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.     

Microstructure of carbon molecular sieve membranes and their application to separation of aqueous bioethanol

Pyrolytic carbons were fabricated from a Kapton precursor. The microstructure of the carbon molecular sieve membranes (CMSMs) was examined by means of sorption tests using pure liquid sorbates of different molar volumes and with the application of positron annihilation lifetime spectroscopy (PALS). The pore sizes of the CMSMs were calculated by PALS and our recently proposed equation relating positron lifetime with free volume radius. The mean pore radius in the CMSMs was demonstrated to be smaller than 3 Å. Their ability to separate water from bioethanol was determined. Results of aqueous bioethanol sorption showed evident molecular sieving behavior of the CMSMs despite their hydrophobic surface. This behavior became significant at a high pyrolysis end temperature of 700 °C, at which the carbon content was high. The c700 membrane delivered a high permeation flux of 1199 g/m² h and a high separation factor of 683. This performance suggests that CMSMs have more potential to separate water from bioethanol through pervaporation or vapor permeation than organic membranes.     

Pressure-assisted self-assembly technique for fabricating composite membranes consisting of highly ordered selective laminate layers of amphiphilic graphene oxide

We prepare highly ordered flexible layers of graphene oxide (GO) on modified polyacrylonitrile substrates by the pressure-assisted self-assembly technique. This composite membrane shows excellent performance during the pervaporation separation of a 70 wt.% isopropyl alcohol (IPA)/water mixture: 99.5 wt% water in permeate and 2047 g m⁻² h⁻¹ permeation flux. Despite the specific GO deposition increase from 4.3 to 43.3 × 10⁻⁵ g cm⁻² (ninefold layer thickness growth), its effect on the permeation flux is not significant, as manifested by only a little decrease in the flux. At 70 °C feed temperature, the permeate water concentration remains 99.5 wt% and the permeation flux reaches 4137 g m⁻² h⁻¹. The high selectivity may be due to the dense GO film consisting of highly ordered and packed laminates, allowing water but inhibiting IPA molecules to pass through. GO is demonstrated to be amphiphilic: water molecules adsorb first at the hydrophilic edge (hydroxides) and then rapidly diffuse through the hydrophobic core (mainly carbon), forming a water passage channel that promotes high permeation flux. When water molecules permeate through the GO layers, they accumulate and form a monolayer structure that pushes the successive layers away from each other, leading to widening of the d-spacing.     

Concentration of glycerol from dilute glycerol wastewater using sweeping gas membrane distillation

In this work, experimental results for the concentration of dilute glycerol wastewater using membrane distillation (MD) with a microporous hydrophobic flat-sheet PTFE membrane are reported. Experiments were performed using the sweeping gas mode of the MD (SGMD) process. The effects of various operating variables, such as feed temperature, glycerol concentration in aqueous phase, feed flow rate and sweeping gas flow rate were studied. A Taguchi analysis has been performed on the experimental results which determined the effects and contribution of each of the factors on the distillate flux and the interactions between the operating variables. Results showed that the most influential factor was feed temperature. The second significant contribution was observed for the sweeping gas flow rate. Feed concentration had a negative effect on the distillate flux. At optimum conditions (i.e. 65 °C, 400 mL/min, 1 mass%, and 0.453 Nm³/h), the Taguchi model predicted the value of the response (the distillate flux) as 20.93 L/m² h, which had good agreement with the experimental results.     

Study of pervaporation for dehydration of caprolactam through PVA/nano silica composite membranes

We investigated nano silica/PVA composite membranes to propose an improved caprolactam pervaporation (PV) dehydration process. The membranes were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and contact angle measurement. Compared with the pure PVA membranes, the nano silica/PVA composite membranes showed different surface morphologies with enhanced hydrophilicity because of their unique formation. To evaluate PV performance and mechanism, we assessed the permeation flux, separation factor, diffusivity/sorptivity selectivity, and activation energy of the composite membranes. The evaluated results indicate that the nano silica/PVA composite membranes induced a breakthrough in the dehydration of a caprolactam-water mixture with a maximum flux of 3.8 kg m^? 2 h^? 1 and an acceptable separation factor of 150.     

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.     

Evaluation of commercial PTFE membranes in desalination by direct contact membrane distillation

In this study, nine flat-sheet commercially available hydrophobic PTFE membranes were used in desalination by direct contact membrane distillation and their characteristics were investigated under different operating conditions including feed temperature, feed flow rate, cold stream flow rate, and feed concentration. Membrane properties, i.e. pore size, thickness, support layer, and salt rejection were also studied. Moreover, membrane module designs including flow arrangements (co-current, counter-current and tangential) for process liquid and depth both on hot and cold sides were tested experimentally. Finally, the long-term performance of the selected membranes for direct contact membrane distillation as a stand-alone desalination process was investigated. The results indicated that increasing feed temperature, hot feed flow rate, and module depth on the cold side led to increase permeate flux. On the other hand, increasing membrane thickness and module depth on the hot side (at constant flow rate) had negative effects on the flux. The highest permeation flux and salt rejection was achieved when the membranes with a pore size of 0.22 μm were used in the cross-current follow arrangement of hot and cold streams. In addition, the requirements for support layer for a successful DCMD process has been extensively discussed.     

Development of novel grafted hybrid PVA membranes using glycidyltrimethylammonium chloride for pervaporation separation of water–isopropanol mixtures

Tetraethylorthosilicate incorporated hybrid poly(vinyl alcohol) membranes were grafted with glycidyltrimethylammonium chloride (GTMAC) in different mass%. The resulting membranes were subjected to physico-chemical investigations using Fourier transform infrared (FTIR) spectroscopy, wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA) and scanning electron microscopy (SEM). The effects of grafting and feed composition on pervaporation performance of the membranes were systematically investigated. The membrane containing 30 mass% of GTMAC exhibited the highest separation selectivity of 1570 with a flux of 1.92 × 10^?2 kg/m² h at 30 °C for 10 mass% of water in the feed. The total flux and flux of water are almost overlapping each other, manifesting that these membranes could be used effectively to break the azeotropic point of water–isopropanol mixtures. From the temperature dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. The activation energy values obtained for water permeation (E_pw) are two to three times lower than those of isopropanol permeation (E_pIPA), suggesting that the developed membranes have higher separation ability for water–isopropanol system. The E_p and E_D values ranged between 63.73 and 33.07, and 62.78 and 32.75 kJ/mol, respectively. The positive heat of sorption (ΔH_s) values was obtained for all the membranes, suggesting that Henry's mode of sorption is predominant in the process.     

Application of response surface methodology for modeling and optimization of membrane distillation desalination process

In this work, response surface methodology (RSM) was applied for modeling and optimization of operating parameters for water desalination by direct contact membrane distillation (DCMD) process using polypropylene membrane (PP) with low pore size. Operating parameters including vapor pressure difference, feed flow rate, permeate flow rate and feed ionic strength were selected and the optimum parameters were determined for DCMD permeate flux. The developed model for permeate flux response was statistically validated by analysis of variance (ANOVA) which showed a high value coefficient of determination value (R² = 0.989). The obtained optimum operating parameters were found to be 0.355 × 10⁵ Pa of vapor pressure difference, feed flow rate of 73.6 L/h, and permeate flow rate of 17.1 L/h and feed ionic strength of 309 mM. Under these conditions, the permeate flux was 4.191 L/(m² h). Compared to a predicted value, the deviation was 3.9%, which confirms the validity of the model for the DCMD process desalination optimization. In terms of product water quality, the DCMD process using hydrophobic PP membrane can produce high quality of water with low electrical conductivity for all experimental runs.     

Processing of alumina-coated clay–diatomite composite membranes for oily wastewater treatment

Crack-free alumina-coated clay–diatomite composite membranes were successfully prepared by a simple pressing and dip-coating route using inexpensive raw materials at a temperature as low as 1000 °C in air. The changes of porosity, flexural strength, pore size, flux, and oil rejection rate of the membranes were investigated while changing the diatomite content. A simple burn-out process subjected to the used membranes in air completely recovered the specific surface area, steady state flux, and oil rejection rate of the virgin membranes. The recycled membranes showed an exceptionally high oil rejection rate (99.9%) with a feed oil concentration of 600 mg/L at an applied pressure of 101 kPa. The typical porosity, pore size, flexural strength, oil rejection rate, and steady state flux of the recycled alumina-coated clay–diatomite composite membrane were 36.5%, 0.12 μm, 32 MPa, 99.9%, and 6.91×10⁻⁶ m³ m⁻² s⁻¹, respectively, at an applied pressure of 101 kPa.     

Enhanced water desalination performance through hierarchically-structured ceramic membranes

Developments of membrane water desalination are impeded by low water vapor flux across the membrane. We present an innovative membrane design to significantly enhance the water vapor flux. A bilayer zirconia-based membrane with a thick hierarchically-structured support and a thin functional layer is prepared using a combined freeze drying tape casting and screen printing method. The hierarchically-structured YSZ support has a porosity of 42.6%, pores of 4.5 μm or larger, and a relatively low tortuosity of 1.58 along the thickness direction. The bilayer membrane is then converted from naturally hydrophilic to hydrophobic via grafting with a fluoroalkylsilane. A water flux of 28.7 Lm⁻² h⁻¹ and a salt rejection of 99.5% are achieved by exposing the functional layer to 80 °C salt water of 2 wt.% NaCl and the support layer to 20 °C distilled water. These results are the best performing ones for ceramic membranes in direct contact membrane distillation operation.     

Synthesis and characterization of PVA/PES thin film composite nanofiltration membrane modified with TiO2 nanoparticles for better performance and surface properties

Novel polyethersulfone (PES)/poly (vinyl alcohol) (PVA)/titanium dioxide (TiO₂) composite nanofiltration membranes were prepared by dip-coating of PES membrane in PVA and TiO₂ nanoparticles aqueous solution. Glutaraldehyde (GA) was used as a cross-linker for the composite polymer membrane in order to enhance the chemical, thermal as well as mechanical stabilities. TiO₂ nanoparticles with different concentrations (0, 0.05, 0.1, 0.5 wt.%) were coated on the surface of PVA/PES composite membrane. The morphological study was investigated by atomic force microscopy (AFM), scanning surface microscopy (SEM) and along with X-ray diffraction (XRD). In addition, the membranes performances, in terms of permeate flux, ion rejection and swelling factor were also investigated. It was found that the increase in TiO₂ solution concentration can highly affect the surface morphology and filtration performance of coated membranes. The contact angle measurement and XRD studies indicated that the TiO₂ nanoparticles successfully were coated on the surface of PVA/PES composite membranes. However, rougher surface was obtained for membranes by TiO₂ coating. The filtration performance data showed that the 0.1 wt.% TiO₂-modified membrane presents higher performance in terms of flux and NaCl salt rejection. Finally, TiO₂ modified membranes demonstrated the lower degree of swelling.     

CO2-tolerant Ni-La5.5WO11.25-δ dual-phase membranes with enhanced H2 permeability

Enhancing the ambi-polar conductivity of the ceramic hydrogen permeable membrane by introducing an electron conductive metallic phase is quite effective, which is helpful for the hydrogen permeation flux improvement. To develop CO₂-tolerant hydrogen permeable membranes with better hydrogen permeability, Ni-La_5.5WO_11.25-δ (Ni-LWO) cermet membranes are fabricated. The alkaline earth metal-free ceramic LWO is used as the main proton-conductive phase and Ni is used as the main electron-conductive phase. The Ni-LWO membrane exhibits good chemical stability in CO₂-containing atmosphere since its hydrogen permeability maintains well in the measurement for about 180 h. Compared with the LWO ceramic membrane, the hydrogen permeability of the Ni-LWO membrane has been improved significantly. The Ni/LWO ratio has great impact on the performance of the cermet membrane. Meanwhile, among all the dual-phase Ni-LWO membranes with different Ni/LWO volume ratios, the membrane with 60 vol% Ni shows the highest hydrogen permeation flux of 0.18 ml min⁻¹ cm⁻² at 1000 °C when the feed gas contains 50% H₂.     

Polysiloxaneimide membranes for removal of VOCs from water by pervaporation

For the separation of volatile organic compounds (VOCs) from water by pervaporation, three polysiloxaneimide (PSI) membranes were prepared by polycondensation of three aromatic dianhydrides of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA), 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA), and pyromellitic dianhydride (PMDA) with a siloxane‐containing diamine. The PSI membranes were characterized using ¹H‐NMR, ATR/IR, DSC, XRD, and a Rame‐Hart goniometer for contact angles. The degrees of sorption and sorption selectivity of the PSI membranes for pure organic compounds and organic aqueous solutions were investigated. The pervaporation properties of the PSI membrane were investigated in connection with the nature of organic aqueous solutions. The effects of feed concentration, feed temperature, permeate pressure, and membrane thickness on pervaporation performance were also investigated. The PSI membranes prepared have high pervaporation selectivity and permeation flux towards hydrophobic organic compounds. The PSI membranes with 150‐μm thickness exhibit a high pervaporation selectivity of 6000–9000 and a high permeation flux of 0.031–0.047 kg/m² h for 0.05 wt % of the toluene/water mixture. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2691–2702, 2000     

Experimental investigation and mathematical modeling of oxygen permeation through dense Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) perovskite-type ceramic membranes

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) perovskite powder was synthesized via EDTA/citrate complexation method. BSCF membranes were formed by pressing powder at 400 MPa and sintering at 1100 °C for 10 h. XRD patterns showed that a high pure powder with cubic structure was obtained. SEM micrographs revealed that the membranes are dense with large grains. Effects of temperature, feed and permeate side oxygen partial pressures, flow rates and membrane thickness on oxygen permeation flux were studied experimentally. A Nernst–Planck based mathematical model, including surface exchange kinetics and bulk diffusion, was developed to predict oxygen permeation flux. Considering non-elementary surface reactions and introducing system hydrodynamics into the model resulted in an excellent agreement (RMSD = 0.0617, AAD = 0.0487 and R² = 0.985) between predicted and measured fluxes. The results showed that oxygen permeation flux increases with temperature, feed side oxygen partial pressure and flow rates, however decreases with permeate side oxygen partial pressure and membrane thickness. Contribution of feed side surface exchange reactions, bulk diffusion and permeate side surface exchange reactions resistances in the total resistance are in the range of 8–32%, 10–81% and 11–59%, respectively. Permeation rate-limiting step was determined using the membrane dimensionless characteristic thickness.     

Poly(octylmethylsiloxane)/oleyl alcohol supported liquid membrane for the pervaporative recovery of 1-butanol from aqueous and ABE model solutions

Supported liquid membranes (SLM) composed of oleyl alcohol (OA) and poly(octylmethylsiloxane) (POMS) in microporous flat sheets were investigated for the pervaporation of 1-butanol. Water contact angle and partition coefficients were used to characterize the SLMs. Optimum pervaporation performance was attained at 30 wt% OA SLM wherein high separation factor (α = 279) and total flux (J_T = 95.9 g/(m² h)) were achieved from 2.5% (w/v) 1-butanol/water feed, at 60 °C. In these conditions, 27% reduction in J_T was observed when fed with model fermentation broths but remained highly selective toward 1-butanol (α = 76.4). SLM stability was demonstrated with <4% LM loss after operation.     

Effect of additives on the properties and performance of cellulose acetate derivative membranes in the separation of isopropanol/water mixtures

In this work, various cellulose acetate (CA) membranes for pervaporation were prepared by the incorporation of different additives, i.e. polyethylene glycol-600 (PEG-600), propylene glycol (PG), and ethylene glycol (EG) to enhance the separation of isopropanol (IPA)/water mixtures. These membranes were characterized by FTIR, DSC, TGA, SEM and UTM. Each additive was responsible for its characteristic effect on the membrane morphology, mechanical strength, permeation flux and separation factor. The SEM micrograph showed that the additives were evenly dispersed in the membrane matrix with the formation of dense membranes. The UTM tests for the membrane reveled that both the Young's Modulus and tensile strength increased with the increase in additive contents. TGA studies for the CA/PEG blend membrane exhibited the highest thermal stability as compared to the CA/PG and CA/EG blends. For each of these synthesized membranes, the separation factor decreased while the permeation flux increased with the increase in additive contents, while the CA/PG membrane with 20 wt.% additive content showed highest permeation flux of 452.27 g/m²h.     

Separation of Phenol from Aqueous Streams by a Composite Hollow Fiber Based Pervaporation Process Using Polydimethyl siloxane (PDMS)/Polyether-Block-Amide (PEBA) as Two-Layer Membranes

Abstract

In order to simultaneously achieve both high permselectivity and permeability (flux) for the recovery of aromatic compounds such as phenol from aqueous streams, a composite organophilic hollow fiber based pervaporation process using PDMS/PEBA as two-layer membranes has been developed. The process employed a hydrophobic microporous polypropylene hollow fiber, having thin layers of silicones (PDMS) and PEBA polymers coating on the inside diameter. The composite membrane module is used to investigate the pervaporation behavior of phenol in water in a separate study; and that of a mixture of phenol, methanol, and formaldehyde in an aqueous stream (a typical constituent of wastewater stream of phenol-formaldehyde resin manufacturing process) in another study. The fluxes of phenol and water increase relatively linearly with increasing concentration especially at low feed concentration, and exhibit a near plateau with further increase in concentration. As a result, the phenol/water separation factor decreases as the feed concentration increases. Significant improvement in phenol/water separation factor and phenol flux is achieved for this two-layer (PDMS/PEBA) membranes as compared to that achieved using only PDMS membrane. The phenol and water fluxes and the separation factor are highly sensitive to permeate pressure as all decrease sharply with increase in permeate pressure. For this membrane, an increase in temperature increases the separation factor, and also permeation fluxes of phenol and water. An increase in feed-solution velocity does not have a significant effect on phenol and water fluxes, and also on the separation factor at least within the range of the feed-solution velocity considered. In the study of pervaporation behavior of a typical constituent of wastewater stream of phenol-formaldehyde resin manufacturing process, phenol permeation shows a much higher flux and a higher increase in flux with increase in concentration is also exhibited as compared to that exhibited by methanol permeation. This thus indicates that the membrane is more permeable to phenol than to methanol and formaldehyde.     

Pervaporation of water/alcohol mixtures through chitosan/cellulose acetate composite hollow‐fiber membranes

For the purpose of separating aqueous alcohol by the use of pervaporation technique, a composite membrane of chitosan (CT) dip‐coated cellulose acetate (CA) hollow‐fiber membranes, CT‐d‐CA, was investigated. The effects of air‐gap distance in the spinning of CA hollow‐fiber membranes, chitosan concentration, and sorts of aqueous alcohol solutions on the pervaporation performances were studied. Compared with unmodified CA hollow‐fiber membrane, the CT‐d‐CA composite hollow‐fiber membrane effectively increases the permselectivity of water. The thickness of coating layer increases with an increase in chitosan concentration. As the concentration of chitosan solution increased, the permeation rate decreased and the concentration of water in the permeate increased. In addition, the effects of feed composition and feed solution temperature on the pervaporation performances were also investigated. The permeation rate and water content in permeate at 25°C for a 90 wt % aqueous isopropanol solution through the CT‐d‐CA composite hollow‐fiber membrane with a 5‐cm air‐gap distance spun, 2 wt % chitosan dip‐coated system were 169.5 g/m² h and 98.9 wt %, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1562–1568, 2004     

Effects of hypochlorite exposure on flux through polyethersulphone ultrafiltration membranes

Polyethersulphone ultrafiltration membranes with a nominal molecular weight cut off of 10 kDa were degraded in solutions of sodium hypochlorite over a range of pH values at 55 °C to achieve exposure measured in ppm-days of chlorine exposure. The degraded membranes were tested, using an ÄKTAcrossflow? system, for clean water flux, demineralised whey flux and protein rejection. The water fluxes for three membranes (new, 10,000 ppm-day pH 12, and 10,000 ppm-day pH 9) were found to be about 100, 200 and 400 L m^?2 h^?1, respectively with cross flow at 1 bar transmembrane pressure. However whey fluxes were about 23, 5, and 6 L m^?2 h^?1 for the same three membranes. Size exclusion chromatography of the permeates showed significant permeation of α-lactalbumin and β-lactoglobulin through membranes degraded at pH 9 for 20,000 ppm-days, while almost no permeation was found for degradation at pH 12.These results show that hypochlorite degradation affected fluxes by at least two mechanisms. It was likely that membrane pitting increased the pore size causing increased water flux and reduced protein rejection. However hypochlorite also seemed to alter the membrane surface properties, causing the protein to form a less permeable layer that reduced the flux of whey.