Recovery of esters from dilute aqueous solutions by vapor permeation

The vapor permeation characteristics of ester compounds (ethyl acetate, EA; ethyl propionate, EP; and ethyl butyrate, EB) through a tube-type surface-modified alumina-silane hydrophobic membrane were investigated. Experiments were performed to evaluate the effects of the feed concentration (0.15–0.60 wt%) and temperature (30–50 °C) on the separation of EA, EP, and EB from aqueous solutions. It was found that the permeation flux increased with increasing feed ester concentration and operating temperature. The fluxes of EA, EP, and EB at 0.60 wt% feed concentration and 40 °C were 282, 506, 742 g/m²h, which were much higher than those of PDMS polymer membrane. The separation factors for the 0.15–0.60 wt% feed solutions of EA, EP, and EB at 40 °C were in the range of 28.1–93.9, 145.3–162.6, and 260.4–268.8, respectively. Phase separation occurred in the permeate when collected in a cold trap, because the concentration of the ester in the permeate was much higher than its solubility.     

Pervaporation of esters with hydrophobic membrane

Surface-modified alumina membrane (A1₂O₃) was used for ester flavor recovery by pervaporation. This study focused on the permeation characteristics of ester compounds (ethyl acetate, EA; ethyl propionate, EP; ethyl butyrate, EB) through tube-type hydrophobic membrane. Experiments were performed to evaluate the effects of the feed concentration (0.15-0.60 wt%) and temperature (30-50 ‡C) on separation of EA, EP, and EB from aqueous solutions. It was found that the permeation flux increased with increasing feed ester concentration and operating temperature. The fluxes of EA, EP, and EB at 0.60wt% feed concentration and 40 ‡C were 254, 343, and 377 g/m² hr, which was much higher than those of polymer membranes. It was reported that the permeate flux of EA with PDMS was 1.1-58 g/m²Phr at feed concentration of 90-4,800 ppm and 45 ‡C. The separation factors for the 0.15-0.60 wt% feed solution of EA, EP, and EB at 40 ‡C were in the range of 66.9-78.9, 106.5-97.3, and 120.5-122.8, respectively. Due to the high separation factor, phase separation occurred in permeate stream because the ester concentration in permeate was much above the saturation limit.     

Vapor permeation of ethyl acetate,propyl acetate,and butyl acetate with hydrophobic inorganic membrane

This study is focused on the permeation characteristics of ester compounds from aqueous solutions through hydrophobic membrane; ethyl acetate (EA), propyl acetate (PA) and butyl acetate (BA). A surface-modified tube-type alumina membrane (Al₂O₃) was used for ester compounds recovery by vapor permeation. Experiments were performed to evaluate the effects of the feed concentration (0.15–0.60 wt.%) and feed temperature (30–50 °C) on the separation of EA, PA, and BA from dilute aqueous solutions. It was found that the permeation flux increased with increasing feed ester concentration and operating temperature. The fluxes of EA, PA, and BA at 0.60 wt.% feed concentration and 40 °C were 282, 526, 661 g/m² h, which were much higher than those of polymer membranes. The separation factors for the 0.15–0.60 wt.% feed solution of EA, PA, and BA at 40 °C were in the range of 28.1–93.9, 83.6–129.4, and 190.7–209.9, respectively. The membrane tested showed high flux and high selectivity.     

Pervaporation properties of polyvinyl alcohol/ceramic composite membrane for separation of ethyl acetate/ethanol/water ternary mixtures

In further purification of ethyl acetate (EAC) process, azeotropic distillation or extractive distillation is usually applied. High energy consumption limits the economic profit of the process. In this study, pervaporation separation of EAC/ethanol (EA)/water ternary mixtures using the ceramic-supported polyvinyl alcohol (PVA) composite membrane was investigated to substitute the azeotropic distillation or extractive distillation. Swelling experiments were performed to evaluate the sorption characteristic of the membrane. Flory-Huggins theory was applied to study the interaction between the membrane and the penetrant. The UNIFAC model was adopted to investigate the variation of the penetrant activity in the membrane. The effects of operation temperature, feed water content and feed flow rate on the PV performance of the membrane were systematically investigated. The composite membrane exhibited high PV performance with the total flux of 2.1 kg·m⁻²·h⁻¹ and 94.9 wt% permeate concentration of water (operation condition: feed composition 82.6 wt% EAC, 8.4 wt% EA, 9 wt% water, feed temperature 60 °C, feed flow rate 252 mL· min⁻¹). The PV performance of the membrane varied slightly over a continuous PV experiment period of 110 h. Our results demonstrated that the PVA/ceramic membrane was a potential candidate for the purification of EAC/EA/water ternary mixtures.     

A characterization of pdms pervaporation membranes for the removal of trace organic from water

A new silicone pervaporation membrane for the removal of one of trace organies, 1,2-dichloroethane from water has been developed using polydimethylsiloxane (PDMS) and oligomeric silylstyrene as a crosslinking agent of PDMS. Optimal conditions for fabricating the best membrane were determined from swelling measurements ard pervaporation experiments and then the membrane was characterized at different membrane thickness and operating conditions. In the pervaporation separation of 55–70 ppm of l,2-dichlorocthanc aqueous mixtures, the developed membrane has flux of 2.5–330 g/(m².h) and selectivity of 230–1750 depending on membrane thickness, permeate pressure and operating Temperature. Water permeation through thin membrane was found to be subjected to significant desorption resistance, while the desorption resistance and thermodynamic factors as well as the concentration polarization of the organic at the boundary layer in feed can affect the organic permeation, depending on membrane thickness. Selectivity change with permcaic pressure depends on membrane thickness: at small membrane thickness range, selectivity increases with permeate pressure and at large thickness region it decreases. From the Arrhenius plots of each component fluxes, the permeation activation energies were determined. Through an analysis of the permeation activation energies of each components, the desorption resistance as well as the effects of the thermodynamic factors on permeation was qualitatively characterized.     

Separation of fatty acids/triacylglycerol by membranes

Separation of fatty acids from triacylglycerol by membrane separation technique has been studied. Mixtures of triacylglycerols and fatty acids were extracted with alcohol, and the alcohol extracts were treated for recovery of oil by membrane separation technique. The membranes used were of both cellulosic and noncellulosic types. Polyamide membranes showed better selectivity toward fatty acid separation as compared to cellulose acetate and polysulfone membranes. For groundnut oil/fatty acid/alcohol mixture and a polyamide membrane, the free fatty acid (FFA) concentration in the permeate was 86.82% at 0.7 MPa pressure when the feed had 61.71% FFA. A reasonable permeate flux of 67.36 Im⁻²h⁻¹ was obtained. Results obtained have been useful in selecting membrane material suitable for such applications.     

Separation of Pyridine/Water Solutions Using Pervaporation

Abstract

Studies were performed on the separation of pyridine/water solutions using pervaporation. Organic permeation experiments were performed using a ‘silicalite»-filled silicone composite membrane. Effects of feed concentration, feed temperature, and permeate side pressure were examined. Benchmark conditions of 5.0 wt% pyridine, 50°C, and 2 torr were chosen. At the benchmark conditions, an organic selectivity of 34 and a permeate flux of 0.428 kg/m²h was achieved. An increase in feed concentration caused an increase in both the permeate concentration and flux, but caused a decrease in the selectivity. Also, permeate compositions far exceeded standard vapor—liquid equilibrium. Temperature had an Arrhenius-type relationship with regard to flux, but had no effect on the selectivity. Increasing the permeate pressure caused a steady decrease in permeate flux and also decreased the permeate composition and selectivity.     

Optimization and modeling of the performance of polydimethylsiloxane for pervaporation of ethanol−water mixture

Response surface methodology was used to optimize the performance of pervaporation of ethanol aqueous solution using polydimethylsiloxane hollow-fiber membrane. The effects of four operating conditions, that is, the feed temperature (30–50°C), the feed flow rate (10–50 L/h), ethanol concentration (5–20 wt%), and the vacuum pressure (10–50 KPa) on the membrane selectivity and the total flux of permeation were investigated with response surface methodology. The results showed that a quadratic model was suggested for both selectivity and total flux showing a high accuracy with R² = 0.9999 and 0.9995, respectively. The developed models indicated a significant effect of the four studied factors on both selectivity and total flux with some significant interactions between these factors. The optimum selectivity was 15.56, achieved for a feed temperature of 30°C, feed flow rate of 10 L/h, ethanol concentration of 15 wt%, and a permeate pressure of 10.74 KPa whereas the optimum total flux was 1833.66 g/m².h was observed for at a feed temperature of 50°C, a feed flow rate of 50 L/h, ethanol concentration of 15 wt%, and a permeate pressure of 49.38 KPa.     

PDMS/ZSM-5膜的制备及渗透汽化分离水中乙酸正丁酯和乙酸乙酯

为探究出适合分离水中的乙酸正丁酯和乙酸乙酯的新型渗透汽化膜材料,选用沸石ZSM-5 对聚二甲基硅氧烷(PDMS)材料进行填充改性,以聚偏氟乙烯(PVDF)为支撑层,采用刮涂法制备PDMS/ZSM-5/PVDF复合膜渗透汽化分离水中的乙酸正丁酯和乙酸乙酯。采用SEM、接触角测量仪、FTIR、TGA和XRD等对膜材料物理化学性能进行表征,考察了膜材料的溶胀行为及渗透汽化性能。结果表明,ZSM-5在 PDMS 膜中分散均匀,且没有发生化学作用,并提高了膜材料的疏水性和热稳定性。随着ZSM-5添加量的增加,膜在乙酸正丁酯和乙酸乙酯的溶胀度和待分离组分在膜材料中的扩散速率不断增加。随着进料浓度和温度的增加,渗透通量不断增大,分离因子先增大后减小。随着ZSM-5在PDMS/ZSM-5/PVDF复合膜中含量的增加,总渗透通量增加,而分离因子呈现先增加后减小的趋势。当添加量为10%（质量）时,分离因子达到最大值。对于乙酸正丁酯/水体系,渗透通量和分离因子最大值分别为319 g·m ^-2·h ^-1和131;而对于乙酸乙酯/水体系,渗透通量和分离因子最大值分别为1385 g·m ^-2·h ^-1和121。     

Pervaporation of Organic Liquids from Binary Aqueous Mixtures using Poly(trifluoropropylmethylsiloxane) and Poly(dimethylsiloxane) Dense Membranes

In this work we have compared and contrasted the pervaporation behaviour (separation factor and flux) of fluorosilicone dense membranes based on poly(trifluoropropylmethylsiloxane) (PTFPMS) with poly(dimethylsiloxane) (PDMS) dense membranes. In particular, pervaporation experiments were carried out at 298 K using lab-made PTFPMS, lab-made PDMS and commercial PDMS membranes in order to remove three different organic liquids pyridine (PY), isopropanol (IPA) and methylethylketone (MEK) from dilute (<10 wt.%) binary aqueous mixtures. All of the silicone membranes studied were found to be successful for the desired separations. The permeation flux of pyridine–water liquid mixtures for the PTFPMS membranes was found to increase with the pyridine concentration in the feed mixtures. The separation factor for PDMS membranes for the removal of pyridine, IPA and MEK from aqueous binary mixtures (1 wt.%) was found to be higher than that of PTFPMS membranes while the normalized flux was higher for PTFPMS membranes under identical test conditions. The effect of crosslink density of the PTFPMS membranes on the separation of pyridine–water mixtures was also studied. For a 1 wt.% feed solution the total flux increased with the molar mass between crosslinks, whereas the separation factor for pyridine–water was highest for a molar mass between crosslinks of 15,320 g mol⁻¹.     

Effect of additives concentration on performance of cellulose acetate and polyethersulfone blend membranes

Asymmetric micro porous membranes have been prepared successfully from blending of cellulose acetate (CA) and polyethersulfone (PES) by the phase inversion method with N, N-dimethylformamide (DMF) as solvent. Two additives were selected in this study, including polyethylene glycol 600 (PEG 600) and polyvinylpyrrolidone (PVP). The effects of concentration of additives on CA/PES blend membrane performance and cross-section morphology were investigated in detail. CA/PES membranes were compared with CA/PES/PEG and CA/PES/PVP membranes in the performance such as pure water flux, membrane resistance, porosity and cross-section morphology. The resulting blend membranes were also carried out the rejection and permeate flux of Egg Albumin (EA) proteins with molecular weight of 45 Da. The membranes thus obtained with an additive concentration of 5 wt% of both PEG and PVP exhibited superior properties than the 80/20% blend composition of CA and PES membranes. The permeate flux of protein was increased from 44 to 134 lm² h with increase in concentrations of both PVP and PEG in 80/20% blend composition of CA and PES membranes. Cross-sectional images from scanning electron microscopy showed larger macropores in the bottom layer of the membranes with increasing additives content. Observations from scanning electron microscopy provided qualitative evidence for the trends obtained for permeability and porosity results.     

Separation of aqueous salt solution by pervaporation through hybrid organic–inorganic membrane: Effect of operating conditions

Hybrid polymer-inorganic membranes were prepared by crosslinking poly(vinyl alcohol) (PVA), maleic acid (MA) and silica via an aqueous sol–gel route. Membrane characterisation results revealed silica nanoparticles (< 10 nm) were well dispersed in the polymer matrix and significantly reduced swelling of the membrane. The membranes were tested for pervaporation separation of aqueous salt solution with NaCl concentrations of 0.2–5.0 wt% at temperatures 20–65 °C, feed flowrates 30–150 mL/min and permeate pressures 2–40 Torr. The salt rejection remained high (up to 99.9%) under all operating conditions. A high water flux of 11.7 kg/m² h could be achieved at a feed temperature of 65 °C and a vacuum of 6 Torr. The effect of operating conditions on water flux is discussed in relation to diffusion coefficients of water and fundamental transport mechanism through the membrane. The activation energy for water permeation was found to vary from 23.8 to 20.1 kJ/kmol when the salt concentration in the feed was increased from 0.2 to 5.0 wt%.     

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     

Separation of Sunflower Oil from Hexane by Use of Composite Polymeric Membranes

Vegetable oil extraction, as performed today by the oilseed-crushing industry, usually involves solvent extraction with commercial hexane. After this step, the vegetable oil–hexane mixture (miscella) must be treated to separate its components by distillation. If solvent-resistant membranes with good permeation properties can be obtained, membrane separation may replace, or be used in combination with, conventional evaporation. Two tailor-made flat composite membranes, poly(vinylidene fluoride) (PVDF–Si and PVDF–CA) and a commercially available composite membrane (MPF-50), were used to separate a crude sunflower oil–hexane mixture. The effects of temperature, cross-flow velocity (v), transmembrane pressure (Δp), and feed oil concentration (C _f) on membrane selectivity and permeation flux were determined. The PVDF–Si membrane achieved the best results, being stable in commercial hexane and having promising permselectivity properties for separation of vegetable oil–hexane miscella. Improved separation performance was obtained at C _f = 25%, Δp = 7.8 bar, T = 30 °C, and v = 0.8 m s⁻¹; a limiting permeate flux of 12 Lm⁻² h⁻¹ and 46.2% oil retention were achieved. Low membrane fouling was observed under all the experimental conditions studied.     

Pervaporation separation of levulinic acid aqueous solution by ZSM-5/PDMS composite membrane

This work aims at investigating the special application of ZSM-5/polydimethylsiloxane (PDMS) membrane being used for pervaporation separation of levulinic acid aqueous solutions. The effects of temperature, downstream pressure, feed concentration, and raw material ratio on the separation performance are investigated by self-made flat-sheet films. When the flow rate of feed pump remained at 0.4 ml/min (10 wt% levulinic acid), a levulinic acid permeation flux of 334.13 g/(m²h) and a separation factor of 2.382 at 75°C are observed over the composite membrane doped with 10 wt% ZSM-5. In addition, the acid resistance is enhanced after the PDMS membranes are doped with ZSM-5. Besides, the functionalized process also makes the membranes increase in its hydrophobicity. The results demonstrate that the ZSM-5/PDMS-based membranes show profound prospects for separating levulinic acid aqueous solution.     

FLUX ENHANCEMENT USING FLOW REVERSAL IN ULTRAFILTRATION

ABSTRACT

The effect of flow reversal on permeate flux in cross-flow ultrafiltration of bovine serum albumin (BSA) has been investigated experimentally. BSA is a well-studied model solute in membrane filtration known for its fouling and concentration polarization capabilities. Ultrafiltration experiments were performed with BSA feed solutions in a hollow-fiber membrane module. The BSA feed concentrations ranged from 0.01 to 5 wt% and were ultrafiltered at a transmembrane pressure of 20 psia. Permeate flux was determined both with and without the use of flow reversal for each concentration. The experimental results indicate that under flow reversal conditions, the permeate flux is enhanced significantly when compared with runs without flow reversal. The effect of flow reversal on flux enhancement is very pronounced for dilute BSA solutions.     

气液两相流强化卷式纳滤膜分离硫酸镁水溶液

气液两相流强化卷式纳滤膜分离实验是针对DK2540卷式纳滤膜,采用气液两相流强化分离技术,对硫酸镁溶液进行研究,较系统地研究了温度、料液浓度、过膜压力、料液流速、气体流速等因素在分离硫酸镁溶液时,对膜通量、截留率和膜通量增加率的影响,并总结了气液两相流强化效果。结果表明,气液两相流强化卷式纳滤膜分离有明显的效果。温度宜在30~40℃。料液浓度越大、过膜压力越小、气液比越大,气液两相流强化效果越明显。     

Dehydration through pervaporation from HIx solution (HI-H2O-I2 mixture) using a cation exchange membrane for thermochemical water-splitting iodine-sulfur process

Pervaporation (PV) of water from HIx solution (HI-H₂O-I₂ mixture) using Nafion-117 was evaluated aiming at the application to dehydrate the azeotropic composition in HI decomposition reaction of thermochemical IS process. PV experiment was carried out by using HI solutions of 40–65 wt% and an I₂/HI molar ratio of 0–3 in the feed at the room temperature. The permeation flux decreased with increasing HI weight fraction in the feed. The permeation flux is dependent on the I₂ concentration in the feed having an I₂/HI molar ratio. A long time PV experiment was carried out using I₂/HI molar ratio of 1 (in HI solution of 55.9%) in the feed at room temperature. It is expected that the permeation component in the permeate zone using the PV process was mainly H₂O, and H₂O permeation was constant with increasing operation time.     

Study on a new air-gap membrane distillation module for desalination

A new air-gap membrane distillation (AGMD) module for desalination with internal latent-heat-recovery which consisted of parallel hollow fiber membranes and heat exchange hollow fibers was successfully developed. The influences of feed flow rate, feed temperature and feed initial concentration on AGMD process were investigated. The vapor pressure polarization coefficient (η) was introduced to measure the reduction in the effective driving force for mass transfer with regard to the driving force imposed. Among all AGMD experiments, the maximum water vapor permeate flux (J_D) of 5.30 kg/m² h and the gained output ratio (GOR) of 5.70 were obtained. A theoretical model based on the mass and energy balances of the hot feed side was established to calculate the temperature and the local water vapor permeate flux distributions along the hollow fiber membrane, which showed that the temperature drop and local water vapor permeate flux drop were much larger at the upper part than those at the lower part of the membrane module in the hot feed side.     

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。