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.     

Ultrasound-Enhanced Recovery of Butanol/ABE by Pervaporation

The search for renewable sources of energy has led to renewed interests on the biochemical route for the production of butanol. Butanol production suffers from several drawbacks, mainly caused by butanol inhibition to the butanol-producing microorganism which makes it economically uncompetitive against the chemical process. One possible solution proposed is the in situ recovery of acetone–butanol–ethanol (ABE). Among the in situ recovery options, membrane processes like pervaporation have a great potential. Thus, the effects of temperature, feed concentration, and ultrasound irradiation on permeate concentration and permeation flux for the recovery of butanol/ABE by pervaporation from aqueous solutions were investigated in this study. In the butanol–water system, permeate butanol concentration as well as flux increased with an increase in temperature and butanol feed concentration. When pervaporation studies with ABE–water mixture were carried out at 60 °C for 2, 4, 8, 16, and 24 h, pervaporation profile revealed an optimal permeate concentration as well as permeation flux. Applications of ultrasound irradiation on pervaporation improved permeate concentration by about 23 g/L for both butanol and ABE. Ultrasound irradiation also improved butanol and ABE mass permeation flux by about 13 and 11 %, respectively.     

Separation of 2-butanol–water mixtures by pervaporation through PVA–NYL 66 blend membranes

Blend membranes of poly(vinyl alcohol) (PVA) and nylon 66 (NYL) were synthesized and crosslinked with glutaraldehyde (GA) and assessed for their suitability in dehydrating 2-butanol by pervaporation (PV). These blends were subjected to sorption studies to determine the extent of interaction and degree of swelling in pure liquids as well as binary mixtures. Wide-angle X-ray diffraction (WAXD) and thermal gravimetric analysis (TGA) were carried out to investigate changes in crystallinity and thermal stability, respectively. The effect of experimental parameters such as feed water concentration, permeate pressure and barrier thickness on membrane flux and selectivity was evaluated. The membranes were found to have good potential for breaking the azeotrope of 27.6 wt.% water with a flux of 3.07 kg/m² h 10 μm and selectivity of 26.5. Selectivity was found to improve with decreasing feed water concentration and increasing membrane thickness, whereas opposite trends were observed in case of flux. Higher permeate pressure caused a reduction in both flux and selectivity. These effects were clearly elucidated.     

Gas sparging to enhance permeate flux in ultrafiltration using hollow fibre membranes

This study focuses on the use of gas-liquid two-phase crossflow to overcome concentration polarisation in the ultrafiltration of macromolecular solutions as applied to hollow fibre membrane systems. The experimental work was conducted on a purpose built pilot-plant scale rig with albumin and dextran as the test media. The effect of gas injection on the permeate flux and membrane sieving coefficient was examined experimentally at different transmembrane pressures, feed concentrations and gas to liquid flow ratios.The results were encouraging, with flux enhancements of 20–50% obtained for dextrans and 10–60% for albumin, when air was injected into the system over the range of process variables examined. The sieving coefficient of albumin was considerably reduced when gas-liquid two-phase cross-flow was used. These results were compared to those obtained with tubular membrane systems, and an additional mechanism, based on physical displacement of the concentration polarisation boundary layer is proposed. The operational difficulty related to protein foaming is also discussed.     

Multicomponent pervaporation process for volatile aroma compounds recovery from pomegranate juice

The present work describes the possibility of using pervaporation process to recover the pomegranate aroma compounds from an actual pomegranate juice and a model aroma solution. Four different chemicals representing four major kinds of aroma compounds, namely, 3-methyl butanal, isopentyl acetate, n-hexanol and α-ionone, were utilized in this work. Three POMS membranes and two PDMS membranes were tested for pervaporation and compared for their separation performance. The influence of various operating parameters such as feed flow rate, feed temperature and permeate pressure on the permeation flux and aroma compounds enrichment factor was investigated. Feed flow rate was shown to have no significant effect on both total flux and aroma enrichment factor, whereas feed temperature and permeate pressure had highly significant effects. An increase in feed temperature led to higher flux and enrichment factor. As permeate pressure increased, the flux and enrichment factor of some aroma compounds decreased. Some of the aroma compounds showed higher enrichment factor at higher permeate pressures. Finally, the activation energy of permeation and the membrane permeability for each aroma compound were determined.     

Analysis of the slip effect on the permeate flux in membrane ultrafiltration

A method for predicting the mass transfer coefficient as well as the limiting permeate flux in membrane ultrafiltration has been found, based upon the boundary-layer theory which takes into account the slip velocity on the membrane surface. The theory presupposes the existence of a slip flow on a porous membrane surface, especially for the limiting permeate-flux operations. Further, the slip velocity increases with the size of the pores of the membrane, with feed velocity and also with feed concentration. The theory also showed that the permeate flux increases with the increase of the slip velocity. A considerable improvement in theoretical prediction of the permeate flux is expected if the slip flow effect is taken into consideration.     

Treatment of textile desizing wastewater by pilot scale nanofiltration membrane separation

Desizing wastewaters from the bleaching and dyeing industry of Hong Kong were treated by nanofiltration (NF) membrane separation on a pilot scale in the pressure controlled region. The two brown colored wastewaters had chemical oxygen demand (COD) of 14,000 mg l⁻¹ and 5430 mg l⁻¹, respectively. Permeate flux and COD retention were investigated in relation to transmembrane pressure drop, temperature, and feed-solution concentration. The permeate flux was found to increase significantly with transmembrane pressure drop and to decrease with feed concentration. Higher permeate flux was found for wastewater with higher pH. A minor increase in COD retention was found for the increase in transmembrane pressure drop as well as operating temperature. The COD retention was about 95% for wastewater with pH 10.2, and 80–85% for wastewater with pH 5.5. The difference in the results obtained for the two kinds of wastewater was attributed to their compositional difference that resulted from the desizing operation. Fouling of membrane is not a big concern for the NF membrane tested in treating this type of wastewater. The quality of the permeate is all above the discharge standard for foul sewer in Hong Kong. The experimental results are consistent with the theoretical analysis.     

Pervaporation performance of crosslinked polyethylene glycol membranes for deep desulfurization of FCC gasoline

An crosslinked polyethylene glycol (PEG) membrane was prepared for fluid catalytic cracking (FCC) gasoline desulfurization. Sulfur enrichment factor come to 4.75 and 3.51 for typical FCC gasoline feed with sulfur content of 238.28 and 1227.24 μg/g, respectively. Pervaporation performance of membranes kept stable within the long time run of 500 h, which indicated that crosslinked PEG membranes had the property of resisting pollution. Judging from chromatographic analysis, the membranes were more efficient for thiophene species. Effects of operation conditions including permeate pressure, feed temperature, feed flow rate and feed sulfur content level on the pervaporation performance were investigated. Permeation flux decreased with increasing permeate pressure while increased with the operating temperature increase. Sulfur enrichment factor increased firstly and decreased then when permeate pressure and temperature rose. The peak value occurred at 10.5 mm Hg and 358 K for model compounds feed (378 K for FCC gasoline feed). Arrhenius relationship existed between flux and operating temperature. Both sulfur enrichment factor and flux were shown to increase with increasing feed flow rate. Permeation flux increased while sulfur enrichment factor decreased as the feed sulfur content increased, but the influence of increasing sulfur content on pervaporation performance weakened when sulfur content come to 600 μg/g.     

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.     

Blended chitosan and polyvinyl alcohol membranes for the pervaporation dehydration of isopropanol

Homogeneous membranes were prepared by casting the solution of blended chitosan and polyvinyl alcohol (PVA) on a glass plate. The percent weight of chitosan in the membrane was varied from 0 to 100%. The membrane thickness was in the range of 15–30 μm. The membranes were heat treated at 150 °C for an hour. After that the membranes were crosslinked by glutaraldehyde and sulfuric acid in acetone aqueous solution. The membranes were tested at 30–60 °C for dehydration performance of 50–95% isopropanol aqueous solutions. At around 90% of isopropanol in the feed mixture, permeate flux increased whereas the percent of water in permeate tended to decrease when the feed temperature increased for all membranes, except that the water content in permeate from the membrane containing 75 wt.% chitosan remained constant. The swelling degree in water and the total flux increased with increasing chitosan content in membranes. The effect of temperature on permeate flux followed the Arrhenius relationship. The permeate flux decreased when isopropanol in the feed increased for all membranes. However, water content in permeate and isopropanol concentration in the feed formed complex relationship for different chitosan content membranes. Sorption did not appear to have significant effects on separation. The membrane containing chitosan 75% performed the best. For a feed solution containing 90% isopropanol at 60 °C, the permeate flux was 644 g/m² h with water content of nearly 100% in the permeate. At 55% isopropanol in the feed at 60 °C, the permeate flux was 3812 g/m² h. In the range of 55–95% of isopropanol in the feed, the water content in permeate was more than 99.5%. This membrane showed very excellent performance with good mechanical strength. It is promising to develop this membrane for industrial uses.     

Tubular ultrafiltration flux prediction for oil-in-water emulsions: analysis of series resistances

Using the resistance-in-series (RIS) approach to permeate flux modeling, a general relationship between permeate flux, transmembrane pressure, cross-flow velocity, and feed kinematic viscosity was developed for the tubular ultrafiltration (UF) of synthetic oil-in-water emulsions. The fouling layer resistance, R_f, was 63% of the total membrane resistance, R_m′; however, concentration polarization was the predominant factor controlling resistance in the tubular UF system. An explicit form of the resistance index, Φ, was postulated based on the observed interactions between Φ, cross-flow velocity and feed kinematic viscosity and the RIS model was modified to further describe the interactions between permeate flux and operational parameters. The modified model adequately predicted flux–pressure data over the range of experimental variables examined in this study. Additionally, a set point operating pressure was determined as a function of cross-flow velocity and feed viscosity to achieve a balance between polarization and total membrane resistance.     

醇／水混合液分离用聚乙烯醇复合膜的渗透汽化特性

制备了聚乙烯醇（ＰＶＡ）／聚丙烯睛（ＰＡＮ）渗透汽化复合膜，研究了交联剂用量、底膜结构、进料液组成、操作温度等因素对膜的渗透汽化性能的影响．发现ＰＶＡ／ＰＡＮ复合膜对水／醇混合液表现为水优先透过，进料液中乙醇浓度在６０～９９ｗｔ％的范围内，渗透通量Ｊｔ与温度之间符合Ａｒｒｈｅｎｉｕｓ关系，选择分离系数αＷ／Ｅ也随温度上升而增大．进料液为９５ｗｔ％的乙醇／水混合液时，７５℃下Ｊｔ高达３００～４５０ｇ／ｍ２ｈ，αＷ／Ｅ为８００～１１００．对异丙醇／水、异丁醇／水及甘油／水混合体系，复合膜显示出更为优秀的透过、分离性能．就膜的化学、物理结构与其渗透汽化性能间的关系进行了讨论．     

Micellar enhanced ultrafiltration of phenol in synthetic wastewater using polysulfone spiral membrane

The micellar enhanced ultrafiltration (MEUF) of phenol in synthetic wastewater using two polysulfone spiral membranes of 6- and 10-kDa molecule weight cut-off (MWCO) and cetylpyridinium chloride (CPC) as cationic surfactant was studied. The effects on the permeate flux, permeate and retentate concentrations of phenol and CPC of various factors in the practical application of MEUF were studied, including surfactant and phenol concentrations, retentate flux, operating pressure, temperature and electrolyte. It was found that these two membranes could adsorb free phenol so the concentration of permeate phenol was lower than that of free phenol. The retentate phenol concentration kept increasing, then decreased slightly with the increase of the feed CPC concentration. Retentate flux and temperature had great effect on the performance of MEUF, and operating pressure did not. The addition of sodium carbonate (Na₂CO₃) could increase the retentate phenol concentration and decrease the permeate concentrations of phenol and CPC significantly.     

The long-term studies of osmotic membrane distillation

The results of osmotic membrane distillation carried out for 2.5 years were presented in this work. The influence of the process conditions, such as temperature and brine concentration on the permeate flux, was investigated. The saturated NaCl solutions and distilled water were used as a stripping solution and feed, respectively. A continuous regeneration of stripping solution was conducted using a method of natural evaporation from the surface of Bia?ecki rings to the air surrounding the installation. The possibilities of application of Accurel PP S6/2 hydrophobic polypropylene membranes were tested. It was studied whether a saturation stripping solution does not cause scaling and wettability of membranes. It was found that most of the pores in the used membranes were non-wetted, and the salt retention over 99% was maintained during a study period. However, the obtained permeate flux was decreased by 10–20%. The SEM examinations revealed that it was caused by amorphous deposit, which was formed on the membrane surface on the brine side. The SEM–EDS analysis demonstrated that the deposit composition mainly included Si and O.     

Use of pervaporation to separate butanol from dilute aqueous solutions: Effects of operating conditions and concentration polarization

This study deals with the separation of n-butanol from aqueous solutions by pervaporation. The effects of feed concentration, temperature, and membrane thickness on the separation performance were investigated. Over the low feed butanol concentration range (0.03–0.4 wt%) studied, the butanol flux was shown to increase proportionally with an increase in the feed butanol concentration, whereas the water flux was relatively constant. An increase in temperature increased both the butanol and water fluxes, and the increase in butanol flux was more pronounced than water flux, resulting in an increase in separation factor. While the permeation flux could be enhanced by reducing the membrane thickness as expected for all rate-controlled processes, the separation factor was compromised when the membrane became thinner. The effect of membrane thickness on the separation performance was analyzed taking into account the boundary layer effect. This could not be fully attributed to the concentration polarization, which was found not significant enough to dominate the mass transport. A variation in the membrane thickness would vary the local concentration of permeant inside the membrane, thereby affecting the permeation of butanol and water differently. Thus, caution should be exercised in using permeation flux normalized by a given thickness to predict the separation performance of a membrane with a different thickness because the membrane selectivity can be affected by the membrane thickness even in the absence of boundary layer effect.     

Pervaporation dehydration of alcohol–water mixtures: Optimization for permeate flux and selectivity by central composite rotatable design

A central composite rotatable design (CCRD) of response surface methodology was used to analyze pervaporation performance of homogeneous poly(vinyl alcohol) (PVA) membranes. A regression model was developed for the pervaporation flux and selectivity as a function of the operating conditions: temperature, concentration and flow-rate. Dehydration experiments were performed on two different alcohol–water systems: isopropanol–water (IPA–water) and ethanol–water (Et–water) mixtures around their azeotropic concentrations. Based on preliminary experiments and CCRD design, the ranges of values of the operating conditions were selected: temperature 33–67 °C, feed flow-rate 46–114 L/h, and concentration 83–92 wt% for IPA and 93–98 wt% for Et in feed mixtures. A total of 20 pervaporation experiments were conducted for each alcohol–water system. Judged by the lack-of-fit criterion, the analysis of variance (ANOVA) showed the regression model to be adequate. From the regression analysis, the flux and selectivity were expressed with quadratic equations of temperature, feed concentration and flow-rate. The predicted flux and selectivity from the regression model were presented in 3D surface plots. For both alcohol–water systems, quadratic terms of temperature and feed alcohol concentration showed significant (p < 0.0001) influence on the flux and selectivity. A strong interaction effect of temperature and concentration was observed on the selectivity for the Et–water system. However, the interaction of flow-rate with temperature or concentration was found to be less significant. In order to optimize the pervaporation flux and selectivity of azeotropic alcohol–water mixtures, the desirability function approach was applied to analyze the regression model equations by commercial software. For the azeotropic IPA–water mixture (87.5 wt% IPA), the optimized dehydration variables were found to be 50.5 °C and 93.7 L/h for temperature and flow-rate, respectively. For the azeotropic Et–water mixture (95.5 wt% Et), the optimized temperature and flow-rate were found to be 57 °C and 89.2 L/h, respectively. Compared with experiments performed at optimized temperature and flow-rate, the predicted flux and selectivity of the azeotropic mixtures showed errors to be within 3–6%.     

Ceramic membrane ultrafiltration of anionic and nonionic surfactant solutions

The ultrafiltration of two types of surfactants, sodium dodecyl sulfate (SDS, anionic) and Tergitol NP-9 (nonylphenol polyethylene glycol ether, nonionic), using a 20 nm ZrO₂ tubular membrane was investigated. The influence of crossflow velocity, temperature, pressure, and surfactant concentration on the permeate flux, close to and above the critical micelle concentration (CMC), is reported. Permeate flux and surfactant retention were measured in order to evaluate concentration polarization and fouling phenomena, and also the variation of these parameters due to surfactant/membrane interactions. High surfactant retentions (60–70%) were achieved depending on the feed concentration.     

Concentrating the extract of traditional Chinese medicine by direct contact membrane distillation

This study applies direct contact membrane distillation (DCMD) to concentrating the extract of traditional Chinese medicine (TCM). The trans-membrane flux under various operation conditions was measured in real-time during concentration process. By decoupling the factors affecting the trans-membrane flux decline, it was found that the observed flux decline throughout the process could be attributed to the membrane fouling, the reduction of water vapor pressure and the increase of transport resistance at feed side. Analysis of the combined factors was given to show in detail the mechanism of flux decline. Factors that may affect the flux level, such as feed velocity, feed temperature and pretreatment were experimentally examined. Gas bubbling or sparging was introduced into DCMD system for reducing membrane fouling, and it was found that both gas–liquid two-phase flow at the feed side and gas back-washing within membrane module are effective ways to control membrane fouling.     

Dehydration of tetrafluoropropanol (TFP) by pervaporation via novel PBI/BTDA-TDI/MDI co-polyimide (P84) dual-layer hollow fiber membranes

A novel PBI/P84 co-polyimide dual-layer hollow fiber membrane has been specifically fabricated through the dry-jet wet phase inversion process, for the first time, for the dehydration pervaporation of tetrafluoropropanol (TFP). Polybenzimidazole (PBI) was chosen as the outer selective layer because of its superior hydrophilic nature and excellent solvent-resistance together with robust thermal stability, while P84 co-polyimide was employed as the inner supporting layer because of its good solvent-resistance and thermal stability. The PBI/P84 membrane exhibits superior water selectivity and relatively high permeation flux. At 60 °C, the PBI/P84 dual-layer hollow fiber membrane shows a permeation flux of 332 g/(m² h) and a separation factor of 1990 for a feed solution containing of 85 wt% TFP. The preferential water sorption and the significant diffusivity difference between TFP and water are the main causes of high separation factor. However, an increase in feed temperature will greatly increase the permeation flux but seriously decrease the water selectivity. The activation energy data verify that water can preferentially permeate the PBI membrane due to the strong water affinity of PBI and a much smaller molecular size of water.