Pervaporation dehydration of ethanol–water mixtures with chitosan/hydroxyethylcellulose (CS/HEC) composite membranes: I. Effect of operating conditions

Composite hydrophilic pervaporation membranes were prepared from chitosan blended with hydroxyethylcellulose using cellulose acetate as a porous support. The membranes were tested for dehydration performance of ethanol–water mixtures of ethanol concentrations 70–95 wt.% in the laminar flow region, at temperatures 50–70°C and at permeate pressures of 3–30 mmHg. The composite membrane showed an improved dehydration performance compared with dense CS/HEC membrane developed earlier. The effects of operating conditions also revealed that pervaporation of low water content feed carried out at high feed flow rate and at low temperature and permeate pressure was an advantage.     

Effect of sorbitan-based surfactants on glass transition temperature of cellulose esters

Thermal behavior of mixtures composed of cellulose acetate butyrate (CAB), carboxymethylcellulose acetate butyrate (CMCAB), or cellulose acetate phthalate (CAPh), and sorbitan-based surfactants was investigated as a function of mixture composition by means of differential scanning calorimetry (DSC). Surfactants with three different alkyl chain lengths, namely, polyoxyethylenesorbitan monolaurate (Tween 20), polyoxyethylenesorbitan monopalmitate (Tween 40), and polyoxyethylene sorbitan monostearate (Tween 60) were chosen. DSC measurements revealed that Tween 20, 40, and 60 act as plasticizers for CAB, CMCAB, and CAPh (except for Tween 60), leading to a dramatic reduction of glass transition temperature (T _g). The dependence of experimental T _g values on the mixture composition was compared with theoretical predictions using the Fox equation. Plasticization was strongly dependent on mixture composition, surfactant hydrophobic chain length, and type of cellulose ester functional group.     

Chiral separation of trans-stilbene oxide through cellulose acetate butyrate membrane

An enantioselective membrane was prepared using cellulose acetate butyrate as a membrane material. The flux and permselective properties of membrane using 50% ethanol solution of (R,S)-trans-stilbene oxide as feed solution were studied. The top surface and cross-section morphology of the resulting membrane were examined by scanning electron microscopy. The resolution of over 92% enantiomeric excess was achieved when the enantioselective membrane was prepared with 15 wt % cellulose acetate butyrate and 30 wt % N,N-dimethylformamide in the casting solution of acetone, 10 °C temperature of water bath for the gelation of the membrane, and the operating pressure and the feed concentration of the trans-stilbene oxide were 3 kgf/cm² and 5.2 mmol/L, respectively. Since the cellulose acetate butyrate contained a large amount of asymmetric carbons on the backbone structure, it was possible to form helical structure, this was considered to be the reason for the enantioselectivity of the membrane.     

Factors affecting flux and ethanol separation performance in vacuum membrane distillation (VMD)

Membrane distillation (MD) has a great potential as a concentration process for temperature labile liquids such as fruit juices, etc. Besides water, also aroma compounds will permeate through the membrane depending on their volatility and how the MD process is operated on the permeate side.In this paper, an experimental and theoretical investigation of the influence of concentration polarisation and temperature polarisation on the flux and selectivity of binary aqueous mixtures of ethanol is presented for vacuum membrane distillation (VMD) processes. Experimental results include changes of the following parameters: nature of solutions, membrane material and pore size, feed temperature, recirculation flow rate. One method was proposed in order to evaluate the concentration polarisation effects from the fit of the experimental data. General models taking into account Knudsen and viscous flows were proposed, but viscous contribution resulted to be negligible under our operating conditions. Therefore, theoretical fluxes were estimated using Knudsen model and a good agreement between them and the experimental ones was found.     

Chiral separation of (R,S)-2-phenyl-1-propanol through cellulose acetate butyrate membranes

As the cellulose acetate butyrate possessed multichiral carbon atoms in its molecular structure unit, enantioselective membrane was prepared using cellulose acetate butyrate as membrane material. The flux and permselective properties of membrane using aqueous solutions of (R,S)-2-phenyl-1-propanol as feed solution was studied. The top surface and cross-section morphology of the resulting membranes were examined by scanning electron microscopy. When the membrane was prepared with 15 wt.% cellulose acetate butyrate and 20 wt.% DMF in the casting solution, and the operating pressure and feed concentration of racemate were 2 kgf/cm² and 5 mmol/L, respectively, over 98% of enantiomeric excess (e.e.) was obtained. This is a report, for the first time, that the cellulose acetate butyrate is used as optical resolution membrane material for isolating the optical isomers of (R,S)-2-phenyl-1-propanol.     

Separation of ethanol—water mixtures by pervaporation through thin,composite membranes

This paper reports on the separation of ethanol—water mixtures using pervaporation for several membrane types. The FT30 and RC100 membranes pass ethanol selectively at feed concentrations similar to fermentation beers, and the FT30 membrane continues to pass ethanol selectively at higher ethanol feed concentrations. As the ethanol concentration in the feed increases, the ethanol selectivity of both the FT30 and RC100 membranes decreases; near the ethanol—water azeotrope, both membranes pass water selectively. At lower ethanol concentrations, the selectivity of the FT30 membrane increases as the feed temperature increases above 23°C.     

Pervaporation of alcohol-toluene mixtures through polymer blend membranes of poly(acrylic acid) and poly(vinyl alcohol)

Homogeneous membranes were prepared by blending poly(acrylic acid) with poly(vinyl alcohol). These blend membranes were evaluated for the selective separation of alcohols from toluene by pervaporation. The flux and selectivity of the membranes were determined both as a function of the blend composition and of the feed mixture composition. The results showed that a polymer blending method could be very useful to develop new membranes with improved permselectivity. The pervaporation properties could be optimized by adjusting the blend composition. All the blend membranes tested showed a decrease in flux with increasing poly(vinyl alcohol) content for both methanol—toluene and ethanol—toluene liquid mixtures. The alcohols permeated preferentially through all tested blend membranes, and the selectivity values increased with increasing poly(vinyl alcohol) content. The pervaporation characteristics of the blend membranes were also strongly influenced by the feed mixture composition. The fluxes increased exponentially with increasing alcohol concentration in the feed mixtures, whereas the selectivities decreased for both liquid mixtures.     

丙烯酸交联壳聚糖渗透汽化膜研究（Ⅱ）──乙醇／水混合液的渗透汽化分离性能

丙烯酸交联壳聚糖渗透汽化膜研究（Ⅱ）──乙醇／水混合液的渗透汽化分离性能钟伟，李文俊，葛昌杰，陈新（复旦大学高分子科学系，上海，２００４３３）关键词交联壳聚糖，渗透汽化，丙烯酸，乙醇／水混合液混合液体的渗透汽化（简称ＰＶ）膜分离自８０年代实现工业化以...     

Modelling of the pervaporation of binary mixtures through moderately swelling,non-reacting membranes

The pervaporation of binary mixtures through moderately swelling membranes is analyzed as a solution—diffusion process, on the assumption that the diffusion coefficient of each permeant is an exponential function of both concentrations. A model is derived in which changes in selectivity and fluxes are related to major external conditions: the upstream mole fraction in the feed and the downstream total pressure of the pervaporate. This model leads to the computation of the pervaporation selectivity and the fluxes as a function of the parameters of the model. Numerical examples are given, relative to different shapes of curves for selectivity and fluxes. A flowsheet is given and allows, through the comparison with experimental results, the determination of the parameters of the model. Internal concentration profiles in the membrane may also be computed. In order to test the validity of this model, it has been applied to a set of experimental data for the pervaporation of hydrocarbon binary mixtures through nitrile—butadiene and styrene—butadiene copolymers.     

Pervaporation of water-ethanol mixtures through symmetric and asymmetric TPX membranes

In this work, the pervaporation performance and mechanism of water-ethanol mixtures through symmetric and asymmetric TPX [poly(4-methyl-1-pentene)] membranes were investigated. The results show that TPX is a highly water permselective material although it is strongly hydrophobic. It was found that, for a symmetric dense TPX membrane, the feed solution vaporizes first and then permeates through the membrane. The water selectivity stems from the huge difference in diffusivity between water and ethanol vapors. To improve the permeation flux, asymmetric TPX membranes were prepared by a wet inversion method. However, due to the swelling effect of ethanol on TPX, small pores occur when the dense skin contacts the feed solution, resulting in a loss of water selectivity. Stain experiments were carried out to verify this mechanism. In addition, it was found that a parallel model can describe the mechanism quite accurately. Good agreement between the theoretical calculation and experimental measurement has been obtained. Furthermore, we also found that the loss of selectivity can be avoided by turning the asymmetric membrane over; that is, let the dense skin face the permeate.     

Synthesis and Characterization of Poly(ether-block-amide) Membranes

Poly(ether-block-amide) membranes were made via casting a solution on a nonsolvent (water) surface. In this research, effects of different parameters such as ratio of solvent mixture (n-butanol/isopropanol), temperature, composition of coagulation bath (water) and polymer concentration, on quality of the thin film membranes were studied. The mechanism of membrane formation involves solution spreading, solvent–nonsolvent exchange, and partial evaporation of the solvent steps. Solvent- nonsolvent exchange is the main step in membrane formation and determines membrane morphology. However, at higher temperature of polymeric solution greater portion of solvent evaporates. The results showed that type of demixing process (mutual affinity between solvent and nonsolvent) has important role in film formation. Also, addition of solvent to the nonsolvent bath is effective on membrane morphology. The film quality enhances with increasing isopropanol ratio in the solvent mixture. This behavior can be related to increasing of solution surface tension, reduction of interfacial tension between solution and nonsolvent and delayed solvent-nonsolvent demixing. Uniform films were made at a temperature rang of 60–80 °C and a polymer concentration of 4–7 wt%. Morphology of the membranes was investigated with scanning electron micrograph (SEM). Pervaporation of ethyl butyrate/water mixtures was studied using these membranes and high separation performance was achieved. For ethyl butyrate/water mixtures, It was observed that both permeation flux and separation factor increase with increasing ethyl butyrate content in the feed. Increasing temperature in limited range studied resulted in decreasing separation factor and increasing permeation flux.     

Transport of binary water–ethanol mixtures through a multilayer hydrophobic zeolite membrane

Transport of water–ethanol mixtures through a hydrophobic tubular ZSM-5 (Si/Al = 300) zeolite membrane during pervaporation was studied experimentally and theoretically. The zeolite membrane was deposited on a support made of pure titania coated with three intermediate ceramic titania layers. The influence of feed concentration, feed temperature and permeate pressure on permeate fluxes and permeate concentrations was investigated in a wide range. Dusty gas model parameters of the support and all ceramic intermediate layers were calculated on the basis of gas permeation data. Mass transfer resistances and pressure drops in the different membrane layers during pervaporation were calculated for several process conditions. In particular the influence of the undesired but unavoidable pressure drop in the support and the intermediate layers on the effective driving force for pervaporation was evaluated and found to be relevant for predicting the overall process performance. The membrane prepared was found to be suitable for the recovery of highly concentrated ethanol from feed mixtures of relatively low ethanol concentrations at relatively low feed temperatures.     

On the mechanism of separation of ethanol/water mixtures by pervaporation II. Experimental concentration profiles

Ethanol—water concentration profiles in cellulose acetate membranes were measured under steady-state pervaporation conditions. Knowledge of these profiles leads to a better understanding of the diffusion process during pervaporation. The concentration profiles were determined by a film-stack method, using three to six layers. It is shown that permeation of ethanol—water mixtures proceeds in a coupled way and that crossterm diffusion coefficients need to be considered. Furthermore, the occurrence of sorption resistances at the feed/membrane interface can be established from these experiments.     

The Study on Pervaporation Behaviors of Dilute Organic Solution Through PDMS/PTFE Composite Membrane

As an energy-efficient alternative to distillation, pervaporation has been widely combined with fermentation to remove organic compounds from their dilute solutions in a fermentation broth. In this work, the organic permselective composite membrane is prepared by coating polydimethylsiloxane (PDMS) cross-linked with n-heptane on the substrate of polytetrafluoroethylene(PTFE) membrane. The separation behavior is studied in different dilute organic solutions, which include acetone dilute solution, butanone dilute solution, cyclohexanone dilute solution, ethanol dilute solution, isopropanol dilute solution, n-butyl alcohol dilute solution, acetic acid dilute solution, and ethyl acetate dilute solution. Most of these solutions are main reaction products or by-products from fermentation process. The effects of solubility of organics in the membrane, molecular weight, and polarity of the organics on the pervaporation performance are investigated. The effects of operating temperature and organic concentration in the feed solutions on the performance of composite membrane are studied as well. The experimental results show that molecular volume has less influence than solubility and molecular polarity for these organic solvent. The selectivity of PDMS membrane to ethyl acetate is relative high due to good solubility and diffusion of ethyl acetate molecules in polymer.     

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。     

Membrane distillation for dilute ethanol: Separation from aqueous streams

Air-gap membrane distillation was examined as a possible technique for ethanol–water separation using PVDF membranes. The composition and flux of the permeate were monitored as feed concentration, feed temperature, feed flow rate, cooling temperature and cooling flow rate were varied. The effect of salt addition to the feed mixture was also examined. The upper feed concentration tested was 10 wt.% ethanol. Within the feed temperature range of 40–70°C, ethanol selectivity of 2–3.5 was achieved. Two versions of a general mathematical model were solved numerically for the ethanol–water system; one did not include temperature and concentration polarization effects while the other did. Good agreement between experimental and predicted values was obtained with the latter version of the model.     

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.     

Pervaporative separation of ethanol from an alcohol—ester quaternary mixture

As part of a research project focusing on the development of a sustainable biocatalytic process for production of chiral secondary alcohols, the pervaporative separation of ethanol from ethanol/ethyl acetate/1-methoxy-2-propanol/1-methoxy-2-propyl acetate-mixtures through a commercial PVA-based membrane was investigated. Separation behavior of this mixture was studied in a range of mol fractions (10–70%), temperatures relevant for biocatalytic conversions (35–55 °C) and downstream pressures (35–200 mbar).

Pervaporation of the non-diluted multicomponent mixture was shown to be strongly influenced by interactions between the permeants and the membrane. Investigation of these interactions contributed to the understanding of the mass transport mechanism of this mixture. Overall, high fluxes were obtained, but small differences between the fastest permeating species were found. The fastest permeating species was ethanol, ethyl acetate or 1-methoxy-2-propanol depending on the feed composition.     

壳聚糖膜结构与乙醇／水混合液的渗透汽化性能

用渗透汽化膜分离混合液体,纤维素、赛璐玢等作醇/水分离膜有较高的渗透通量,但分离系数低.甲壳素是广泛存在于自然界的一类天然高分子.前文报道了用甲壳素脱乙酰基的产物壳聚糖(CS)作醇/水渗透汽化(PV)分离膜,在一定的原料液浓度下具有较好的选择渗透性.本文讨论CS膜结构对乙醇/水混合液PV性能的影响,并探讨了提高选择性的途径.     

The separation of mixtures of organic liquids by hyperfiltration

Two solid-membrane methods exist for separating mixtures of organic liquids. They are pervaporation, in which the product phase is a vapour, and hyperfiltration in which feed and product phases are both liquid. Technically hyperfiltration is similar to reverse osmosis but, if that term is to be used at all, it should be restricted to dilute solutions of solutes to which the membrane is almost semi-permeable. The polymer membranes which have been found so far to give significant degrees of separation and fluxes with organic liquid mixtures have been crystalline polar polymers with high glass temperatures. The problems of membrane preparation are thus more severe than with almost amorphous, freely soluble polymers such as cellulose acetate.The absorption of liquids from a mixture by a polymer and their permeation in the polymer have received relatively little attention and it is not yet possible to infer the behaviour from that of the polymer towards each liquid alone. Nevertheless a theory of hyperfiltration can be developed based on Henry's and Fick's laws and neglecting any direct coupling of flows. The equations which predict the separation and fluxes are useful in the first place to predict the thermodynamic restraints on any potentially useful separation process. It turns out that relatively large pressures are required, 100 atm or more, and hyperfiltration is better adapted to further purifying a relatively good product than to recovering a small amount of a valuable substance from a large volume of waste.The equations lend themselves to a direct experimental test. An apparatus for doing this has been constructed and two liquid mixtures and membranes have been studied. They are toluene + n-heptane with an asymmetric polyacrylonitrile membrane and methanol + isobutanol with a uniform cellulose membrane. The mixtures were chosen as being thermodynamically close to ideal because this simplifies the interpretation of the data. Their nonideality has been taken fully into account.The results show that the simple theory accounts very well for the observed facts. For the first system the selectivity coefficient was about 2 and for the second, about 15.The mechanism of transport is found to be the normal solution-diffusion mechanism for permeation of organic solvents in polymers. There is some positive frictional coupling between the two liquids as a result of which the improvements in separation to be expected from an increase in the applied pressure are not achieved quantitatively. The increasing absorption of liquid by the membrane as the mole fraction of the preferentially absorbed liquid in the mixture is increased increases its permeability to both components by about