Gas‐separation properties of amine‐crosslinked polyimide membranes modified by amine vapor

The modification of a polyimide (PI) membrane by aromatic amine vapor was performed in this work to increase the crosslinking of the membrane and to study the effect on gas permeability and the corresponding selectivity. The single‐gas permeability of the membranes at 35 °C was probed for H₂, O₂, N₂, CO₂, and CH₄. From the relationship between the combinations of gases and ideal permselectivities, this study showed that amine‐crosslinked PI membranes tended to increase gas permselectivities exponentially with the increasing difference in gas kinetic diameter. Moreover, this study illustrated that the permeability of the membranes was influenced by the formation rate of amine‐crosslinked networks or chemical structures after the reaction. The membranes had the highest level of permselectivities among crosslinked PI membranes for O₂/N₂, and the H₂/CH₄ permselectivity increased 26 times after vapor modification. Furthermore, the modification method that used aromatic amine vapor produced thin and strongly modified layers. These findings indicate that modification is an advantageous technique for improving gas‐separation performance, even considering thinning. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44569.     

Facile CO2 Separation in Composite Membranes

CO₂ emission from anthropogenic sources has raised worldwide environmental concerns and hence proficient energy paradigm has tilted towards CO₂ capture. Membrane technology is one of the efficient technologies for CO₂ separation since it is environmentally friendly, inexpensive, and offers high surface areas. Various approaches are discussed to improve membrane performance focusing mainly on permeability and selectivity parameters. Different types of fillers are incorporated to reach the Robeson's upper bound curve. In this review, polymer‐inorganic nanocomposite membranes for the separation of CO₂, CH₄, and N₂ from various gas mixtures are comprehensively discussed. Metal organic frameworks (MOFs) and ionic liquid (ILs) mixed‐matrix membranes are also considered.     

Carbon molecular sieve membranes derived from Matrimid® polyimide for nitrogen/methane separation

A commercial polyimide, Matrimid® 5218, was pyrolyzed under an inert argon atmosphere to produce carbon molecular sieve (CMS) dense film membranes for nitrogen/methane separation. The resulting CMS dense film separation performance was evaluated using both pure and mixed N₂/CH₄ permeation tests. The effects of final pyrolysis temperature on N₂/CH₄ separation are reported. The separation performance of all CMS dense films significantly exceeds the polymer precursor dense film. The CMS dense film pyrolyzed at 800 °C shows very attractive separation performance that surpasses the polymer membrane upper bound line, with N₂ permeability of 6.8 Barrers and N₂/CH₄ permselectivity of 7.7 from pure gas permeation, and N₂ permeability of 5.2 Barrers and N₂/CH₄ permselectivity of 6.0 from mixed gas permeation. The temperature dependences of permeabilities, sorption coefficients, and diffusion coefficients of the membrane were studied, and the activation energy for permeation and diffusion, as well as the apparent heats of sorption are reported. The high permselectivity of this dense film is shown to arise from a significant entropic contribution in the diffusion selectivity. The study shows that the rigid ‘slit-shaped’ CMS pore structure can enable a strong molecular sieving effect to effectively distinguish the size and shape difference between N₂ and CH₄.     

High oxygen permeable Zeolite-4A poly(dimethylsiloxane) membrane for air separation

High oxygen permeability with optimal selectivity of the membrane is required for advancement in air separation membrane technology. Zeolite 4A-PDMS composite membranes were prepared by incorporation of Zeolite 4A nanoscale crystals during the polymerization process of PDMS membrane using toluene and n-heptane solvents, and their oxygen gas permeability and selectivity were explored. Small angle neutron scattering (SANS) technique was further used to study the polymer chain conformation and structure of membranes influenced by Zeolite 4A loading. The intersegmental distance between polymer chains and polymer chain aggregation or clustering were found to be increased on increasing the Zeolite 4A content in the membranes. Increment in the O₂ permeability and O₂/N₂ selectivity were observed for both type of membranes (toluene and n-heptane) with 1 wt% Zeolite 4A loading. The best performance result with O₂/N₂ selectivity of 2.6, and O₂ permeability of 1052 Barrer was exhibited by PDMS/toluene membrane loaded with 1 wt% Zeolite 4A. The PDMS/toluene membranes with 10 wt% Zeolite 4A loading exhibited increased O₂ permeability of 1245 Barrer with a fair O₂/N₂selectivity of ~1.7, while the PDMS/n-heptane membrane with the same loading exhibited excellent O₂ permeability of 6773 Barrer but lesser O₂/N₂ selectivity of ~1.2. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48047.     

Vapor Permeation and Pervaporation of Aqueous 2‐Propanol Solutions through the Torlon® Poly(amide imide) Membrane

Abstract

In the present study, vapor permeation and pervaporation of aqueous 2‐propanol mixtures were investigated using Torlon^® poly(amide imide) as a membrane material. Torlon membranes preferentially permeated H₂O from aqueous 2‐PrOH mixtures both by vapor permeation and pervaporation. Diffusion experiments led to the conclusion that both solubility selectivity and diffusivity selectivity showed a preference for H₂O. Solubility selectivity is by far the dominant factor governing permselectivity, and as a result, Torlon membranes showed permselectivity toward water in vapor permeation and pervaporation. The present study showed that Torlon^® poly(amide imide) is a membrane material potentially applicable to the dehydration of water miscible organics.     

A novel polymeric gel electrolyte systems containing magnesium salt with ionic liquid

A new polymeric gel electrolyte system consisting of poly(ethylene oxide)-modified polymethacrylate (PEO-PMA) with organic ionic liquid dissolving magnesium salt, Mg[(CF₃SO₂)₂N]₂, has been developed. The ionic conductance and electrochemical properties of the gel films were investigated. The obtained gel film was self-standing, transparent and flexible with sufficient mechanical strength. Thermal analysis of the gel film showed that it is homogeneous and amorphous over a wide temperature range. The highest conductivity, ca. 3.5 mS cm⁻¹ at 60 °C, was obtained for the polymeric gel containing 80 wt.% of the liquid component that consists of 80 mol% of EMITFSI (1-ethyl-3-methylimidazolium bis(trofluoromethylsulfonyl)imide) and 20 mol% of Mg[(CF₃SO₂)₂N]₂. The sort of the ionic liquid affected much on the ionic conductivity of the gel. The dc polarization of a Pt/polymeric gel electrolyte/Mg cell proved that the magnesium ion (Mg²⁺) can mobile in the present polymeric gel system.     

Characterization of Nanocomposite Polymeric Membrane

Composite membrane has good permeability and selectivity for gases, which depends upon the operating conditions. The solubility and diffusivity of the penetrant in the polymer matrix control the transport through non-porous dense membrane. In the present work, the nano sized particles of Co_0.6Zn_0.4Fe₂O₄ were prepared by the co-precipitation method and characterized by the XRD technique with particle size of 10 nm. Nanocomposite polycarbonate membranes were studied before and after irradiation by the ³⁵Cl⁹⁺ ion of 120 MeV at the Nuclear Science Centre, New Delhi. The distribution of nanoparticles throughout the membrane was characterized by the optical microscope. Gas transport properties of H₂, CO₂ and air for these nanocomposite membranes were investigated. It was found that membrane containing nanoparticles shows low permeability with high permselectivity. After irradiation by swift heavy ions (SHI), high gas permeability and high permselectivity has been observed for these nanocomposite membranes.     

Selective Separation of Toluene/n‐Heptane by Supported Ionic Liquid Membranes with [Bmim][BF4]

Room‐temperature ionic liquids serve as alternative solvents for volatile organic compounds in liquid‐liquid extraction and liquid membrane separation. 1‐Butyl‐3‐methylimidazolium tetrafluoroborate ([Bmim][BF₄]) was applied for extraction and supported ionic liquid membranes (SILMs) to separate toluene and n‐heptane. A high separation factor of toluene was achieved due to the strong interaction between ionic liquid cations and toluene. The mass transfer performance of the SILM process was enhanced by higher operating temperature. With the increase of initial toluene concentration in the feed phase, the mass transfer flux and removal efficiency of the SILM process were improved, while the separation factor decreased. The mass transfer flux was growing with the increase of flow rate at both sides. The SILM process was stable over a long time period due to the high viscosity and low volatility of [Bmim][BF₄].     

Hybrid sol–gel membranes of polyacrylonitrile–tetraethoxysilane composites for gas permselectivity

Sol–gel reaction of tetraethoxysilane (TEOS) with fumed silica–polyacrylonitrile (PAN) membrane was carried out to prepare hybrid gas permeable membranes for oxygen and nitrogen separation. Various amounts of fumed silica microparticles with a few μm diameters were compounded in PAN–dimethylsulfoxide (DMSO) solution. After casting of the viscous compound solution on a flat sheet with 100 μm thickness, DMSO was evacuated under vacuum at 80°C. Then, the silica–PAN composite membranes were treated with TEOS for 1 day at 40°C in methanol. Air permeation was examined and compared in silica–PAN composite membranes with and without TEOS treatment. The latter hybrid membranes showed selective oxygen permeability, which depended on amounts of fumed silica in the membrane. The TEOS hybrid PAN membranes have a high ability of oxygen permselectivity for O₂/N₂ gas mixture with α(O₂/N₂) = 13–17, when the silica content was in the range of 13–20 wt %. This is attributed to siloxane network formation in hybrid silica–PAN composite membranes. Favorable siloxane network formation resulted in high oxygen permeability of the hybrid composite membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1752–1759, 2003     

Gel electrolytes based on lithium modified silica nano-particles

In this work lithium modified silica (Li-SiO₂) nano-particles were synthesized and used as a single ion lithium conductor source in gel electrolytes. It was found that Li-SiO₂ exhibited good compatibility with DMSO, DMA/EC (a mixture of N,N-dimethyl acetamide and ethylene carbonate) and the ionic liquid, N-methyl-N-propyl pyrrolidinium bis(trifluoromethylsulfonyl) amide ([C₃mpyr][NTf₂]). Several gel electrolytes based on Li-SiO₂ were obtained. These gel electrolytes were investigated by DSC, solid state NMR, conductivity measurements and cyclic voltammetry. Conductivities as high as 10⁻³ S/cm at room temperature were observed in these nano-particle gel electrolytes. The results of electrochemical tests showed that some of these materials were promising for using as lithium conductive electrolytes in electrochemical devices, with high lithium cycling efficiency evident.     

Gas permeability and permselectivity of plasma‐treated polypropylene membranes

The effects of NH₃‐plasma and N₂‐plasma treatment on rubbery polypropylene (PP) membrane upon permeation behavior for CO₂, O₂, and N₂ were investigated from their permeability measurements. The NH₃‐plasma and N₂‐plasma treatment on PP membranes could increase both the permeability coefficient for CO₂ and the ideal separation factor for CO₂ relative to N₂. For O₂ transport, both the permeability coefficient for O₂ and the ideal separation factor for O₂ relative to N₂ also increased. NH₃‐plasma and N₂‐plasma treatment on PP membranes possibly brings about an augmentation of permeability for CO₂ and permselectivity of CO₂ relative to N₂ simultaneously, but unfortunately the plasma‐treated PP membrane does not reach the level of CO₂ separation membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

A study of gas transport through interfacially formed poly(N,N-dimethylaminoethyl methacrylate) membranes

Gas transport through interfacially formed poly(N,N-dimethylaminoethyl methacrylate) membranes was investigated. The membrane performance for the separation of binary CO₂/N₂, CO₂/CH₄ and CO₂/H₂ mixtures was studied, and the coupling effects between the permeating species were evaluated by comparing the permeance of individual components in the mixture with their pure gas permeance. For the permeation of these binary gas mixtures, the presence of CO₂ was shown to influence the permeation of the other components (i.e., N₂, H₂ and CH₄), whereas the permeation of CO₂ was not affected by these components. In consideration that water vapor is often encountered in applications involving CO₂ separation, the presence of water vapor on the membrane permselectivity was also studied. When hydrated, the membrane was shown to be more permeable to CO₂, while the membrane selectivity did not change significantly. Unlike membranes based on size-sieving of penetrant molecules, the present membranes exploit the favorable interactions between the hydrophilic quaternary amines in the membrane and CO₂, especially in the presence of water vapor in the feed.     

Mixed matrix metal–organic framework membranes for efficient CO2/N2 separation under humid conditions

Mixed matrix metal–organic framework (MOF) membranes show excellent application prospects in gas separation. However, their stability in various practical application scenarios is poor, especially under humid conditions. Herein, we encapsulated a hydrophobic ionic liquid (IL) into the cavity of MOFs, which effectively mitigated the competition between H₂O and CO₂ in humid gas mixtures, leading to stable and high-performance gas separation. For this reason, the resulting membranes using polymer of intrinsic miroporosity-1 (PIM-1) as a polymer matrix show good CO₂/N₂ separation performance and long-term test stability under humid environment. In particular, the 20 wt% IL-UiO/PIM-1 shows a high permeability of 13,778 Barrer and competitive CO₂/N₂ separation factor of ~35.2, transcending the latest upper bound. Besides, the according membrane module exhibits slightly decreased CO₂ permeability and selectivity, promoting the application of self-supporting membranes. This work provides a reliable strategy for the rational design of MOF-based hybrid membranes under extreme conditions.     

Synthesis and characterization of soluble poly(amide‐imide)s bearing triethylamine sulfonate groups as gas dehumidification membrane material

A series of soluble poly(amide‐imide)s (PAIs) bearing triethylammonium sulfonate groups were synthesized directly using trimellitic anhydride chloride (TMAC) polycondensation with sulfonated diamine such as 2,2′‐benzidinedisulfonic acid (BDSA), 4,4′‐diaminodiphenyl ether‐2,2′‐disulfonic acid (ODADS), and nonsulfonated diamine 4,4‐diaminodiphenyl methane in the presence of triethylamine. The resulting copolymers exhibited high molecular weights (high inherent viscosity), and a combination of desirable properties such as good solubility in dipolar aprotic solvents, film‐forming capability, and good mechanical properties. Wide‐angle X‐ray diffraction revealed that the polymers were amorphous. These copolymers showed high permeability coefficients of water vapor because of the presence of the hydrophilic triethylammonium sulfonate groups. The water vapor permeability coefficients (P_w) and permselectivity coefficients of water vapor to nitrogen and methane [α(H₂O/N₂) and α(H₂O/CH₄)] of the films increased with increasing the amount of the triethylammonium sulfonated groups. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Prediction of CO2 gas permeability behavior of ionic liquid–polymer membranes (ILPM)

Predicting the gas permeability of ionic liquid‐polymeric membranes (ILPM) is of great importance for the design of efficient gas separation membrane materials. The available models for the prediction of CO₂ gas permeability through ionic liquid‐polymeric membranes were analyzed using the literature data. Maxwell model was selected for modification due to relatively accurate prediction capability. The Maxwell model was modified for ionic liquid‐polymeric membranes by incorporating model parameter k for the effectiveness of volume fraction of dispersed phase. The established methodology was tested for different ionic liquid‐polymeric membrane systems for validation. A satisfactory agreement was observed for predicted and experimental permeability by using the current approach. This method can be used for the prediction of CO₂ gas permeability through ionic liquid‐polymeric membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44761.     

Fabrication of Homogenous Polymer‐Zeolite Nanocomposites as Mixed‐Matrix Membranes for Gas Separation

Interfacial void‐free mixed‐matrix membranes (MMMs) of polyimide (PI)/zeolite were developed using 13X and Linde type A nano‐zeolites and tested for gas separation purposes. Fabrication of a void‐free polymer‐zeolite interface was verified by the decreasing permeability developed by the MMMs for the examined gases, in comparison to the pure PI membrane. The molecular sieving effect introduced by zeolite 13X improved the CO₂/N₂ and CO₂/CH₄ selectivity of the MMMs. Separation tests indicated that the manufactured nanocomposite membrane with 30 % loading of 13X had the highest permselectivity for the gas pairs CO₂/CH₄ and CO₂/N₂ at the three examined feed pressures of 4, 8 and 12 atm.     

Preparation of plasma-polymerized membranes from I-(trimethylsilyl)-I-propyne and gas permeability through the membranes

Summary Plasma-polymerized membranes for gas separation were prepared from 1-(trimethylsilyl)-1-propyne. The permeation data of He, H₂ 0₂, N₂, CO₂, and CH₄ through the membranes showed plasma-polymerized 1-(trimethylsilyl)-1-propyne had high permselectivity but low permeability compared with poly[l-(trimethylsilyl)-1-propyne]. This behavior is considered to be due to the crosslinking structure of the plasma-polymerized membrane. The correlation between plasma polymerization conditions and the membrane performance was studied. The optimum condition at which the deposition rate of the plasma polymer is maximized agreed with the optimum value to yield maximum separation factor of gases through the membrane.     

The additive effect of zwitterion and nano-particles on ion dissociation in polyelectrolytes

To realise the battery potential of gel polyelectrolytes greater ion dissociation, ultimately leading to higher conductivities, must be achieved. Higher conductivities will result through increasing the ion-dissociating properties of the gel polyelectrolyte. The poor degree of ion dissociation arises as the active ion tends to remain in close proximity to the backbone charge. Nano-particle inorganic oxides, and zwitterionic compounds have been shown to act as dissociation enhancers in certain polyelectrolyte systems. In an attempt to further increase ion dissociation the addition of both TiO₂ nano-particles and a zwitterionic compound based on 1-butylimidazolium-3-N-(butanesulphonate) were added to the gel polyelectrolyte system poly (Li-2-acrylamido-2-methyl-1-propane sulphonate-co-N,N′-dimethylacrylamide), poly(Li-AMPS-co-DMAA) to determine if a synergistic effect occurs. Two different solvents were used to determine the breadth of applicability of the additive effect. The use of both dissociators resulted in the maximum ionic conductivity being achieved at lower nano-particle concentrations when compared to an identical system without zwitterion.     

Enhanced solubility of hydrogen and carbon monoxide in propane‐ and propylene‐expanded liquids

Conventional propylene hydroformylation occurs in a gas‐expanded liquid phase. Reliable knowledge of the phase equilibria of such systems, including the solubilities of CO and H₂ in propylene‐expanded solvents, is essential for rational process design and development. Herein, we report the vapor–liquid equilibrium (VLE) data of the following ternary systems involving CO, H₂, propane, propylene, toluene and NX‐795 at temperatures from 70 to 90°C and pressures up to 1.5 MPa: propane/H₂/toluene, propane/CO/toluene, propylene/H₂/toluene, propylene/CO/toluene, propane/H₂/NX‐795, propane/CO/NX‐795, propylene/H₂/NX‐795 and propylene/CO/NX‐795. The solubilities of H₂ and CO in either propane‐expanded or propylene‐expanded phases are observed to be greater than those in the neat organic solvents, by as high as 78% at 70°C and 1.5 MPa. By modeling the vapor and the liquid phases as pseudo‐binary systems, the Peng‐Robinson equation of state (PR‐EoS) with van der Waals’ mixing rules and binary interaction parameters is shown to satisfactorily predict the experimental VLE data. © 2017 American Institute of Chemical Engineers AIChE J, 64: 970–980, 2018     

Mixed matrix membranes of 6FDA-6FpDA with surface functionalized γ-alumina particles. An analysis of the improvement of permselectivity for several gas pairs

Herein, mixed matrix membranes including alumina particles whose surfaces have been differently modified have been made and characterized. The polymeric matrix is a fluorinated polyimide, 6FDA-6FpDA, whereas the inorganic constituent parts are neat, silanized or poly-vinyl-pirrolidone-coated nanometric γ-Al₂O₃ particles of 40 nm in diameter, which have been added in an approximated percentage of a 12% w/w.All the modified or unmodified added particles lead to similar improvements in the permselectivity of the gas pairs studied. Only in the case of the O₂/N₂ pair the increase in selectivity for the silanized particles is not as effective as the observed permeability enhancement for the uncoated and PVP-coated particles. In case of CO₂/CH₄, the 1991 Robeson's upper bond line is overpassed.The characteristics of the permselectivity improvement for the different inorganic particles have been analyzed in terms of the properties of the particle–polymer interfacial properties.