Preparation,characterization, and performance evaluation of coated PES polymer materials fabricated via dry/wet phase inversion technique

Sulfur dioxide (SO₂) is the major air pollutant which is emitted from the power plant. In this study, hollow fiber membrane (HFM) separation process is applied for the improvement of SO₂ removal efficiency in the post‐combustion gas. HFM was produced by dry/wet phase inversion method and then coated with Polydimethylsiloxane (PDMS). The membrane morphology and characterization were examined with help of scanning electron microscope (SEM), energy dispersion of X‐ray spectroscopy (EDX), Fourier transform infrared (FT‐IR) and atomic force microscopy (AFM). Polyethersulfone (PES) hollow fiber membranes were tested for the SO₂/N₂ binary mixed gas separation. Single gas permeance of SO₂, N₂, and binary mixture gas (200 ppm of SO₂) separation experiment was initiated to observe membrane behavior according to temperature and pressure difference and retentate flow rate. As a result, permeance of SO₂ was 24.9–47.4 GPU and selectivity of SO₂/N₂ was 1.6–4.2. From the mixture gas separation experiment, SO₂ removal efficiency increased according to stage cut and operating pressure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39711.     

Separation of SF6 from Binary Mixtures with N2 Using Commercial Poly(4-Methyl-1-Pentene) Films

Systematic studies on gas permeation of pure SF₆ and N₂ as well as their mixture in poly(4-methyl-1-pentene) (PMP) at different temperatures and pressures, using commercially available thin PMP films, are reported in this article. The effective separation of SF₆ from binary mixtures with N₂ is critical for the proposed replacement of pure SF₆, used as an insulating gas in high power industry, by the mixtures of these two gases. This replacement is driven by the fact that SF₆ is the most potent greenhouse gas, with a global warming potential of 22,200 times that of CO_2. The experiments with a 1:1 mixture of N₂ and SF₆ revealed the permselectivity of PMP as high as 476 with the corresponding N₂ permeability coefficient of 7.6 Barrer. These properties, which are much better than those of other glassy polymers considered for this separation, were not affected by a long-term exposure to SF₆, which indicates the excellent resistance of PMP to plasticization by this gas. Using a single stage membrane system utilizing the PMP membrane would allow separating the above gas mixture into a 99% pure SF₆ product with the corresponding recovery rate of SF₆ greater than 99%.     

Modeling and parametric analysis of hollow fiber membrane system for carbon capture from multicomponent flue gas

The modeling and optimal design/operation of gas membranes for postcombustion carbon capture (PCC) is presented. A systematic methodology is presented for analysis of membrane systems considering multicomponent flue gas with CO₂ as target component. Simplifying assumptions is avoided by namely multicomponent flue gas represented by CO₂/N₂ binary mixture or considering the co/countercurrent flow pattern of hollow‐fiber membrane system as mixed flow. Optimal regions of flue gas pressures and membrane area were found within which a technoeconomical process system design could be carried out. High selectivity was found to not necessarily have notable impact on PCC membrane performance, rather, a medium selectivity combined with medium or high permeance could be more advantageous. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Permeation of H2, N2, CH4, C2H6, and C3H8 through asymmetric polyetherimide hollow‐fiber membranes

Permeation properties of pure H₂, N₂, CH₄, C₂H₆, and C₃H₈ through asymmetric polyetherimide (PEI) hollow‐fiber membranes were studied as a function of pressure and temperature. The PEI asymmetric hollow‐fiber membrane was spun from a N‐methyl‐2‐pyrrolidone/ethanol solvent system via a dry‐wet phase‐inversion method, with water as the external coagulant and 50 wt % ethanol in water as the internal coagulant. The prepared asymmetric membrane exhibited sufficiently high selectivity (H₂/N₂ selectivity >50 at 25°C). H₂ permeation through the PEI hollow fiber was dominated by the solution‐diffusion mechanism in the nonporous part. For CH₄ and N₂, the transport mechanism for gas permeation was a combination of Knudsen flow and viscous flow in the porous part and solution diffusion in the nonporous part. In our analysis, operating pressure had little effect on the permeation of H₂, CH₄, and N₂. For C₂H₆ and C₃H₈, however, capillary condensation may have occurred at higher pressures, resulting in an increase in gas permeability. As far as the effect of operating temperature was concerned, H₂ permeability increased greatly with increasing temperature. Meanwhile, a slight permeability increment with increasing temperature was noted for N₂ and CH₄, whereas the permeability of C₂H₆ and C₃H₈ decreased with increasing temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 698–702, 2002     

Preparation of poly(phthalazinone ether sulfone ketone) hollow fiber membrane for gas separation

Poly(phthalazinone ether sulfone ketone) (PPESK) asymmetric hollow fiber membranes for gas separation were prepared by dry/wet phase inversion technique. The effects of various preparation conditions such as solvent, nonsolvent-additives(NSA), PPESK concentration, and air gap on the membrane performance were studied. The heat resistance of the PPESK hollow fiber membrane was also examined. The hollow fiber membrane prepared from solvent with stronger solubility showed low gas permeation and high O₂/N₂ selectivity due to the denser skin layer. Hollow fiber membrane made from PPESK/DMAc/EtOH/THF system had thicker skin layer than that made from PPESK/DMAc/GBL system with the same ratio of near-to-cloud-point of NSA, which resulted in the higher O₂/N₂ selectivity. Along with the increase of NSA content, the gas permeation increased and the O₂/N₂ selectivity decreased. The O₂/N₂ selectivity of hollow fiber membranes made from PPESK/DMAc/GBL and PPESK/DMAc/EtOH/THF systems were 4.9 and 4.8 respectively, when the membrane forming systems contained appropriate content of NSA. The high polymer concentration resulted in low gas permeation and high O₂/N₂ selectivity. When the air gap was excessively long, the membrane performance dropped because of the damage to the dense skin layer. There was no significant drop on the membrane performance when the operation temperature was elevated to 90°C. The average O₂/N₂ selectivity was higher than 3.0 at 70°C during a long period of 55 days' test time. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Separation of CO2 by 2-amino-2-methyl-1-propanol aqueous solution in microporous hydrophobie hollow fiber contained liquid membrane

The absorption of CO₂ from a mixture of CO₂/N₂ gas was carried out using a flat-stirred vessel and the polytetrafluoroethylene hollow fiber contained aqueous 2-amino-2-methyl-1-propanol (AMP) solution. The reaction of CO₂ with AMP was confirmed to be a second order reversible reaction with fast-reaction region. The mass transfer resistance in the membrane side obtained from the comparison of the measured absorption rates of CO₂ in a hollow fiber contained liquid membrane with a flat-stirred vessel corresponded to about 90% of overall-mass-transfer resistance. The mass transfer coefficient of hollow fiber phase could be evaluated, which was independent of CO₂ loading.     

Hydrogen separation from the H2/N2 mixture by using a single and multi-stage inorganic membrane

The separation characteristics of hydrogen from a gas mixture were investigated by using a single and two-stage inorganic membrane. Three palladium impregnated membranes were prepared by using the sol-gel, hydrolysis, and soaking-and-vapor deposition (SVD) techniques. A two-stage gas separation system without a recycling stream was constructed to see how much the hydrogen separation factor would be increased. Numerical simulation for the separation system was conducted to predict the separation behavior for the multi-stage separation system and to determine the optimal operating conditions at which the highest separation factor is obtained. Gas separation through each prepared membrane was achieved mainly by Knudsen diffusion. The real separation factor for the H₂/ N₂ mixture was increased with the pressure difference and temperature for a single stage, respectively. For the twostage separation system, there was a maximum point at which the highest separation factor was obtained and the real hydrogen separation factor for H₂/N₂ mixture was increased about 40 % compared with a single stage separation. The numerical simulation for the single and two-stage separation system was in a good agreement with the experimental results. By numerical simulation for the three-stage separation system, which has a recycle stream and three membranes that have the same permeability and hydrogen selectivity near to the Knudsen value, it is clear that the hydrogen separation factors for H₂/N₂ mixture are increased from 1.8 to 3.65 and hydrogen can be concentrated up to about 80 %. The separation factors increased with increasing recycle ratio. Optimal operating conditions exist at which the maximum real separation factor for the gas mixture can be obtained for three-stage gas separation and they can be predicted successfully by numerical simulation.     

CO2 removal by single and mixed amines in a hollow‐fiber membrane module—investigation of contactor performance

This work investigates CO₂ removal by single and blended amines in a hollow‐fiber membrane contactor (HFMC) under gas‐filled and partially liquid‐filled membrane pores conditions via a two‐scale, nonisothermal, steady‐state model accounting for CO₂ diffusion in gas‐filled pores, CO₂ and amines diffusion/reaction within liquid‐filled pores and CO₂ and amines diffusion/reaction in liquid boundary layer. Model predictions were compared with CO₂ absorption data under various experimental conditions. The model was used to analyze the effects of liquid and gas velocity, CO₂ partial pressure, single (primary, secondary, tertiary, and sterically hindered alkanolamines) and mixed amines solution type, membrane wetting, and cocurrent/countercurrent flow orientation on the HFMC performance. An insignificant difference between the absorption in cocurrent and countercurrent flow was observed in this study. The membrane wetting decreases significantly the performance of hollow‐fiber membrane module. The nonisothermal simulations reveal that the hollow‐fiber membrane module operation can be considered as nearly isothermal. © 2014 American Institute of Chemical Engineers AIChE J, 61: 955–971, 2015     

Characterization of hollow fiber membranes in a permeator using binary gas mixtures

We have studied the CO₂/CH₄ mixed gas permeation through hollow fiber membranes in a permeator. An approach to characterize the true separation performance of hollow fiber membranes for binary gas mixtures was provided based on experiments and simulations. Experiments were carried out to measure the retentate and permeate flow rates and compositions at each outlet. The influences of pressure drop within the hollow fibers, non-ideal gas behavior in the mixture and concentration polarization were taken into consideration in the mathematics model. The calculation results indicate that the net influence of the non-ideal gas behavior, competitive sorption and plasticization yields the calculated CO₂ permeance in a mixed gas permeator close to that obtained in pure gas tests. Whereas the CH₄ permeance is higher in the mixed gas tests than that in the pure gas tests, as the plasticization caused by CO₂ dominates the permeation process. As a result, the CO₂/CH₄ mixed gas selectivity is smaller than those obtained in pure gas tests at equivalent pressures.The calculated membrane performance shows little changes with stage cut if the effect of concentration polarization is accounted for in the calculation. The integration method developed in this study could provide more accurate characterizations of mixed gas permeance of hollow membranes than other estimation methods, as our model considers the roles of non-ideal gas behavior and concentration polarization properly.     

Designing an atmosphere controlling hollow fiber membrane system for mango preservation

We devised an atmosphere controlling facility to gain a longer life span for mango. A membrane module made of polyethersulfone/polydimethylsiloxane (PES/PDMS) composite membrane was applied to selectively permeate CO₂ from the gas mixture of the fruit container. To design the membrane separation system, two models were introduced into our mathematical simulations: (1) an equilibrium model giving the optimal membrane area, the compositions of CO₂ and O₂ in the fruit container, feed flow rate and pressures on both the feed and permeate sides of the module, and (2) a dynamic model simulating the change in the gas composition of the fruit container with time. The pressure build-up in the bore side of the hollow fiber was also discussed using the Hagen-Poiseuille equation. The best membrane module configuration was obtained based on the pressure build-up analysis. That was (1) the vacuum pressure should be set at 0.1 bar, (2) the hollow fiber inner diameter should be 0.45 mm, and (3) the vacuum should be applied at both ends of the hollow fiber bore sides.     

Optimization of the separation of sulfur hexafluoride and nitrogen by selective adsorption using monte carlo simulations

We present molecular simulations to find the optimal conditions for the separation by adsorption of SF₆ from a gaseous mixture with N₂, a mixture of key interest in electrical applications. The effect of pore size, pressure, and mixture compositions on the selective adsorption of SF₆ was investigated by using Grand Canonical Monte Carlo simulations with simple fluid models and a simplified model of MCM‐41. Simulations performed with multisite fluid models confirm that general trends are predicted using simple models, including a maximum in SF₆ selectivity for pore diameters around 1.1 nm. Simulations were also performed using two atomistic models of zeolite‐templated carbon (ZTC), FAU‐ZTC, and EMT‐ZTC, materials with average pore sizes close to 1.1 nm, obtaining high selectivities for both materials. Selectivities for FAU‐ZTC are approximately four times higher than the best materials published for this mixture separation, opening excellent opportunities to use it for recovering SF₆ from SF₆/N₂ mixtures. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

High H2 permeable SAPO-34 hollow fiber membrane for high temperature propane dehydrogenation application

SAPO-34 hollow fiber zeolite membranes are successfully synthesized on α-Al₂O₃ hollow fiber ceramic substrates by secondary growth method, and used to separate H₂ from a binary mixture (H₂, C₃H₈) or ternary mixture (H₂, C₃H₈, and C₃H₆) under a wide temperature range (25–600°C) with the aim of using them for propane dehydrogenation (PDH) reactions at high temperature. The results show excellent performance for H₂/C₃H₈ and H₂/ C₃H₈ & C₃H₆ separation, with high H₂ permeance of 3.1 × 10⁻⁷ mol/m²/s/Pa and H₂/C₃H₈ selectivity of 41 at 600°C. Additionally, the membrane shows stable performance for 140 hr of H₂/C₃H₈ separation test at 600°C. The high performance of this membrane is mainly attributed to the thin (∼2 μm) zeolite layer and asymmetric-wall of the hollow fiber support. So far, this membrane offers the highest hydrogen permeation and selectivity for H₂/C₃H₈ separation at high temperature (600°C) compared to those reported in literature.     

Preparation and performance evaluation of composite hollow fiber membrane for SO2 separation

Emission of sulfur dioxide (SO₂) from coal power plants has to be controlled and minimized to reduce environmental risk. This study aimed to investigate the hollow fiber composite membrane was used for the removal of SO₂ from a SO₂/CO₂/N₂ mixed gas. Moreover, for the improvement of SO₂ removal efficiency, the polyetherimide (PEI) membrane was coated with poly(vinyl chloride)‐graft‐poly(oxyethylene methacrylate) (PVC‐g‐POEM). The PVC‐g‐POEM/PEI composite hollow fiber membrane was extensively characterized by various techniques including scanning electron microscopy, Fourier transform infrared spectroscopy, and atomic force microscopy. Experiments with permeation of SO₂, CO₂, N₂, and a ternary gas mixture were carried out to observe membrane behavior in response to different operating conditions. As a result, permeance of SO₂ was 105–2705 GPU and selectivity of SO₂/CO₂ was 3.9–175.6. From the mixed gas separation experiment, the maximum SO₂ removal efficiency reached up to 84.5%. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2298–2306, 2014     

Study of transport of pure and mixed CO2/N2 gases through polymeric membranes

The permeations of pure CO₂ and N₂ gases and a binary gas mixture of CO₂/N₂ (20/80) through poly(dimethylsiloxane) (PDMS) membrane were carried out by the new permeation apparatus. The permeation and separation behaviors were characterized in terms of transport parameters, namely, permeability, diffusion, and solubility coefficients which were precisely determined by the continuous‐flow technique. In the permeation of the pure gases, feed pressure and temperature affected the solubility coefficients of CO₂ and N₂ in opposite ways, respectively; increasing feed pressure positively affects CO₂ solubility coefficient and negatively affects N₂ solubility coefficient, whereas increasing temperature favors only N₂ sorption. In the permeation of the mixed gas, mass transport was observed to be affected mainly by the coupling in sorption, and the coupling was analyzed by a newly defined parameter permeation ratio. The coupling effects have been investigated on the permeation and separation behaviors in the permeation of the mixed gas varying temperature and feed pressure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 179–189, 2000     

New absorption liquids for the removal of CO2 from dilute gas streams using membrane contactors

A new absorption liquid based on amino acid salts has been studied for CO₂ removal in membrane gas-liquid contactors. Unlike conventional gas treating solvents like aqueous alkanolamines solutions, the new absorption liquid does not wet polyolefin microporous membranes. The wetting characteristics of aqueous alkanolamines and amino acid salt solutions for a hydrophobic membrane was studied by measuring the surface tension of the liquid and the breakthrough pressure of the liquid into the pores of the membrane. The dependence of the breakthrough pressure on surface tension follows the Laplace-Young equation. The performance of the new absorption liquid in the removal of CO₂ was studied in a single fiber membrane contactor over a wide range of partial pressures of CO₂ in the gas phase and amino acid salt concentrations in the liquid. A numerical model to describe the mass transfer accompanied by multiple chemical reactions occurring during the absorption of CO₂ in the liquid flowing through the hollow fiber was developed. The numerical model gives a good prediction of the CO₂ absorption flux across the membrane for the absorption of CO₂ in the aqueous amino acid salt solutions flowing through the hollow fiber.     

Synthesis and characterization of alumina supported sub-nanoporous SiO2–10 wt%TiO2 membrane for nitrogen separation

Membrane of SiO₂–10TiO₂ was produced by dip coating on mesoporous-titania-coated macroporous alumina support. The amorphous SiO₂–10TiO₂ top layer with thickness of 0.9 μm was obtained as a homogenous and defect free surface. Gas permeation tests show a decrease in permeation in order of CH₄ > N₂ for the support, and N₂ > CH₄ for the multilayer membrane. The membrane delivering promised single gas separation factor for N₂/CH₄ (1.75). It was also observed that the membrane separation factor in binary gas mixture was 12–15% of the single gas separation factor, while the permeation revealed a decrease in gas mixture.     

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.     

Absorption of SO<Subscript>2</Subscript> using PVDF hollow fiber membranes with PEG as an additive

In this study, removal of SO₂ from gas stream was carried out by using microporous polyvinylidene fluoride (PVDF) asymmetric hollow fiber membrane modules as gas-liquid contactor. The asymmetric hollow fiber membranes used in this study were prepared polyvinylidene fluoride by a wet phase inversion method. Water was used as an internal coagulant and external coagulation bath for all spinning runs. An aqueous solution containing 0.02 M NaOH was used as the absorbent. This study attempts to assess the influence of PEG additive, absorbent flow rate, SO₂ concentration, gas flow rate and gas flow direction on the SO₂ removal efficiency and overall mass transfer coefficient. The effect of liquid flow rate on SO₂ removal efficiency shows that at very low liquid flow rate, the NaOH available at the membrane surface for reacting with SO₂ is limited due to the liquid phase resistance. As liquid flow rate is above the minimum flow rate which overcomes the liquid phase resistance, the SO₂ absorption rate is controlled by resistance in the gas phase and the membrane. The SO₂ absorption rate with inlet SO₂ concentration was sharply increased by using hollow fiber membranes compared to a conventional wetted wall column because the former has higher gas liquid contacting area than the latter. The mass transfer coefficient is independent of pressure. When the gas mixture was fed in the shell side, the removal efficiency of SO₂ declined because of channeling problems on the shell side. Also, the addition of PEG in polymer dopes increased SO₂ removal efficiency. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

The effect of ethane on the performance of commercial polyphenylene oxide and Cardo-type polyimide hollow fiber membranes in CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> separation applications

Impurities such as hydrogen sulfide, water vapor and heavy hydrocarbons in natural gas have considerable effects on the membrane performance. Small amounts of condensable and polymer soluble components in the feed gas cause swelling or plasticization of glassy membranes, leading to a reduction in membrane selectivity. In the present research the influence of ethane was investigated on the permeance and selectivity of two commercially available hollow fiber membranes, namely Cardo-type polyimide and PPO hollow fibers for CO₂/CH₄ separations. It was concluded that the gas mixture permeation rate was increased in the presence of C₂H₆. However, the CO₂/CH₄ separation factors remained almost the same in the presence and absence of the C₂H₆.     

Reduction of CO2 emissions by a membrane contacting process☆

A membrane-based gas–liquid contacting process was evaluated in this work for CO₂ removal from flue gases. The absorption of CO₂ from a CO₂–N₂ mixture was investigated using a commercial hollow fiber membrane contactor and water or diethanolamine as absorbing solvents. Significant CO₂ removal (up to 75%) was achieved even with the use of pure water as absorbent. By using aqueous amine solutions and chemical absorption, mass transfer improved, and CO₂ removal was nearly complete (∼99%). A mathematical model was developed to simulate the process and it was validated with experimental data. Results show that membrane contactors are significantly more efficient and compact than conventional absorption towers for acid gas removal.