50 wt % ethanol–water mixtures with poly(1‐trimethylsilyl‐1‐propyne) membranes at high temperatures

Poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) membranes have been used to separate ethanol–water mixtures by pervaporation. This polyacetylene is known to present high affinity toward ethanol, showing high selectivity and ethanol permeation flux. The performance of this polymer in the separation of alcohol–water solutions has been evaluated over long periods (572 h) at a high temperature (75°C) to examine the deterioration of the transport properties in the separation of 50 wt % ethanol–water solutions. Although PTMSP membranes present good characteristics for the separation of gases and liquid mixtures, their organic selectivity decrease with the operating time because of the relaxation processes of the polymeric chains, which affect the free volume of the polymer, the deterioration being more evident for concentrated solutions. The effects of the operation temperature on the characteristic parameters of pervaporation have also been studied to establish how this variable affects the performance of PTMSP membranes. The selectivity increases slightly with the operation temperature, but the effect of the temperature on the separation factor decreases as membranes are degraded with the operation time. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2843–2848, 2007     

A Review of Membrane Materials for Ethanol Recovery by Pervaporation

Due to an emerging scarcity of oil resources and an associated increase of oil prices, biofuels (e.g., ethanol) play an important role in the energy crisis. Fermentation is a common process for producing ethanol from renewable biomass. Pervaporation is an attractive technique for the recovery of ethanol from the fermentation systems. Separation membrane is the key element in the pervaporation separation equipments. In this article, the pervaporation performances of ethanol-permselective membranes presented in the recovery of ethanol from dilute ethanol aqueous solution are reviewed. An analytical overview on the challenges and opportunities, and the prospect of ethanol-permselective membranes by pervaporation is also discussed.     

Pervaporation performance of surface-modified zeolite/PU mixed matrix membranes for separation of phenol from water

Polyurethane (PU) is a kind of promising pervaporation membrane material and silica-rich zeolite is a potential modifier to PU, but the pristine zeolite particles suffer from the bad dispersion in the polymer. This work presents a new route to modify zeolite (ZSM-5) particles via bridging with isocyanate to prepare a membrane for the recovery of phenol from the water. Zeolite ZSM-5 particles were successfully grafted by TDI, β-cyclodextrin, and oleyl alcohol, consecutively. The corresponding zeolites filled PU membranes were prepared and characterized by FTIR, TGA and SEM techniques. The effects of the grafted structures on the pervaporation performances of the zeolites/PU membranes were investigated in the recovery of phenol from the water. The results showed that the modified ZSM-5 particles had a good dispersion in PU, while the pristine ones demonstrated an obvious sedimentation. The modified zeolite/polyurethane membranes achieved better comprehensive separation performance than the neat PU and pristine ZSM-5 modified PU membranes. Depending on the good affinity of the β-cyclodextrin to phenol, ZSM-5 particles grafted by toluene diisocyanate and β-cyclodextrin (ZSM-TC) showed the optimal separation performance with the flux of 46.03 kg μm m^?2 h^?1 and the separation factor of 15.64 for the 0.3 wt% aqueous phenol solution at 80 °C. With the increase in the zeolite loading from 5 to 25%, ZSM-5/PU membrane showed the decreased separation factor and flux comparing to the neat PU. However, ZSM-TC/PU membrane showed higher flux and better selectivity than the neat PU and pristine ZSM-5 filled PU membranes.     

渗透汽化-隔壁塔精馏耦合初步分离费托合成水的过程研究

费托合成水中含有醇、酮、酸等多种高附加值含氧有机物可提取出来作为高附加值产品,但由于费托合成水处量大,共沸体系复杂,通常需要首先对其进行初步分离。设计了直接两塔精馏、渗透汽化-两塔精馏、直接隔壁塔精馏、渗透汽化-隔壁塔精馏四种可供选择的初步分离工艺。根据渗透汽化实验数据在Aspen Plus中构建渗透汽化过程模型并进行模拟,结合灵敏度分析得到精馏过程的最佳工艺参数和模拟结果,并对四种工艺的能耗和有效能损失进行对比。结果表明,渗透汽化-隔壁塔精馏工艺具有明显的节能优势,其能耗较直接两塔精馏可降低15.85%,有效能损失降低45.74%。经渗透汽化膜预浓缩后,溶液的浓度可进入隔壁塔的适宜分离浓度区间,以充分发挥隔壁塔优势。由于渗透汽化所需能量可由余热等低品位热源提供,在余热充足的煤化工领域中可显著降低有效能损失。对于该过程而言,当渗透汽化膜价格低于438元/m²时,渗透汽化-隔壁塔精馏耦合工艺将会表现出较高的经济性。     

Separation of methanol‐tetrahydrofuran mixtures by heteroazeotropic distillation and pervaporation

The experimental investigation of the separation of tetrahydrofuran‐methanol by heteroazeotropic‐batch‐distillation and methanol‐hexane by pervaporation is presented. In particular for this last task, four different specialty commercial membranes were tested (varying feed concentration and temperature). The “pore filling” PolyAn membranes show methanol permeance values higher than 5100 GPU (Typ M2^®); separation factor of 19; and a selectivity of about 119 (Typ M1^®). From the results, a coupling phenomenon was observed. An assessment of the temperature effect in the pervaporation process corroborates the hypothesis of the presence of a coupling phenomenon. Finally, a discussion is made on two industrial scale units for the separation of the same mixture: a system of a distillation column integrated with a decanter and stand‐alone pervaporation unit. The energetic comparison shows that when using pervaporation a large reduction of the energetic consumption compared to a conventional distillation system (up to 29%) can be obtained. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2584–2595, 2014     

Dehydration of Isopropanol by Pervaporation Using Aromatic Polyetherimide Membranes

Abstract

Aromatic polyetherimide membranes were prepared by the phase inversion method and tested for the pervaporation separation of water from isopropanol with emphasis on the breaking of azeotropic composition and the dehydration of high concentrations of isopropanol. It was found that the membrane selectivity was enhanced by partial evaporation of the solvent in the cast polymer films prior to the gelation step during membrane formation. The membrane performance was shown to be dependent on the feed concentration and the operating temperature. At a feed temperature of 25°C and a permeate pressure of 133 Pa, separation factors of 173 and 384 were achieved for the dehydration of isopropanol solutions at 0.68 (azeotropic composition) and 0.96 mole fractions isopropanol, respectively, with reasonably high permeation rates. The utility of the membranes for the proposed separation was demonstrated; however, these membranes were not prepared under optimized conditions and thus a continuous study is required to rationalize the effects of membrane preparation parameters on membrane performance.     

Application of ionically crosslinked latex membranes to the separation of ethanol–water mixtures by pervaporation

Ionically crosslinked latex membrane is prepared by treating the latex membrane containing carboxyl groups with salt solutions. Pervaporation separation with these membranes shows that the ionic crosslinking raises the permeability, with the selectivity being maintained or increased. Ionically crosslinked membranes also have a higher pervaporation separation efficiency than the nontreated membranes. Permeability and selectivity increase with increasing ethanol content in feed. The temperature dependence of permeability can be correlated by the Arrhenius relationship. © 1994 John Wiley & Sons, Inc.     

用于渗透汽化的有机—无机杂化膜研究进展

近年来,有机-无机杂化膜的研究受到学术界广泛关注,随着有机-无机杂化膜制备方法的多样化和分离性能的提高,其研究前景也越来越广阔。该文首先分析了有机-无机杂化膜相比于普通无机膜和有机膜在结构和性能上存在的优势,其次综述了有机-无机杂化膜的制备方法以及其在醇类、有机酸等有机溶剂或有机混合物中的分离提纯应用,重点讨论了其在渗透汽化中的应用。最后,对有机-无机杂化膜的研究前景进行展望。未来有机-无机杂化膜的研究应借助于新的计算工具,侧重于材料的选择或制备方法的改进,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,使有机-无机杂化膜具有更加广阔的应用前景。     

Effect of Film Aging on the Pervaporation Properties of Latex Membranes

Abstract

Latex membranes have recently been investigated for their application in pervaporation separation processes. Acrylonitrile-butyl acrylate copolymer latex membrane showed selective permeation to water in pervaporation with water-ethanol mixtures. Different from solvent-cast membranes, the pervaporation properties of latex membranes were found to change with the membrane aging time or under different aging conditions. It is shown that aging leads to better membrane fusion, thus decreasing the permeation rate and increasing the separation factor. Aging the membrane in a medium which keeps the latex particle from good fusion would cause a high permeation rate but a low separation factor. Based on our observations, a comprehensive transport mechanism of the permeant through latex membranes during pervaporation is proposed.     

Pervaporation of Acetaldehyde Aqueous Solution through Zeolite 3A-Polyurethane (PU) Composite Membrane

3A-filled hydrophilic polyurethane (PU) membranes were prepared by incorporating zeolite 3A into PU for pervaporation separation of acetaldehyde and water mixtures (acetaldehyde concentration 2 wt%–20 wt%). The composite membranes were characterized by Fourier transform infrared spectroscopy and X-ray diffraction. The morphology and thermal stability of these membranes were also investigated. The effects of zeolite 3A on the sorption, diffusion, and pervaporation performance were evaluated. The swelling study showed that 3A-PU membrane had higher swelling degree in acetaldehyde aqueous solution than in pure water. And the swelling degree of the composite membrane in acetaldehyde solution increased with the 3A content. The permeation flux and water/acetaldehyde separation factor first increased and then decreased with increasing 3A content. The reason may be that a proper quantity of 3A will enlarge the free volume fraction of PU while excessive 3A lead to its poor dispersion. The highest permeation flux of the composite membrane could reach 223 g · m^?2 · h^?1 and the maximum water/acetaldehyde selectivity achieved 7.5. The calculation of sorption selectivity and diffusion selectivity showed that diffusion played a more important role in this process.