Design and operation of an enhanced pervaporation device with static mixers

Pervaporation has a high potential for separating miscible solutions, particularly azeotropic mixtures. However, mass transfer limitations have long been a common concern in pervaporation device design. Therefore, in this work, we design a static mixer-based pervaporation device using water–ethanol separation as a model system and further develop computational fluid dynamics tools to investigate systematically all the influencing parameters. In the experiments, we use three-dimensional printed helical static mixers in the feed liquid channel to enhance mass transfer and implement a Sulzer pervaporation membrane for fast removal of water from ethanol. Using flow and mass-transfer simulations, we fit the membrane mass transfer coefficient and provide predictive models for optimal process design. Our pervaporation assembly exhibits promising performance and potential toward pervaporation processes for the removal of water from organics and is preferably scaled out by using stackable designs.     

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     

Pervaporation performance analysis and prediction—using a hybrid solution-diffusion and pore-flow model

A hybrid mathematic model for pervaporation is proposed which incorporates the concepts of solution-diffusion model and pore model. The model allows performance prediction as well as the establishment of the internal concentration and pressure profiles within the membrane. The model parameters specific to the particular membrane and mixture system are determined using liquid sorption and pervaporation experimental data. The model is experimentally examined using ethanol–water mixtures and poly(dimethyl siloxane)–poly(vinyldiene fluoride) (PDMS–PVDF) composite membranes. The characteristics of flux and separation factor predicted using the model are in fair agreement with the experimental data under various feed concentrations and downstream pressures for different membrane arrangements, including single-layer, reverse single-layer and double-layer PDMS–PVDF composite membranes. Internal profiles of pressure, concentration and component mole fraction can be established using the model. Concentration polarization phenomena for ethanol and water are located at membrane interfaces and vapor–liquid interfaces, respectively. Performances of several different membrane designs are compared using the model.     

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%.     

Crosslinked blended poly(vinyl alcohol)/N-methylol nylon-6 membranes for the pervaporation separation of ethanol–water mixtures

Crosslinked blended membranes of poly(vinyl alcohol) (PVA) and N-methylol nylon-6 were prepared either by thermal crosslinking at 180°C or by chemical crosslinking with maleic acid. The pervaporation performance for the separation of ethanol–water mixtures of these membranes was investigated in terms of feed concentration, PVA content, and crosslinking agent content. The pervaporation performance of two differently crosslinked membranes was strongly influenced by the nature of the crosslinkage. Significant improvement in the pervaporation separation index can be achieved for chemically crosslinked membranes. From the comparison between the pervaporation and sorption tests, it is suggested that, for hydrophilic membranes, sorption properties dominate the pervaporation performance at feed solutions of higher water content, while diffusion properties govern at feed solutions of higher ethanol content. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 317–327, 1998     

Mixed matrix membranes of Matrimid 5218 loaded with zeolite 4A for pervaporation separation of water–isopropanol mixtures

Mixed matrix membranes were prepared by incorporating zeolite 4A into polyimide of Matrimid 5218 using solution-casting technique. The fabricated membranes were characterized by scanning electron microscopy (SEM), differential scanning calorimeter (DSC) and thermo gravimetric analysis (TGA). It was found that the higher annealing temperature of 250 °C is more favorable to improve adhesion between zeolite and polymer phases. Effects of different parameters such as temperature (30–60 °C), water content in feed (10–40 wt.%), zeolite loading (0–15 wt.%) and polymer content (10 and 15 wt.%) on pervaporation dehydration of isopropanol were studied. Sorption studies were carried out to evaluate degree of swelling of the membranes in feed mixtures of water and isopropanol. The experimental results showed that both pervaporation flux and selectivity increase simultaneously with increasing the zeolite content in the membranes. The membrane containing Matrimid 5218 (10 wt.%)–zeolite 4A (15 wt.%) exhibits the highest separation factor (α) of 29,991 with a substantial permeation flux (J) of 0.021 kg/m² h at 30 °C for 10 wt.% of water in the feed. The PV performance was also studied in term of pervaporation separation index (PSI). Permeation flux was found to follow the Arrhenius trend over the investigated temperature range.     

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 Aqueous Ethanol Mixtures through Poly(Dimethyl Siloxane) Membranes

Abstract

The separation of ethanol/water mixtures by pervaporation with a poly (dimethyl siloxane) membrane has been studied. The membrane exhibited ethanol selectivity during all process runs. Investigations focused on the effects of temperature and permeate-side pressure on membrane transport with dilute ethanol feed solutions. An increase in temperature increased the flux exponentially but had little effect on selectivity. As the permeate-side pressure was increased, the flux decreased. Selectivity did not change appreciably over the pressure range evaluated. Studies also analyzed the effect of feed concentration on flux and selectivity. Flux increased and selectivity decreased as the ethanol feed concentration increased. The permeate concentration profile is superior to a standard vapor–liquid equilibrium curve at low ethanol feed concentrations.     

Separations of Hazardous Organics from Gas and Liquid Feedstreams Using Phosphazene Polymer Membranes

Abstract

In this paper the liquid-liquid and gas separation properties for the separation of hazardous organic feed streams using pervaporation and gas separation methods with poly[bis(phenoxy)phosphazene] based membranes are reported. Liquid transport behavior was determined using pervaporation techniques. The preliminary gas separations were studied using a mixed gas separation method which we have described previously. Using the membrane pervaporation technique, separation factors of 10,000 have been routinely achieved for the separation of methylene chloride from water. Other tests have shown similar results for the removal of hydrocarbon vapors from air. Membranes were prepared using solution casting techniques. Solvent evaporation rates during the casting and subsequent curing processes were controlled to provide a consistent membrane microstructure. These results suggest that polyphosphazene membrane technology could effectively be used in cleaning up air and ground water that has been contaminated with chlorinated hydrocarbons.     

Pervaporative Dehydration of Binary Ethanol/Water and Ternary Ethanol/Water/Methanol Mixtures Using a Methylated Silica Membrane: A Mechanistic Approach

The pervaporation properties of a methylated-silica membrane were studied on binary ethanol/water and ternary ethanol/water/methanol mixtures. The aim was to acquire a better understanding of the pervaporation mechanisms by studying the effects of feed temperature, permeate pressure, and feed composition on molecular transport. Emphasis was placed on the role of competitive adsorption and dragging and blocking effects between the components in the context of the adsorption-diffusion model. The results show the potential of the membrane for the coupled removal of water and methanol from bioethanol. This attractive application for process intensification was suggested for the first time in this paper.     

Thermo pervap: The next step in energy efficient pervaporation

Thermo pervaporation (PV) is a pervaporation process that makes use of low quality heat to recover or purify solvents from water. Based on this technology it is possible to integrate the condensation energy for the direct heating of the feed during pervaporation in one single module.This concept was experimentally investigated for the separation of ethanol from a mixture of ethanol-water. It was possible to obtain a heat recovery of 33% (meaning that 33% of the heat transferred to the feed stream is condensation heat) and fluxes up to 0.5 kg/m² h at high ethanol concentration.     

Hydrophilic hollow fiber membranes for water desalination by the pervaporation method

Hydrophilic ion-exchange membranes based on sulfonated polyethylene hollow fibers were manufactured, and their suitability for a water pervaporation process was studied for possible application in water desalination systems. The effects of the following parameters on the average water flux were determined: membrane properties (diameter (0.4–1.8 mm) and wall thickness (0.05–0.18 mm)); charge density (0.6–1.2 meq g⁻¹); and operating conditions (brine inlet temperature (30–68°C), air sweep velocity (0–6 m s⁻¹), and salt concentration in the feed brine (0–3 M)). A water flux of 0.8–3.3 kg m⁻² h⁻¹ was obtained using this type of hollow fiber with an inlet brine temperature of 25–65°C. It was found that, for our application, the optimal specifications for the ion-exchange hollow fibers were an outside diameter of 1.2 mm, a wall thickness of 0.1 mm, and an ion-charge density of about 1.0 meq g⁻¹. This information is required as basic data for the design of a prototype water desalination system based on a pervaporation system that uses this type of ion-exchange hollow fiber membrane.     

Separation and purification of isobutanol from dilute aqueous solutions by a hybrid hydrophobic/hydrophilic pervaporation process

In this study, a hybrid hydrophobic/hydrophilic pervaporation process was employed to separate and purify isobutanol from its dilute aqueous solutions. For this purpose, composite polydimethylsiloxane membranes were initially used for the recovery of isobutanol by hydrophobic pervaporation. Then the hydrophilic pervaporation with a composite polyvinyl alcohol membrane was utilized to separate water from the organic phase of the permeate stream of the hydrophobic pervaporation. The effect of feed flow rate on the performance of pervaporation was investigated. The resistance in series model was also applied to calculate the transport resistances through the composite membranes. It was observed that an enhancement in the feed flow rate led to higher permeation flux and selectivity of the more permeable component, while the flux of the less permeable component was almost constant. Also, the ratio of liquid boundary layer resistance to membrane layer resistance decreased by an increase in the feed flow rate. The isobutanol with a purity of higher than 99 wt.% was produced by the hybrid hydrophobic/hydrophilic pervaporation technique from a 2 wt.% aqueous isobutanol solution.     

Effect of operation conditions in the pervaporation of ethanol–water mixtures with poly(1‐trimethylsilyl‐1‐propyne) membranes

Poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) is known to show preferential permeation of ethanol in the pervaporation of ethanol–water mixture. Although this polymer presents good characteristics for the separation of organic–water solutions, operation conditions and membrane characteristics, such as thickness, affect its pervaporation performance. The effect of temperature and feed concentration on pervaporation was studied. During pervaporation of 10 wt % ethanol–water solution, the separation factor (α_H2O^EtOH) remains almost constant, whereas the permeation flux (F) increases exponentially with operation temperature. On the other hand, the separation factor decreases, whereas the permeation flux increases with ethanol content in the feed mixture. The membrane thickness also affects the performance of PTMSP polymer films: selectivity increases sharply with membrane thickness up to 50 μm, whereas it remains constant for thicker membranes. The permeation flux decreases with membrane thickness in the whole range studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94:1395–1403, 2004     

Pervaporative aroma compounds recovery from lemon juice using poly(octyl methyl siloxane) membrane

BACKGROUND: In this research, a pervaporation process was used to recover volatile aroma compounds from lemon juice using a poly(octyl methyl siloxane) membrane. The majority of previous studies have been with binary model feed systems, while the results with actual feed mixtures did not always match those with model feeds. In order to successfully optimize the pervaporation process, it is essential to work with actual fruit juice. The influences of various operating parameters such as feed flow rate, feed temperature and permeate pressure on the permeate flux and selectivity were investigated. For this purpose, three compounds that make a significant contribution to lemon juice aroma, namely, α‐pinene, β‐pinene and limonene were studied. RESULTS: It was shown that decreasing the permeate pressure increased both permeation flux and enrichment factor, while an increase in feed temperature increased the water flux more significantly than the aroma compounds flux, resulting in lower enrichment factor. Also, the results indicated that feed flow rate had no significant effect on the performance of the process. CONCLUSION: The membrane used was found to be very selective towards α‐pinene, β‐pinene and limonene. It can be concluded that pervaporation is an attractive technology for the recovery of lemon aroma compounds as it yields good separation and operates under mild conditions. Copyright © 2010 Society of Chemical Industry     

Synthesis and characterization of polyacrylamide‐grafted sodium alginate copolymeric membranes and their use in pervaporation separation of water and tetrahydrofuran mixtures

Polyacrylamide‐grafted sodium alginate (PAAm‐g‐Na‐Alg) copolymeric membranes have been prepared, characterized, and used in the pervaporation separation of 10–80 mass % water‐containing tetrahydrofuran mixtures. Totally three membranes were prepared: (1) neat Na‐Alg with 10 mass % of polyethylene glycol (PEG) and 5 mass % of polyvinyl alcohol (PVA), (2) 46 % grafted PAAm‐g‐Na‐Alg membrane containing 10 mass % of PEG and 5 mass % of PVA, and (3) 93 % grafted PAAm‐g‐Na‐Alg membrane containing 10 mass % of PEG and 5 mass % of PVA. Using the transport data, important parameters like permeation flux, selectivity, pervaporation separation index, swelling index, and diffusion coefficient have been calculated at 30°C. Diffusion coefficients were also calculated from sorption gravimetric data of water–tetrahydrofuran mixtures using Fick's equation. Arrhenius activation parameters for the transport processes were calculated for 10 mass % of water in the feed mixture using flux and diffusion data obtained at 30, 35, and 40°C. The separation selectivity of the membranes ranged between 216 and 591. The highest permeation flux of 0.677 kg/m² h was observed for 93% grafted membrane at 80 mass % of water in the feed mixture. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 272–281, 2002     

Pervaporation separation of water/dimethylformamide mixtures using poly(vinyl alcohol)‐g‐polyacrylamide copolymeric membranes

Grafted copolymeric membranes of poly(vinyl alcohol) with acrylamide (PVA‐g‐AAm) were developed and used in the pervaporation separation of water–dimethylformamide mixtures by varying the amount of water in the feed from 0 to 100%. From these data, the permeation flux, pervaporation separation index, diffusion coefficient, swelling index, and separation selectivity were calculated at 25, 35, and 45°C. The Arrhenius activation parameters for permeation flux ranged between 22 and 63 kJ/mol, while the activation energy for diffusion ranged between 23 and 67 kJ/mol. Separation selectivity was between 15 and 22. The highest permeation flux of 0.459 kg m^?2 h^?1 was obtained for the 93% grafted membrane at 90% of water in the feed mixture. The results are discussed using the principles of the solution–diffusion model. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 273–282, 2002     

POMS Membrane for Selective Separation of Ethanol from Dilute Alcohol-Aqueous Solutions by Pervaporation

Lignocellulosic biomass has potential as an alternative to corn as starting material for the production of ethanol for the development of non-fossil fuel energy sources. In this case, low concentration bioethanol is gained by yeast fermentation and it has to be efficiently recovered and concentrated. For this purpose pervaporation separation of dilute alcohol-aqueous solutions was carried out using a poly(octhylmethyl siloxane) [POMS] membrane. The effect of different process parameters (feed composition, feed temperature, feed flow rate, permeate pressure) on pervaporation performance were investigated and discussed in terms of the separation factor and the total flux. The membrane studied was ethanol to water selective at ethanol feed concentrations lower than 2.5% w/w, while the highest permeability was achieved at feed temperature of 95°C.     

Pervaporative separation of bioethanol produced from the fermentation of waste newspaper

In this study, a hydrophobic polymeric polydimethylsiloxane (PDMS) membrane was used for the pervaporative separation of bioethanol produced from fermentation of lignocellulosic biomass (waste newspaper) and glucose. As a preliminary study, the pervaporation permeation performance showed strong dependence on feed concentration and temperature. The pervaporation of bioethanol produced by the fermentation of waste newspaper by Saccharomyces cerevisiae decreased process performance. However, the process performance was restored reversibly by water cleaning. The pervaporative separation of bioethanol from the fermentation of waste newspaper was carried out without any significant decreasing process performance in the study.     

碳分子筛填充硅橡胶膜用于渗透蒸发分离稀醋酸-水溶液

From the reference[1] it is known that the addition of silicalite-1 in silicone rubber membranes results in an increase of both flux and selectivity for alcohol in the separation of alcohol/water by pervaporation.In order to enhance performance of pervaporation toward the aqueous solution of acetic acid,incorporation of carbon molecular sieve(CMS)into a PDMS membrane was investigated. CMS is widely used in adsorption processes because of its high selectivity toward certain compounds[2]. It was assumed that the flux and selectivity of pure PDMS membrane could be enhanced owing to the preferential adsorption of CMS to organics.CMS content in the membrane and several important pervaporation operation parameters, including feed concentration of acetic acid, and feed temperature, were investigated.