The influence of the porous support layer of composite membranes on the separation of binary gas mixtures

Thin film composite (TFC) membranes exhibit a high flux for gas and vapor permeation and are viable for a wide range of applications. The high flux may also increase the importance of the resistance of the porous support structure depending on the application and process conditions. A comprehensive modeling approach for TFC membranes is introduced, which considers boundary layer resistances near the membrane surface, solution-diffusion through the coating, and the influence of the porous sublayer. Permeation through the support structure is described by the dusty gas model (DGM) with the support treated as a two-layered structure with a dense but porous skin and a more open substructure.The model accurately describes experimental data on TCE/nitrogen separation using a sweep gas on the permeate side very well. The main resistance towards TCE permeation through two different membranes tested is the porous support. It is shown that changes in the support morphology can greatly enhance the performance of the composite membranes. Model calculations were also performed for vacuum assisted permeation. The pressure drop across the support is considerable depending on the coating thickness. The TCE permeation is again dominated by the resistance of the support layer, which can be reduced by altering the morphological parameters of the structure.The proposed model is able to describe the performance of the composite membrane and to identify optimum process conditions for given performance characteristics. It can be used to aid in the development of membrane structures for enhanced performance.     

Preparation of stable MCM-48 tubular membranes

Stable mesoporous membranes with a cubic structure, based on the MCM-48 material, were successfully prepared on alumina supports by hydrothermal synthesis, starting from sols having both CTABr and TPAOH structure directing agents. The inclusion of a zeolite (MFI-type) precursor during membrane synthesis led to partial zeolite incorporation into the porous structure, giving rise to a hydrothermally stable membrane. The mean pore diameter of the membrane was 2.5 nm, and permeation experiments confirmed that transport across the membrane was governed by Knudsen diffusion and that there were no pinholes.     

Investigation of gas transport through porous membranes based on nonlinear frequency response analysis

Theoretical development of a new experimental method for investigation of mass transport in porous membranes, based on the principle of the modified Wicke-Kallenbach diffusion cell and the nonlinear frequency response analysis is presented. The method is developed to analyze the transport of a binary gas mixture in a porous membrane. The mixture is assumed to consist of one adsorbable and one inert component. Complex mass transfer mechanism in the membrane, where bulk or transition diffusion in the pore volume and surface diffusion take place in parallel, is assumed. Starting from the basic mathematical model equations and following a rather standardized procedure, the frequency response functions (FRFs) up to the second order are derived. Based on the derived FRFs, correlations between some characteristic features of these functions on one side, and the whole set of equilibrium and transport parameters of the system, on the other, are established. As the FRFs can be estimated directly from different harmonics of the measured outputs, these correlations give a complete theoretical basis for the proposed experimental method. The method is illustrated by quantifying the transport of helium (inert gas) and C₃H₈ and CO₂ (adsorbable gases) through a porous Vycor glass membrane.     

Pore Modification in Porous Ceramic Membranes With Sol-Gel Process and Determination of Gas Permeability and Selectivity

Summary: The aim of the study was to investigate the variation in total surface area, porosity, pore size, Knudsen and surface diffusion coefficients, gas permeability and selectivity before and after the application of sol-gel process to porous ceramic membrane in order to determine the effect of pore modification. In this study, three different sol-gel process were applied to the ceramic support separately; one was the silica sol-gel process which was applied to increase porosity, others were silica-sol dip coating and silica-sol processing methods which were applied to decrease pore size. As a result of this, total surface area, pore size and porosity of ceramic support and membranes were determined by using BET instrument. In addition to this, Knudsen and surface diffusion coefficients were also calculated. After then, ceramic support and membranes were exposed to gas permeation experiments by using the CO₂ gas with different flow rates. Gas permeability and selectivity of those membranes were measured according to the data obtained. Thus, pore surface area, porosity, pore size and Knudsen diffusion coefficient of membrane treated with silica sol-gel process increased while total surface area was decreasing. Therefore, permeability of ceramic support and membrane treated with silica sol-gel process increased, and selectivity decreased with increasing the gas flow rate. Also, surface area, porosity, pore size, permeability, selectivity, Knudsen and surface diffusion coefficients of membranes treated with silica-sol dip coating and silica-sol processing methods were determined. As a result of this, porosity, pore size, Knudsen and surface diffusion coefficients decreased, total surface area increased in both methods. However, viscous flow and Knudsen flow permeability were detected as a consequence of gas permeability test and Knudsen flow was found to be a dominant transport mechanism in addition to surface diffusive flow owing to the small pore diameter in both methods. It was observed that silica-sol processing method had lower pore diameter and higher surface diffusion coefficient than silica-sol dip coating method.     

Gas permeation characteristics of a hydrogen selective supported silica membrane

A highly hydrogen permeable silica membrane, referred to as Nanosil, was obtained by chemical vapor deposition of a thin SiO₂ layer on a porous Vycor glass support. This composite membrane showed good permeance (10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹) for the small gas molecules (He, Ne, and H₂) at 873 K with high selectivity (10⁴) over other larger gas molecules (CO₂, CO, and CH₄). The characteristics of gas transport on the Vycor and Nanosil membrane were investigated with several gas diffusion models. The experimental gas permeation data on Vycor glass could be explained by the occurrence of Knudsen diffusion in parallel with surface diffusion. The permeance of the small gas molecules (He, Ne, and H₂) on the Nanosil membrane was activated, and increased as temperature increased. However, this permeance was limited at high temperature because of the limited permeance on the Vycor support. The gas permeance on the deposited silica layer was obtained by applying a series analysis of gas permeation on the combined silica layer and Vycor support composite system. The order of permeance through the silica layer was He>H₂>Ne which was the same as that through vitreous silica glass, but occurred with lower activation energies. The order of permeation of these small gas molecules did not follow either mass or molecular size but could be explained using a statistical gas permeance model.     

The catalytic oxidation of H2S in a stainless steel membrane reactor with separate feed of reactants

The oxidation of H₂S is studied in a membrane reactor with separate feed of reactants. As a novelty in the concept of separate introduction of the reactants, a sintered stainless steel membrane is used, because this type of material is easy to integrate into the reactor, and the catalytic properties of the membrane itself makes the often difficult activation superfluous. The macropore membrane (d_p>1 μm) is characterized in the absence of a pressure difference by diffusion and conversion experiments for determining the porosity to tortuosity ratio. Because the relative large pore diameter of the membrane, Knudsen diffusion is of minor importance and the last important structure parameter of the membrane, B₀, is determined in a permeation experiment.This membrane reactor is also studied in the presence of a pressure difference over the membrane; a situation where both diffusion and convection affect the overall mass transfer. For this reason, a model based on the dusty gas model (DGM) is used, where the structure parameters are estimated from isobaric conversion and permeation measurements and the physical constants are taken from literature. This model predicts the conversion in the presence of a pressure difference very well, without using fit parameters. Generally, it can be concluded that the performance of this sintered metal membrane reactor can be described and operated equally compared to ceramic membrane reactors with separate feed of reactants. Regarding the fact that there are several other types of sintered metals (e.g. nickel, silver or platinum), this type of membrane reactor seems to be applicable for several other chemical applications.     

Separation of organic binary mixtures by pervaporation

Pervaporation is a membrane separation process which has the inherent advantage of excellent selectivity for a number of mixtures that are otherwise difficult to separate (e.g. azeotropic mixtures or mixtures of liquids with only small differences in vapor pressures). Important parameters for pervaporation are the operating pressure on the permeate side and the temperature drop at the membrane interface caused by the phase change from liquid to vapor. This paper presents a mathematical model for the mass transport of binary mixtures within the membrane. The calculations are based on the transport equations of Shelden and co-workers [1]. These equations were solved without any simplifying assumptions and tested experimentally with benzene—cyclohexane mixtures. The limitations of the mathematical model and possible methods of improving it are discussed. The temperature drop at the membrane interface and its influence on the rate of permeation are also examined.     

Influence of the transport direction on gas permeation in two-layer ceramic membranes

Experimental and theoretical results of studying gas permeation through porous membranes are presented. In order to mimic an asymmetric membrane two porous ceramic disks with different pore radii were arranged in series. Besides the possibility to perform conventional permeation measurements, the applied experimental setup permits the determination of the pressure at the interface between the two discs. To predict the performance of the asymmetric structure, in preliminary experiments structure parameters were determined for both membranes separately. For the same total pressure difference across the two-disk arrangement, different interlayer pressures and fluxes were predicted and detected experimentally depending on the flow direction.     

Highly hydrothermally stable microporous silica membranes for hydrogen separation

Fluorocarbon-modified silica membranes were deposited on gamma-Al2O3/alpha-Al2O3 supports by the sol-gel technique for hydrogen separation. The hydrophobic property, pore structure, gas transport and separation performance, and hydrothermal stability of the modified membranes were investigated. It is observed that the water contact angle increases from 27.2+/-1.5 degrees for the pure silica membranes to 115.0+/-1.2 degrees for the modified ones with a (trifluoropropyl)triethoxysilane (TFPTES)/tetraethyl orthosilicate (TEOS) molar ratio of 0.6. The modified membranes preserve a microporous structure with a micropore volume of 0.14 cm3/g and a pore size of approximately 0.5 nm. A single gas permeation of H2 and CO2 through the modified membranes presents small positive apparent thermal activation energies, indicating a dominant microporous membrane transport. At 200 degrees C, a single H2 permeance of 3.1x10(-6) mol m(-2) s(-1) Pa(-1) and a H2/CO2 permselectivity of 15.2 were obtained after proper correction for the support resistance and the contribution from the defects. In the gas mixture measurement, the H2 permeance and the H2/CO2 separation factor almost remain constant at 200 degrees C with a water vapor pressure of 1.2x10(4) Pa for at least 220 h, indicating that the modified membranes are hydrothermally stable, benefiting from the integrity of the microporous structure due to the fluorocarbon modification.     

Multicomponent effective medium-correlated random walk theory for the diffusion of fluid mixtures through porous media

Molecular transport in nanoconfined spaces plays a key role in many emerging technologies for gas separation and storage, as well as in nanofluidics. The infiltration of fluid mixtures into the voids of porous frameworks having complex topologies is common place to these technologies, and optimizing their performance entails developing a deeper understanding of how the flow of these mixtures is affected by the morphology of the pore space, particularly its pore size distribution and pore connectivity. Although several techniques have been developed for the estimation of the effective diffusivity characterizing the transport of single fluids through porous materials, this is not the case for fluid mixtures, where the only alternatives rely on a time-consuming solution of the pore network equations or adaptations of the single fluid theories which are useful for a limited type of systems. In this paper, a hybrid multicomponent effective medium-correlated random walk theory for the calculation of the effective transport coefficients matrix of fluid mixtures diffusing through porous materials is developed. The theory is suitable for those systems in which component fluxes at the single pore level can be related to the potential gradients of the different species through linear flux laws and corresponds to a generalization of the classical single fluid effective medium theory for the analysis of random resistor networks. Comparison with simulation of the diffusion of binary CO(2)/H(2)S and ternary CO(2)/H(2)S/C(3)H(8) gas mixtures in membranes modeled as large networks of randomly oriented pores with both continuous and discrete pore size distributions demonstrates the power of the theory, which was tested using the well-known generalized Maxwell-Stefan model for surface diffusion at the single pore level.     

Influence of Water Vapor on Silica Membrane: Adsorption Properties and Percolation Effect

The influence of water vapor on silica membrane with pore size of 4 ? has been investigated in terms of adsorption properties and percolation effect at 50 and 90 oC. Two methods are employed: spectroscopic ellipsometry for water vapor adsorption and gas permeation of binary mixture of helium and H₂O. The adsorption behaviors on the silica membrane comply with the first-order Langmuir isotherm. The investigation demonstrates that helium flux through the silica membrane decreases dramatically in presence of H₂O molecules. The transport of gas molecules through such small pores is believed not to be continuous any more, whereas it is reasonably assumed that the gas molecules hop from one occupied site to another unoccupied one under the potential gradient. When the coverage of H₂O molecules on the silica surface increases, the dramatic decrease of helium flux could be related to percolation effect, where the adsorbed H₂O molecules on the silica surface block the hopping of helium molecules.     

An advanced gas/vapor permeation system for barrier materials: Design and applications to poly(ethylene terephthalate)

A new gas/vapor mixture permeation system is described to investigate the effect of organic molecules on oxygen (O₂) and carbon dioxide (CO₂) transport in barrier materials. Methanol vapor was considered as a flavor simulant mainly because of its conveniently high diffusion coefficient, which makes the experimental time accessible. A highly accurate syringe pump was used to introduce a desired activity level of vapor into gas feed stream. Adsorption of methanol on high energy surfaces is carefully characterized to prevent underestimation of methanol permeability. A special permeation cell was also developed to study the effect of interacting vapors on O₂ and CO₂ transport in barrier materials. Systematic permeation measurements were conducted for binary and ternary gas/vapor permeation measurements (e.g., MeOH/O₂ and O₂/CO₂/MeOH) to verify the feasibility of our new vapor/gas permeation system. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Effects of dip coating parameters on the morphology and transport properties of cellulose acetate–ceramic composite membranes

This work presents the fabrication of cellulose acetate (CA)–ceramic composite membranes using dip coating technique. Ceramic supports used in this work were prepared from kaolin with an average pore size of 560 nm and total porosity of 33%. The dip coating parameters studied experimentally were the concentration of CA solution (varying from 2 wt% to 8 wt%) in acetone and dipping time (varying from 30 s to 150 s). The fabricated composite membranes were characterized using scanning electron microscope, gas permeation, pure water flux and ultrafiltration (UF) experiments using bovine serum albumin (BSA). It was observed that the membrane prepared with 2 wt% and 4 wt% CA were suitable for microfiltration applications and those with 6 wt% and 8 wt% were for ultrafiltration applications. Theoretical investigation was conducted to know the macroporous and mesoporous structure of the prepared membranes using Knudsen and viscous permeability analysis of air. A resistance in series model was applied to identify different resistances responsible for the flux decline. Phenomenological models were proposed to illustrate the dependency of hydraulic resistance of membrane on the structural parameters such as average pore size, effective porosity as well as dip coating parameters like dipping time and concentration of CA. It was found that, the growth rate of CA film on the ceramic support followed exponential growth law with respect to dipping time. The total hydraulic resistance of the membrane was evaluated to be inversely proportional to the ratio of pore sizes of top layer and ceramic support. The resistance due to the CA film was found to be depended to the order of 1.73 with respect to concentration of CA. An increase in the concentration of CA was found to be more effective than dipping time to reduce the membrane pore size.     

Analysis of transient permeation as a technique for determination of sorption and diffusion in supported membranes

Systematic membrane selection, process design as well as elucidation of structure–property relationships for pervaporation and vapor permeation require knowledge of sorption and diffusion properties. Direct measurement of sorption is not possible in the case of commercial membranes due to the presence of a support layer. Sorption measurements may also be difficult if the polymer is synthesized or crosslinked directly on the support and its properties are different from the bulk polymer. This work describes a technique to obtain sorption as well as diffusion parameters for supported membranes using transient permeation data. Computer simulations for transient permeation were carried out using sorption and diffusion data from the literature. It was demonstrated that the desired parameters could be estimated using data having a reasonable degree of error (±2%) by the least squares method. Alternatively, a time-lag analysis may be used instead of direct regression of the parameters by the least squares method. A general method for estimating the sorption as well as diffusion parameters using the time-lag and steady-state flux is described. Analytical solutions are derived for the various transport models, wherever possible.     

Asymmetric molecular sieve carbon membranes

An asymmetric molecular sieve carbon membrane is obtained by conventional pyrolysis of a thermosetting polymeric film, followed by unequal oxidation. Morphology, pore size distribution, and gas separation characteristics of the membrane are discussed. The transport mechanism for gas permeation is clearly non-Knudsen diffusion since heavier oxygen permeates faster than lighter nitrogen. The proposed mass transfer mechanism is that of a molecular sieve.     

Pervaporation separation and mass transport of ethylbutanoate solution by polyether block amide (PEBA) membranes

Dense and composite membranes were developed from polyether block amide (PEBA). Polyacrylonitrile (PAN) and polysulfone (PSf) were used as the porous supports for the composite membranes. The membranes were tested for pervaporation separation of ethylbutanoate (ETB) solutions. Sorption and desorption experiments were also performed to provide data for analysis of mass transport based on resistance-in-series model.

The composite membranes with polyether block amide (PEBA) casted on PSf (PEBA/PSf) showed superior pervaporation performance than that casted on PAN (PEBA/PAN). The analysis of transport resistances revealed that: (1) the resistances in liquid boundary of ETB were highest and, therefore, were the controlling resistances; and (2) the transport resistances in the porous supports were much lower than those in the membrane top layers.

The results on plasticizing coefficients showed that ETB plasticized the membranes (positive, k_ii) but water did not (negative, k_jj). Negative coupling coefficients (k_ij) indicated that water reduced diffusivity of ETB in the membranes and the presence of ETB enhanced water diffusion in the membranes due to positive k_ji.     

The effect of mass transfer on electrochemical impedance of a solid oxide fuel cell anode

This paper presents electrochemical impedance simulation of a solid oxide fuel cell (SOFC) anode in order to investigate the effect of mass transport processes on the impedance spectra. The current model takes in to account the gas-phase transport processes both in the gas channel and within the porous electrode and couples the gas transport processes with the electrochemical kinetics. The impedance simulation is carried out in time domain, and the correlation between the anode harmonic responses to the sinusoidal excitation and the impedance spectra is analyzed. In order to solve the system of non-linear equations, an in-house code based on the finite difference method is developed and utilized. Results show a depressed semicircle in the Nyquist plot, which originates from gas transport processes in the gas channel, in addition to a Warburg diffusion impedance originates from gas transport in the thick porous anode. The influence of parameters such as electrode thickness, inlet gas composition, and temperature is also investigated and the results are discussed. The simulation results are in good agreement with published data.     

Theoretical modeling of water vapor transport in cellulose-based materials

The theory of mass transport in porous media is of fundamental importance for different applications such as food, paper packaging, textiles, and wood for building materials. In this study, a theoretical water vapor transport model has been developed for cellulose-based materials, such as paper and regenerated cellulose film. Pore diffusivities were determined from the dynamic moisture breakthrough experiments comprising a stack of paper sheets and regenerated cellulose films in a configuration similar to a packed adsorption column. Other mass transfer parameters were determined from transient moisture uptake rate measurements. The model incorporates pore and surface diffusion as a lump parameter into a variable effective diffusion coefficient. The mass transport, involving both pore and surface diffusions, is evaluated independently. The theoretical water vapor transmission rates (WVTRs) obtained from the model were compared with experimentally determined WVTRs measured under steady-state conditions. The theoretical model, based on intrinsic diffusion, stipulates higher WVTR values compared to the experimental results. However, the theoretical water vapor transfer rates agree well with the experimental results when external mass transfer resistance is incorporated in the model.