STUDY ON PERMEATION OF ACETONE/NITROGEN MIXED GAS THROUGH AL2O3 MICROPOROUS MEMBRANES: MOLECULAR DYNAMICS

In this work, by applying Materials Studio 2.2 software package, molecular dynamics (MD) was performed to investigate the dynamic processes of 1:4 acetone/nitrogen mixed gas permeating through different Al₂O₃ microporous membranes. Three systems were modeled by considering different box lengths, microporous sizes, and textures of Al₂O₃ membranes to compare different permeation behaviors. In each system, initial mixed gas contained 20 acetone molecules and 80 nitrogen molecules, and its density was set to 0.1 g/cm³. Analysis on the concentration profiles of nitrogen molecules (N2) and acetone molecules (Ace) in each system at different sampling times was implemented to discuss the permeation behaviors of smaller N2 and larger Ace. The results showed that adsorption and diffusion occurred synchronously but adsorption was dominant for acetone molecules and that the adsorption on the floor surface of the feed gas region more easily reached equilibrium (local equilibrium) than the diffusion and the adsorption on the ceiling of the initially vacuum region. Furthermore, for nitrogen, adsorption followed diffusion. Higher temperature is in favor of the enrichment of acetone on the floor surface of the feed gas region but against the adsorption of nitrogen. The adsorptive layer was found to be a double-layer with COMPASS force field and to be a monolayer with PCFF force field.     

Porous Ceramic Membranes: Preparation, Transport Properties and Applications

The preparation and characterization of porous ceramic membranes is presented. These membranes consist of a macroporous support system, with or without a mesoporous intermediate layer, and a microporous top layer. For the macroporous support membranes two manufacturing routes are described: a conventional and a RBAO (Reaction Bonded Aluminium Oxide) route. The mesoporous -Al₂O₃ layer is obtained by means of a sol-gel dipcoating technique. Three microporous top layers are considered: SiO₂, Al₂O₃-pillared montmorillonite and Laponite. These top layers have different pore structures which results in different gas transport properties. A SiO₂ membrane can be used for H₂ removal from a gas mixture. Al₂O₃-pillared montmorillonite and Laponite membranes do not show specific gas separation properties. Dehydration of water/2-propanol mixtures by means of pervaporation also proved a different behavior for these microporous membranes.     

CO2 sorption and transport behavior of ODPA-based polyetherimide polymer films

Plasticization phenomena can significantly reduce the performance of polymeric membranes in high-pressure applications. Polyetherimides (PEIs) are a promising group of membrane materials that combine relatively high CO₂/CH₄ selectivities with high chemical and thermal stability. In this work sorption, swelling, and mixed gas separation performance of 3,3′,4,4′-oxydiphthalic dianhydride (ODPA)-based PEI polymers, with 1, 2 or 3 para-aryloxy substitutions in the diamine moeiety, is investigated under conditions where commercial membranes suffer from plasticization. Particular focus is on the influence of the amount of para-aryloxy substitutions and the film thickness. Results are compared with those of commercially available polymeric membrane materials (sulphonated PEEK, a segmented block-co-polymer PEBAX and the polyimide Matrimid).The glassy polymers display increasing CO₂ sorption with increasing T_g. The larger extent of sorption results from a larger non-equilibrium excess free volume. Swelling of the polymers is induced by sorption of CO₂ molecules in the non-equilibrium free volume as well as from molecules dissolved in the matrix. Dilation of the polymer is similar for each molecule sorbed. Correspondingly, the partial molar volume of CO₂ is similar for molecules present in both regions.Mixed gas separation experiments with a 50/50% CO₂/CH₄ feed gas mixture showed high CO₂/CH₄ selectivities for the ODPA PEI films at elevated pressure. This shows that these materials could potentially be interesting for high-pressure gas separation applications, although additional gas permeation experiments using different feed gas compositions and thin films are required.     

Preparation of highly mesoporous carbon membranes via a sol-gel process using resorcinol and formaldehyde

This paper reports the preparation of highly mesoporous carbon membranes, which are obtained by the pyrolysis of sol-gel derived mesoporous polymer membranes using resorcinol and formaldehyde (RF). Two series of RF carbon membranes were prepared by changing the resorcinol to catalyst molar ratio. The nitrogen adsorption-desorption measurement shows that the RF carbon membranes possess a well-developed mesoporous structure with controlled pore diameters of 5.48 nm and 13.9 nm. The helium and nitrogen permeances of both RF carbon membranes were independent of the feed pressure, indicating that there was no contribution of viscous flow and the membranes are initially crack-free. The gas permeation result showed that the dominant mechanism of gas transport through both the RF carbon membranes is Knudsen diffusion. With regard to the permeation of condensable gases such as CH₄ and CO₂, it was observed that the surface flow also contributes to the total permeation.     

Effects of Synthesis Temperature and Support Material on CO2 and CH4 Permeation through SAPO-34 Membranes

In this research, continuous SAPO-34 membranes were synthesized via secondary growth method onto both α-Al₂O₃ and mullite supports at three levels of synthesis temperature: 185, 195, and 220°C for 24 h. The synthesized membranes were characterized using XRD and SEM analysis and single gas permeation experiments. It was found out that support material and synthesis temperature both have significant effects on the membrane performance. At higher synthesis temperature, SAPO-34 crystals grown over the mullite support become more uniform and smaller in size but those grown on the α-Al₂O₃ support become larger. Effect of synthesis temperature on single gas permeation properties of the synthesized SAPO-34 membranes was also studied. For the mullite supported membranes, the CH₄ and CO₂ permeances decrease as synthesis temperature increases; but in the case of the alumina supported membranes, by increasing synthesis temperature, CH₄ and CO₂ permeances first decrease up to 195°C and then increase up to 220°C. Even in equal membrane thicknesses, the mullite supported membrane shows lower gas permenaces. Increasing synthesis temperature decreases CO₂/CH₄ ideal selectivity for the α-Al₂O₃ supported membranes, while increases for the mullite supported membranes. Under optimum synthesis conditions, at room temperature and 2 bar feed pressure, the CO₂ permeance through the α-Al₂O₃ and the mullite supported SAPO-34 membranes are 8.2 × 10^?7 and 8.5 × 10^?8 (mol/m² · s · Pa), respectively, and CO₂/CH₄ ideal selectivities are 51 and 61, respectively.     

Synthesis and preliminary gas permeation studies of a tubular NaA zeolite membrane (NZM)

Different from traditional seeded method, NaA zeolite membranes (NZMs) were prepared by in situ synthesis onto the inner side of porous α-alumina tubular supports in a hydrothermal synthesis reactor. The influences of pretreatment of porous tubular support, temperature, time, and synthetic cycle for the synthesis of the zeolite membranes were investigated. The operating conditions were optimized. Characterization of the membranes by scanning electron microscopy and X-ray diffraction showed that the crystalline materials on the inner surface of the porous α-alumina tubes were NaA-type zeolite. Single- and binary-gas permeation tests were conducted. Single-component permeabilities of hydrogen and nitrogen through the NZM changed slightly when the transmembrane pressure difference varied from 80 to 420?kPa. Its selectivity for H₂ relative to N₂ was about 5.3, which was greater than that of the Knudsen diffusion. The separation factors of binary gases H₂/N₂ and H₂/CO₂ at 473?K were 3.9 and 5.7, respectively, again exceeding the Knudsen diffusion level. The separation of binary gases suggests that the NaA-type zeolite membranes on α-alumina substrate were defect free and able to provide molecular sieving. The results demonstrate that the unseeded synthetic method presented in this work is successful and reliable.     

Hydrogen generation and separation using Gd0.2Ce0.8O1.9−δ–Gd0.08Sr0.88Ti0.95Al0.05O3±δ mixed ionic and electronic conducting membranes

Decomposition of steam under a chemical driving force at moderate temperatures offers a simple and economical way to generate hydrogen. A significant amount of hydrogen can be generated and separated by splitting steam and removing the oxygen using Gd_0.2Ce_0.8O_1.9−δ (GDC)–Gd_0.08Sr_0.88Ti_0.95Al_0.05O_3±δ (GSTA) mixed oxygen ionic and electronic conducting membranes. Hydrogen generation experiments for the self-supported thick membranes and porous supported thin membranes were conducted at different oxygen partial pressure gradients across the membrane established using H₂–H₂O mixture gas. Experimental results indicate that the hydrogen generation from steam using GDC–GSTA MIEC membranes at elevated temperatures is mainly controlled by the bulk diffusion of oxygen for the self-supported thick membranes, while the permeation process for the porous supported thin membranes is mixed controlled, i.e. the hydrogen generation/oxygen permeation process is controlled by the surface exchange reactions and bulk diffusion of oxygen through the MIEC membrane. A mathematical model for the calculation of the area specific hydrogen generation rate is proposed in this paper based on the measured oxygen partial pressures, gas compositions, and gas flow rates of the inlet and outlet gases on feed side of the membrane, as well as the permeation area of the membrane.     

Effect of metal‐support interface on hydrogen permeation through palladium membranes

Thin palladium membranes of different thicknesses were prepared on sol‐gel derived mesoporous γ‐alumina/α‐alumina and yttria‐stabilized zirconia/α‐alumina supports by a method combining sputter deposition and electroless plating. The effect of metal‐support interface on hydrogen transport permeation properties was investigated by comparing hydrogen permeation data for these membranes measured under different conditions. Hydrogen permeation fluxes for the Pd/γ‐Al₂O₃/α‐Al₂O₃ membranes are significantly smaller than those for the Pd/YSZ/α‐Al₂O₃ membranes under similar conditions. As the palladium membrane thickness increases, the difference in permeation fluxes between these two groups of membranes decreases and the pressure exponent for permeation flux approaches 0.5 from 1. Analysis of the permeation data with a permeation model shows that both groups of membranes have similar hydrogen permeability for bulk diffusion, but the Pd/γ‐Al₂O₃/α‐Al₂O₃ membranes exhibit a much lower surface reaction rate constant with higher activation energy, due possibly to the formation of Pd‐Al alloy, than the Pd/YSZ/α‐Al₂O₃ membranes. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Comparative CO2 Adsorption Analysis in Pure and Amine-Modified Composite Membranes

In this study, the CO₂ adsorption analysis in cellulose acetate–TiO₂- and cellulose acetate–3-aminopropyl-trimethoxysilane TiO₂-blended membranes was performed. The membranes were also characterized using scanning electron microscopy and Fourier transform infrared analysis techniques. The adsorption results indicated that 120 and 90°C were considered as optimized temperatures for regeneration of cellulose acetate–TiO₂ and cellulose acetate–3-aminopropyl-trimethoxysilane-modified TiO₂ membranes. The testing results revealed that adsorption capacity reached maximum at 3.0 bars. Validation of experimental results was performed by pseudo-first-order, second-order and intraparticle diffusion models. The correlation factor R² represented that the second-order model was fitted well with the experimental data. The intraparticle diffusion model represented that adsorption is not a single-step process.     

Membrane separation process modeling for CO2 partial removal in prepurification of air separation units

A novel membrane/adsorption hybrid system was proposed for air prepurification in large scale air separation units. Mathematical models were established for cocurrent and countercurrent flow patterns with crude nitrogen as purge stream to describe the membrane separation performance. The experimental and predicted results are in good agreement confirming the validity of the mathematical models. Effects of membrane properties and operation parameters on O₂ recovery, N₂ recovery, and membrane area requirement were investigated. For countercurrent flow pattern, O₂ recovery and N₂ recovery were larger than 98 and 99%, respectively, and membrane area requirement was less than 0.25?m²/m³?h^?1 with feed side pressure of 0.6?MPa and the purge gas/feed gas ratio of 0.2.     

Prediction of a highly sensitive molecule sensor for SOx detection based on TiO2/MoS2 nanocomposites: a DFT study

First principles calculations within density functional theory have been carried out to investigate the adsorptions of SO_x (x?=?1, 2) molecules on TiO₂/MoS₂ nanocomposites in order to fully discover the gas sensing capabilities of TiO₂/MoS₂ composite systems. The van der Waals interactions were included to obtain the most stable geometrical structures of TiO₂/MoS₂ nanocomposites with adsorbed SO_x molecules. SO_x molecules preferentially interact with the doped nitrogen and fivefold coordinated titanium sites of the TiO₂ anatase nanoparticles because of their higher activities in comparison with the other sites. The results presented include structural parameters such as bond lengths and bond angles and energetics of the systems such as adsorption energies. The variation of electronic structures are discussed in view of the density of states and molecular orbitals of the SO_x molecules adsorbed on the nanocomposites. The results show that the adsorption of the SO_x molecule on the N-doped TiO₂/MoS₂ nanocomposite is energetically more favorable than the adsorption on the undoped one, implying that the nitrogen doping helps to strengthen the interaction of SO_x molecules with TiO₂/MoS₂ nanocomposites. These calculated results thus provide a theoretical basis for the potential applications of TiO₂/MoS₂ nanocomposites in the removal and sensing of harmful SO_x molecules.     

SULPHUR DIOXIDE ABSORPTION IN HOLLOW FIBRE MEMBRANE MODULES

The performance of non-porous silicone rubber and microporous hydrophobic polypropylene hollow fibre membranes coupled with liquid absorbent were assessed for the removal of SO₂; from a gas stream. This approach combines the advantages of absorption technology (high selectivity) with membrane systems (compactness of equipment). The advantages of such gas absorption membranes were evident in the increased selectivities of both membranes. A mathematical model which incorporates the effective permeabilities of the gases has been developed to simulate the separation process. Numerical simulations agreed well with the experiment. Further investigations were carried out to study the combined removal of CO₂ and SO₂ and any possible interactive effects of these gases during absorption in these contactors.     

Modification of polycarbonate membrane by polyethylene glycol for CO2/CH4 separation

In this study, permeation of carbon dioxide (CO₂) and methane (CH₄) through the polycarbonate/polyethylene glycol (PC/PEG) blend membrane was investigated. The effect of PEG content (0–5 wt%) on the permeability and selectivity was studied. Permeability measurements were carried out at pressures of 1–7 bar and at room temperature. The membranes were characterized by Fourier transform infrared-attenuated total reflectance spectroscopy (FTIR-ATR), X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and density measurement. The results revealed that the PC/PEG blends are miscible/partially miscible without considerable micro-phase separation. The effect of PEG content and gas pressure on the diffusion and solubility of coefficients were also investigated and analyzed. It was concluded that the most influential parameter for the permeation is the diffusion coefficient of the gases. The permeability and selectivity decrease as the operating pressure and PEG content are increased. Furthermore, the results showed that the addition of 5 wt% of PEG into PC increases the CO₂/CH₄ selectivity from 26.6 ± 0.99 to 40.9 ± 2.14 (more than 53%) at 1 bar.     

Preparation of hollow fibers for the removal of volatile organic compounds from air

Hollow-fiber membranes were prepared to remove volatile organic vapors (VOCs) from a nitrogen or air stream. Conditions were found to spin hollow fibers of high performance for the removal of VOCs. The effect of temperature on the permeation of nitrogen gas and acetone vapor was studied. It was found that nitrogen permeation was governed by diffusion while vapor permeation was governed by sorption. There were two distinct mechanisms for vapor permeation, depending on temperature. Performance data for hollow fibers with and without a silicone rubber coating at the internal surface were compared. The effect of the presence of water vapor in the feed was also studied. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 371–379, 1998     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

Gas absorption of carbon dioxide in a hollow fiber contained liquid membrane absorber

Experiments on the absorption of CO₂ into a hollow fiber contained liquid membrane absorber were performed. The feed gas was a mixture of CO₂ and N₂, absorbent liquid was 2-amino-2-methyl-l-propanol and the hollow fiber was a microporous hydrophobic polytetrafluoroethylene membrane. Outlet concentration of CO₂ from the absorber decreased as absorbent concentration increased, gas flow rate increased and were held constant for speed of agitation, but had a maximum value in the range of inlet concentration of CO₂ from 5 to 40 mole%. The reaction rate constant obtained for CO₂-amine system was 231 I/mol · s at 25 °C using a flat stirred vessel, and the membrane-side-mass-transfer coefficient was 1.217 × 10⁻⁵ mol/cm² · s · atm in CO2/N2-amine system. A diffusion model based on mass transfer with fast-reaction was proposed to predict the performance of the absorber.     

NO x uptake mechanism on Pt/BaO/Al2O3 catalysts

The NO _x adsorption mechanism on Pt/BaO/Al₂O₃ catalysts was investigated by performing NO _x storage/reduction cycles, NO₂ adsorption and NO + O₂ adsorption on 2%Pt/(x)BaO/Al₂O₃ (x = 2, 8, and 20 wt%) catalysts. NO _x uptake profiles on 2%\Pt/20%BaO/Al₂O₃ at 523 K show complete uptake behavior for almost 5 min, and then the NO _x level starts gradually increasing with time and it reaches 75% of the inlet NO _x concentration after 30 min time-on-stream. Although this catalyst shows fairly high NO _x conversion at 523 K, only ~2.4 wt% out of 20 wt% BaO is converted to Ba(NO₃)₂. Adsorption studies by using NO₂ and NO + O₂ suggest two different NO _x adsorption mechanisms. The NO₂ uptake profile on 2%Pt/20%BaO/Al₂O₃ shows the absence of a complete NO _x uptake period at the beginning of adsorption and the overall NO _x uptake is controlled by the gas–solid equilibrium between NO₂ and BaO/Ba(NO₃)₂ phase. When we use NO + O₂, complete initial NO _x uptake occurs and the time it takes to convert ~4% of BaO to Ba(NO₃)₂ is independent of the NO concentration. These NO _x uptake characteristics suggest that the NO + O₂ reaction on the surface of Pt particles produces NO₂ that is subsequently transferred to the neighboring BaO phase by spill over. At the beginning of the NO _x uptake, this spill-over process is very fast and so it is able to provide complete NO _x storage. However, the NO _x uptake by this mechanism slows down as BaO in the vicinity of Pt particles are converted to Ba(NO₃)₂. The formation of Ba(NO₃)₂ around the Pt particles results in the development of a diffusion barrier for NO₂, and increases the probability of NO₂ desorption and consequently, the beginning of NO _x slip. As NO _x uptake by NO₂ spill-over mechanism slows down due to the diffusion barrier formation, the rate and extent of NO₂ uptake are determined by the diffusion rate of nitrate ions into the BaO bulk, which, in turn, is determined by the gas phase NO₂ concentration.     

Modified gas‐translation model for prediction of gas permeation through microporous organosilica membranes

A modified gas‐translation (GT) model was applied for the theoretical analysis of gas permeation through microporous organosilica membranes derived from bis(triethoxysilyl)ethane (BTESE) via a sol–gel method using different water/alkoxide molar ratios. The pore sizes of BTESE‐derived membranes were quantitatively determined by normalized Knudsen‐based permeance analysis, which was based on a modified‐GT model, using experimentally obtained permeances of He, H₂, N₂, C₃H₈, and SF₆. The pore sizes of BTESE‐derived membranes were successfully controlled from 0.65 to 0.46 nm by increasing the H₂O/BTESE ratio from 6 to 240. Furthermore, theoretical correlations of all possible pairs of permeance ratios were calculated based on the modified‐GT model. The experimental data were in good agreement with the theoretical correlation curves, indicating that the modified‐GT model can clearly explain gas permeation mechanisms through microporous membranes, and, thus, can be used to predict the gas permeation properties for these membranes. © 2014 American Institute of Chemical Engineers AIChE J 60: 4199–4210, 2014     

Transport Phenomena of Chitosan Membrane in Pervaporation of Water-Ethanol Mixture

ABSTRACT

The pervaporation transport process of H₂O-EtOH solution was studied on a chitosan membrane and on a H₂SO₄ crosslinked chitosan membrane. The influence of concentration, temperature, and crosslinking was also studied. The dependence of permeation fluxes on feed concentration showed strong coupling effects existed in the permeation process. That the thermodynamic swelling—distribution relationship changed with the feed concentration also showed that a strong coupling effect existed in the thermodynamic swelling process. The permeation fluxes and thermodynamic swelling processes showed analogous relationships versus the concentration in the feed. The high swelling ratio and the high selectivity of the membrane in the thermodynamic swelling distribution process was the basis ofhigh flux and high permselectivity of pervaporation. With an increase of temperature, the permeation fluxes increased quickly, but the swelling ratio of water and EtOH in the membrane scarcely changed. This showed that an increase of temperature promoted the diffusion process but had little influence on permselectivity. The permselectivity of pervaporation depended strongly on the thermodynamic swelling process.