Dialdehyde polyethylene glycol cross-linked poly(vinyl alcohol) membranes with enhanced CO2/N2 separation performance

The development of carbon dioxide (CO₂) separation technology is crucial for mitigating global climate change and promoting sustainable development. In this study, we successfully synthesized an array of cross-linked poly(vinyl alcohol) (PVA) membranes, xALD-PEG-ALD-c-PVA, with enhanced CO₂/N₂ separation performance by employing dialdehyde polyethylene glycol (ALD-PEG-ALD) as a cross-linker. The formation of the cross-linked network structure not only inhibits the crystallization of PVA but also disrupts hydrogen bonding and thus increases fractional free volume of PVA chains. Under the synergistic effect of these multiple factors, the cross-linked PVA membranes exhibit a significantly improved CO₂ permeability. Moreover, they maintain high CO₂/N₂ selectivity, attributing to the CO₂-philic characteristic of ethylene oxide groups in the cross-linked structure. At the ALD-PEG-ALD content of 1.6 mmol g⁻¹, the xALD-PEG-ALD-c-PVA membrane demonstrates a CO₂ permeability of 41.4 barrer and a CO₂/N₂ selectivity of 57.4 at 2 bar and 25°C. Furthermore, compared with the pristine PVA membrane, xALD-PEG-ALD-c-PVA membranes manifest superior mechanical properties and outstanding separation performance for a CO₂/N₂ (15/85, vol%) gas mixture. The excellent combination of permeability and selectivity makes xALD-PEG-ALD-c-PVA membranes highly promising for various CO₂ separation applications.     

Transport properties of gases through integrally skinned asymmetric composite membranes prepared from date pit powder and polysulfone

Studies were conducted on transport properties and separation performance of date pit/polysulfone composite membranes for CO₂, CH₄, N₂, He, and H₂ gases. Date seeds were obtained and processed into powder. Asymmetric flat sheet membrane was prepared by solvent casting method with 2–10 wt % date pit powder. Membrane characterization was done using high pressure gas permeation, X‐ray diffraction, thermogravimetric, and scanning electron microscope analyses. The separation performance and the plasticization resistance property were evaluated in terms of gas permeability, selectivity, and plasticization pressure, respectively. Time dependent performance properties were evaluated up to a pressure of 40 bar for 75 days. Results obtained showed the highest selectivity values of 1.54 (He/H₂), 3.637 (He/N₂), 2.538 (He/CO₂), 2.779 (He/CH₄), 3.179 (H₂/N₂), 3.907 (H₂/CO₂), 1.519 (CH₄/N₂), 1.650 (CO₂/N₂), and 1.261 (CO₂/CH₄) at 10 bar and 35 °C feed pressure and temperature, respectively. The resulting composite membrane showed about 39.50 and 66.94% increase in the selectivity of He/N₂ and CO₂/CH₄, respectively, as compared to the pure polysulfone membrane. Thus, the membrane composites possess some potentials in membrane gas separation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43606.     

Effects of pressure and temperature on fixed-site carrier membrane for CO2 separation from natural gas

In this paper, the effect of testing temperature on the performance of fixed carrier membrane for CO₂ separation were studied. The blend composite membranes were developed respectively with a blend of PEI-PVA (polyetheleneimine-polyvinyl alcohol) as separation layer and PS (polysulfone) ultrafiltration membranes as the substrates. The permselectivity of the membranes was measured with CO₂/CH₄ mixed gas. The effect of testing temperature on membrane separation performance was investigated. The results showed that both the permeances of CO₂ and CH₄ decreased with the increase of temperature, and the permeances decreased more quickly under low pressure than those under high pressure. At the feed pressure of 0.11 MPa, the CO₂/ CH₄ selectivity of PEI-PVA/PS blend composite membrane reduced along with temperature increment. Under the feed pressure of 0.21 MPa, as well as 1.11 MPa, the selectivity decreased with the increase of temperature.     

Effects of pressure and temperature on fixed-site carrier membrane for CO<Subscript>2</Subscript> separation from natural gas

In this paper, the effect of testing temperature on the performance of fixed carrier membrane for CO₂ separation were studied. The blend composite membranes were developed respectively with a blend of PEI-PVA (polyetheleneimine-polyvinyl alcohol) as separation layer and PS (polysulfone) ultrafiltration membranes as the substrates. The permselectivity of the membranes was measured with CO₂/CH₄ mixed gas. The effect of testing temperature on membrane separation performance was investigated. The results showed that both the permeances of CO₂ and CH₄ decreased with the increase of temperature, and the permeances decreased more quickly under low pressure than those under high pressure. At the feed pressure of 0.11 MPa, the CO₂/ CH₄ selectivity of PEI-PVA/PS blend composite membrane reduced along with temperature increment. Under the feed pressure of 0.21 MPa, as well as 1.11 MPa, the selectivity decreased with the increase of temperature.     

Gas transport in partially fluorinated low-density polyethylene

Low-density polyethylene film was subjected to direct fluorination on one surface by exposure to a dilute fluorine gas stream for various periods of time. Various analyses indicate partial fluorination of a thin surface layer. The permeability coefficients for He, CO₂, and CH₄ were measured at 35°C. The permeability of He was not changed by fluorination; whereas, values for CO₂ and CH₄ were decreased by as much as two orders of magnitude. The selectivity of transport for gas pairs of different molecular size was greatly improved, suggesting applications of this technique for membrane separation processes.     

Preparation of poly(acrylic acid)/poly(vinyl alcohol) membrane for the facilitated transport of CO2

Poly(acrylic acid) (PAA)/poly(vinyl alcohol) (PVA) membrane was prepared for the facilitated transport of CO₂. The carrier of CO₂ was monoprotonated ethylenediamine and was introduced in the membrane by ion exchange. The ion‐exchange capacity of the membrane was 4.5 meq/g, which was much higher than that of the Nafion 117 membrane. The membrane was highly swollen by the aqueous solution. Much higher selectivity of CO₂ over N₂ and higher CO₂ permeability were obtained in the PAA/PVA membrane than in the Nafion membrane because of the higher ion‐exchange capacity and solvent content. The highest selectivity was more than 1900 when the CO₂ partial pressure in the feed gas was 0.061 atm. Effects of ion‐exchange capacity, membrane thickness, and annealing temperature in conditions of membrane preparation on membrane performance were investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 936–942, 2001     

Effects of membrane thickness and heat treatment on the gas transport properties of membranes based on P84 polyimide

P84 polyimide membranes with thicknesses ranging from 6 to 310 μm were successfully fabricated by spin coating. The glass transition temperature of the P84 powder was found to be 315°C using differential scanning calorimetry, whereas its decomposition temperature was 536°C using thermogravimetric analysis. Scanning electron microscopy was used to examine the morphology of the membranes. The permeability of single gas (He, N₂, O₂, and CO₂) and the ideal selectivity of gas pair (O₂/N₂, He/CO₂, CO₂/N₂, and He/O₂), as a function of membrane thickness, were determined. The results showed that the permeability of a single gas increased with increasing membrane thickness, whereas the selectivity of a given gas pair was nearly independent of the membrane thickness. The average selectivity of O₂/N₂, He/CO₂, CO₂/N₂, and He/O₂ were found to be 8.2, 10.0, 12.9, and 15.8, respectively. The effects of heat treatment on the membrane morphology and gas transport properties were investigated for three annealing temperatures, i.e., 80°C, 200°C, and 315°C. The membrane annealed at 315°C was cracked due to the stress sustained either during heating or cooling, thereby resulting in little or no selectivity. The permeabilities of P84‐118 membrane (118 μm thickness) annealed at 80°C were 16.2, 0.196, 1.20, and 2.01 Barrer for He, N₂, O₂, and CO₂, respectively. The permeabilities of P84‐118 membrane annealed at 200°C decreased by 9.75%, 47.96%, 25.83%, and 30.85% for He, N₂, O₂, and CO₂, respectively, as compared with those at 80°C, whereas the ideal selectivities increased by 42.65%, 30.52%, 32.85%, and 21.63% for O₂/N₂, He/CO₂, CO₂/N₂, and He/O₂, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Enhanced CO2 separation performance by PVA/PEG/silica mixed matrix membrane

This article focused on segregation of low concentration CO₂ from CO₂/N₂ mixture gas by implementing high‐performance facilitated transport mixed matrix membranes (MMMs) in large‐scale carbon capture techniques. These advanced, novel CO₂‐selective membrane materials were developed by embedding silica nanoparticles at different loading into the poly(vinyl alcohol) (PVA)/poly(ethylene glycol) (PEG) matrix using solution casting. In situ sol–gel technique was applied for the synthesis of the hydrophilic SiO₂ nanoparticles. The compatibility of filler‐polymer matrix plays a crucial role in the optimization of the membrane performance. The dispersion and interaction of the filler into the polymer matrix were confirmed by thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, X‐ray diffraction, field emission scanning electron microscopy, contact angle tests, and swelling ratio analysis. Field emission scanning electron microscopy analysis of the synthesized MMMs established the homogeneous dispersion of the fillers in the polymer matrix. Owing to its good compatibility with PVA/PEG matrix, the inclusion of fillers significantly increased the overall separation efficiency of CO₂ within the membrane. Compared to pristine PVA/PEG membrane, PVA/PEG/silica membrane with 3.34 wt % silica loading showed pronounced improvement in its gas separation properties with 78% augmentation in CO₂ permeability and 45% enhancement in CO₂/N₂ selectivity for fixed conditions pertaining to sweep side water flow rate of 0.04 mL/min and 100 °C temperature. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46481.     

Measurement of helium and carbon dioxide permeability through polyamidoimide films

The helium and carbon dioxide permeability through film samples of polyamidoimides (PAI) of two series at room temperature and a partial pressure drop of 0.1 MPa across the membrane has been studied. A correlation between the chemical structure of the studied PAI and their permeability has been ascertained: the helium permeability through PAI samples grows with increasing content of the diamine fragment, which reduces the chain stiffness; the selectivity of the studied PAI-based membrane samples for the He/CO₂ gas pair declines as the carbon dioxide permeability increases and the diamine fragment of PAI becomes more complex.     

Carbon molecular sieve membranes for natural gas purification: Role of surface flow

Carbon molecular sieve membranes (CMSM) were prepared from the pyrolysis of polyimide films within a temperature range of 600°C-800°C under nitrogen stream. The membrane samples were characterized and tested for the permeation of He, CH₄, CO₂, and N₂ at different pressures and temperatures, respectively. The CMSM700 membrane (pyrolyzed at 700°C) showed an ideal selectivity of ~ 11 for N₂/CH₄ with a permeability of 2.18 × 10⁻¹⁵ mol · m/m² · s · Pa for N₂. The separation mechanism for the N₂/CH₄ pair was shown to be largely molecular sieving rather than surface flow. The membrane showed an ideal selectivity of ~ 500 for the CO₂/CH₄ pair with a CO₂ permeability of 9.72 × 10⁻¹⁴ mol · m/m² · s · Pa. The permeability of He was lower than that of CO₂, suggesting that the surface flow played a significant role in the CO₂ permeation. The updated permeability-selectivity tradeoff curves show that this CMSM membrane compared favourably with other membrane materials reported in the literature for the removal of N₂ and CO₂ from CH₄ for natural gas upgrading.     

Preparation of vinyl amine‐co‐vinyl alcohol/polysulfone composite membranes and their carbon dioxide facilitated transport properties

A vinyl amine–vinyl alcohol copolymer (VAm–VOH) was synthesized through free‐radical polymerization, basic hydrolysis in methanol, acidic hydrolysis in water, and an anion‐exchange process. In the copolymer, the primary amino groups on the VAm segment acted as the carrier for CO₂‐facilitated transport, and the vinyl alcohol segment was used to reduce the crystallinity and increase the gas permeance. VAm–VOH/polysulfone (PS) composite membranes for CO₂ separation were prepared with the VAm–VOH copolymer as a selective layer and PS ultrafiltration membrane as a support. The membrane gas permselectivity was investigated with CO₂, N₂, and CH₄ pure gases and their binary mixtures. The results show that the CO₂ transport obeyed the facilitated transport mechanism, whereas N₂ and CH₄ followed the solution–diffusion mechanism. The increase in the VAm fraction in the copolymer resulted in a carrier content increase, a crystallinity increase, and intermolecular hydrogen‐bond formation. Because of these factors, the CO₂ permeance and CO₂/N₂ selectivity had maxima with the VAm fraction. At an optimum applied pressure of 0.14 MPa and at an optimum VAm fraction of 54.8%, the highest CO₂ permeance of 189.4 GPU [1 GPU = 1 × 10^?6 cm³(STP) cm^?2 s^?1 cmHg^?1] and a CO₂/N₂ selectivity of 58.9 were obtained for the CO₂/N₂ mixture. The heat treatment was used to improve the CO₂/N₂ selectivity. At an applied pressure of 0.8–0.92 MPa, the membrane heat‐treated under 100°C possessed a CO₂ permeance of 82 GPU and a CO₂/N₂ selectivity of 60.4, whereas the non‐heat‐treated membrane exhibited a CO₂ permeance of 111 GPU and a CO₂/N₂ selectivity of 45. After heat treatment, the CO₂/N₂ selectivity increased obviously, whereas the CO₂ permeance decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40043.     

A theoretical comparison of facilitated transport and solution-diffusion membrane modules for gas separation

Computer models were developed to compare the performances of facilitated transport (FT) and conventional solution-diffusion (SD) membrane modules, and sample calculations given for the separation of CO₂/CH₄ mixtures. Previous studies have indicated that high CO₂ fluxes can be obtained with laboratory-sized sheets of FT membranes; but these studies have not examined the performance of these membranes as modules. In the present study, the FT membrane properties are those of an ion exchange membrane with ethylene diamine as the CO₂ carrier, and the SD membrane properties are those of a typical, commercial cellulosic membrane. For the conditions examined, the facilitation effect in the FT membrane module is significant only when the partial pressure of CO₂ is relatively low (< 10 psia). For a low CO₂ partial pressure (7.5 psia) in the feed, the FT membrane with an ethylene diamine concentration of 8 M has a factor of 2 lower area requirement and 2% greater methane recovery than for an SD membrane with a selectivity of 30. Above 50 psia CO₂ partial pressure, the SD and FT membrane modules function identically. We have also shown that the fraction of the total CO₂ flux contributed by the ethylene diamine carrier increases along the flow path of the membrane module, thereby making the choice of an optimum equilibrium constant for the CO₂/diamine reaction more difficult than in a membrane sheet with constant boundary conditions. However, even for the low CO₂ feed partial pressure the required membrane area increases by less than 35% when the actual equilibrium constant is a factor of 10 greater than the optimum value.     

Phosphorylated nanocellulose fibrils/PVA nanocomposite membranes for biogas upgrading at higher pressure

ABSTRACT

High moisture uptake and excellent mechanical properties of cellulose nano-fibril (CNF) make it an interesting material to use as an additive in facilitated transport membranes. The objective of this work is to develop novel phosphorylated nanocellulose fibrils (PCNF)/polyvinyl alcohol (PVA) nanocomposite membranes for biogas upgrading. Results showed that the thickness of membrane increases with increasing concentration of PCNF. The addition of PCNF to pristine PVA membranes has beneficial effect for CO₂/CH₄ separation. However, maximum performance was achieved with 1 wt.% PCNF in 2% PVA at pH 12. Furthermore, increasing feed pressure caused a decrease in both permeability and selectivity.     

Efficient separation of N2 and he at low temperature using MFI membranes

Ultra‐thin MFI membranes were evaluated for N₂/He separation over the temperature range of 85–260 K for the first time. The membranes were rather nitrogen selective at all the conditions investigated. A highest N₂/He selectivity of 75.7 with a high N₂ flux of 83 kg/m²/h was observed at 124 K. The separation was attributed to adsorption selectivity to N₂, effectively hindering the transport of He in the zeolite pores. The exceedingly high permeance even at low temperatures was ascribed to the ultrathin (<1μm) membrane used. As the pressure ratios increased, a better separation performance was obtained. A mathematical model showed the largest difference of adsorbed loading over the film at ca. 120 K was the main reason for the observed maximum selectivity. Further, the modelling indicated the selectivity would increase 2–3 times by reducing the influence of defects, concentration polarization, and pressure drop over the support. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2833–2842, 2016     

Microwave synthesis of tubular zeolitic imidazolate framework ZIF-8 membranes for CO2/CH4 separation

The separation of CO₂/CH₄ is reported in detail by using zeolitic imidazolate framework (ZIF-8) membrane which was prepared on 3-aminopropyltriethoxysilane modified Al₂O₃ tube through microwave heating synthesis. Attributed to the preferential adsorption affinity of CO₂ over CH₄ and a narrow pore window of 0.34 nm, the ZIF-8 membrane shows high separation performances for the separation of CO₂/CH₄ mixtures. For the separation of equimolar CO₂/CH₄ mixture at 100°C and 2 bar feed (1 bar permeate) pressure, a CO₂ permeance of 1.02 × 10^?8 mol/m²· s· Pa and a CO₂/CH₄ selectivity of 6.8 are obtained, which is promising for CO₂ separation.     

Effects of preparation parameters on CO2/N2 gas permselectivity of polyether thin film composite membrane

In this work, ether oxide (EO)-based multilayer composite membranes were prepared via interfacial polymerization (IP) of trimesoyl chloride (TMC) and polyetheramine (PEA) on polydimethylsiloxane precoated polysulfone support membrane. The effects of preparation parameters, such as monomer concentrations, reaction time, and heat-treatment temperature on the membrane performance were investigated. The optimal preparation parameters have been concluded. The results showed the increasing monomers concentration of both PEA and TMC can lead to the decrease of CO₂ permeance and increase of CO₂/N₂ selectivity. The optimal monomers concentration was found. When monomer concentrations are higher than the optimal values, the CO₂ permeance decreases continually while CO₂/N₂ selectivity only shows a very limited improvement with the further increase of monomers concentration. The reaction time has similar effects on membrane performance as the monomers concentration. The effect of heat-treatment temperature was also studied. With the increasing heat-treatment temperature, the CO₂ permeance shows a decrease tendency, while the CO₂/N₂ selectivity shows a maximum at 80 °C. When PEA is 0.013 mol L⁻¹, TMC is 0.020 mol L⁻¹, reaction time is 3 min, and heat-treatment temperature is 80 °C, the optimum preparation conditions are achieved with CO₂ permeance of 378.3 gas permeation unit (GPU) and CO₂/N₂ selectivity of 51.7 at 0.03 MPa. This work may help to design and fabricate gas separation membranes with desired performance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47755.     

Modification of PES/PU membrane by supercritical CO2 to enhance CO2/CH4 selectivity: Fabrication and correlation approach using RSM

Integrally skinned asymmetric gas separation membranes of polyethersulfone (PES)/polyurethane (PU) blend were prepared using supercritical CO₂ (SC-CO₂) as a nonsolvent for the polymer solution. The membrane consisted of a dense and a porous layer, which were conjoined to separate CO₂ from CH₄. The FTIR, DSC, tensile and SEM tests were performed to study and characterize the membranes. The results revealed that an increase in SC-CO₂ temperature causes an increment in permeance and a decrease in membrane selectivity. Furthermore, by raising the pressure, both permeance and selectivity increased. The modified membrane with SC-CO₂ had much higher selectivity, about 5.5 times superior to the non-modified membrane. This higher selectivity performance compared to previous works was obtained by taking the advantages of both using partial miscible blend polymer due to the strong polar–polar interaction between PU PES and SC-CO₂ to fabricate the membrane. The response surface methodology (RSM) was applied to find the relationships between several explanatory variables and CO₂ and CH₄ permeance and CO₂/CH₄ selectivity as responses. Finally, the results were validated with the experimental data, which the model results were in good agreement with the available experimental data.     

Novel fixed‐carrier membranes for CO2 separation

A new membrane material having two kinds of CO₂ carriers was obtained. Composite membranes were prepared with the material and support membranes. The facilitated transport of CO₂ through these membranes was performed with pure CH₄ and CO₂ as well as CH₄/CO₂ mixtures containing 50 vol % CO₂. The results show that the membranes possess better CO₂ permeance than that of other fixed carrier membranes reported in the literature. In the measurements with pure gases, at 26°C, 0.013 atm of CO₂ pressure, the membrane with polysulfone support displays a CO₂ permeance of 7.93 × 10^?4 cm³ /cm² s cmHg and CO₂/CH₄ ideal selectivity of 212.1. In the measurements with mixed gases, at 26°C, 0.016 atm of CO₂ partial pressure, the membrane displays a CO₂ permeance of 1.69 × 10^?4 cm³ /cm² s cmHg and CO₂/CH₄ selectivity of 48.1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2222–2226, 2002     

Pervaporation separation of binary organic-aqueous liquid mixtures using crosslinked poly(vinyl alcohol) membranes. IV. Methanol–water mixtures

The pervaporation separation of methanol–water (M/W) mixtures was carried out using crosslinked poly(vinyl alcohol) (PVA) membranes with the low molecular weight of poly(acrylic acid) (PAA) as the crossinking agent. The PVA/PAA ratio in the crosslinked membrane was 90/10, 85/15, and 80/20 by weight. The operating temperatures were 50, 60, and 70°C, and the compositions of methanol–water mixtures to be separated were 70/30, 80/20, 90/10, and 95/5 (M/W) solutions. In all cases, the PVA/PAA = 80/20 membrane showed the best results. For M/W = 90/10 solution, the separation factor, α_w/m = 465, and the permeation rate, 0.109 kg/m²h, at 70°C were obtained using the PVA/PAA = 80/20 menbrane. The permeation rate and the separation factor for M/W = 95/5 solution showed 0.033 kg/m²h and α_w/m = 2650, respectively, when PVA/PAA = 80/20 membrane was used. © 1996 John Wiley & Sons, Inc.     

Study on CO2 facilitated separation of mixed matrix membranes containing surface modified MWCNTs

Mixed matrix membranes (MMMs) for CO₂-facilitated separation were prepared by incorporating different surface-modified multiwalled carbon nanotubes (MWCNTs) in a fixed carrier membrane material. Polymer containing amino groups, poly(vinylalcohol-co-vinylamine) (VA-co-VAm) was synthesized as polymeric matrix. MWCNTs as well as MWCNTs surface-modified with  OH and  NH₂ were applied as nanofillers. The physical property, chemical structure, and membrane morphology were characterized by FT-IR, TG, XRD, DSC, CA, XPS, and SEM. The effects of content, functional group, temperature, and pressure on gas permselectivity were studied. Results show that the incorporation of nanofillers can effectively restrict the polymer chain packing and lead to low crystallinity. The MMMs exhibited higher CO₂ permselectivity than the pure polymeric membrane. For all the MMMs, the CO₂ permeance and selectivity increased with MWCNTs contents to a maximum and then decreased. MWCNT-NH₂ can be regarded as the most effective nanofiller. MMMs with 2.0 wt % MWCNT-NH₂ displayed the highest CO₂ permeance of 132 GPU and CO₂/N₂ selectivity of 74. Both CO₂ permeance and selectivity were decreased with feed gas pressure and temperature. The membrane exhibited good stability in the testing with the binary gas mixtures of CO₂/N₂ for 110 h under 0.54 MPa. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47848.