Polymer Membranes for Gas Separation

A special issue of Membranes (ISSN 2077-0375). This special issue belongs to the section "Membrane Processing and Engineering".

Deadline for manuscript submissions: closed (30 July 2020) | Viewed by 35258

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School of Engineering, University of Edinburgh, Robert Stevenson Road, Edinburgh EH9 3FB, UK
Interests: membrane technology; gas separation; nanofibres; thin-film composite; mixed-matrices membranes
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EaStCHEM, School of Chemistry, University of Edinburgh, David Brewster Road, Edinburgh, UK
Interests: polymers of intrinsic microporosity; thermally rearranged polymers; polymer design and synthesis; gas separation membranes

Special Issue Information

Dear Colleagues,

Over the past decade, polymeric membranes have been widely investigated for a variety of industrial gas separation applications. In today’s competitive and ever-changing environment, membrane gas separation is now widely accepted as an economic process to produce moderate purity stream gases.

This Special Issue on “Polymer Membranes for Gas Separation” of the journal Membranes seeks contributions to assess the state-of-the-art and future developments in the field of polymeric membranes. Topics include but are not limited to synthesis and characterization of novel membrane materials, preparation and characterization of thin film composite and/or hollow fibres, membrane aging, transport phenomena and demonstration efforts and industrial exploitation. Authors are invited to submit their latest results; both original papers and reviews are welcome.

We look forward to receiving your outstanding work for this Special Issue.

Sincerely,

Dr. Elsa Lasseuguette
Dr. Bibiana Comesaña-Gándara
Guest Editors

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Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Polymeric membranes
  • Gas separation
  • Thin film composite
  • Hollow fibre
  • Aging
  • Transport phenomena
  • High performance membranes

Published Papers (10 papers)

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Editorial

Jump to: Research, Review

3 pages, 216 KiB  
Editorial
Polymer Membranes for Gas Separation
by Elsa Lasseuguette and Bibiana Comesaña-Gándara
Membranes 2022, 12(2), 207; https://doi.org/10.3390/membranes12020207 - 10 Feb 2022
Cited by 11 | Viewed by 3016
Abstract
Over the past decade, polymeric membranes have been widely investigated for a variety of industrial gas separation applications [...] Full article
(This article belongs to the Special Issue Polymer Membranes for Gas Separation)

Research

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16 pages, 34442 KiB  
Article
Hyper Cross-Linked Polymers as Additives for Preventing Aging of PIM-1 Membranes
by Federico Begni, Elsa Lasseuguette, Geo Paul, Chiara Bisio, Leonardo Marchese, Giorgio Gatti and Maria-Chiara Ferrari
Membranes 2021, 11(7), 463; https://doi.org/10.3390/membranes11070463 - 23 Jun 2021
Cited by 9 | Viewed by 2952
Abstract
Mixed-matrix membranes (MMMs) are membranes that are composed of polymers embedded with inorganic particles. By combining the polymers with the inorganic fillers, improvements can be made to the permeability compared to the pure polymer membranes due to new pathways for gas transport. However, [...] Read more.
Mixed-matrix membranes (MMMs) are membranes that are composed of polymers embedded with inorganic particles. By combining the polymers with the inorganic fillers, improvements can be made to the permeability compared to the pure polymer membranes due to new pathways for gas transport. However, the fillers, such as hyper cross-linked polymers (HCP), can also help to reduce the physical aging of the MMMs composed of a glassy polymer matrix. Here we report the synthesis of two novel HCP fillers, based on the Friedel–Crafts reaction between a tetraphenyl methane monomer and a bromomethyl benzene monomer. According to the temperature and the solvent used during the reaction (dichloromethane (DCM) or dichloroethane (DCE)), two different particle sizes have been obtained, 498 nm with DCM and 120 nm with DCE. The change in the reaction process also induces a change in the surface area and pore volumes. Several MMMs have been developed with PIM-1 as matrix and HCPs as fillers at 3% and 10wt % loading. Their permeation performances have been studied over the course of two years in order to explore physical aging effects over time. Without filler, PIM-1 exhibits the classical aging behavior of polymers of intrinsic microporosity, namely, a progressive decline in gas permeation, up to 90% for CO2 permeability. On the contrary, with HCPs, the physical aging at longer terms in PIM-1 is moderated with a decrease of 60% for CO2 permeability. 13C spin-lattice relaxation times (T1) indicates that this slowdown is related to the interactions between HCPs and PIM-1. Full article
(This article belongs to the Special Issue Polymer Membranes for Gas Separation)
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12 pages, 1082 KiB  
Article
Effect of Water and Organic Pollutant in CO2/CH4 Separation Using Hydrophilic and Hydrophobic Composite Membranes
by Clara Casado-Coterillo, Aurora Garea and Ángel Irabien
Membranes 2020, 10(12), 405; https://doi.org/10.3390/membranes10120405 - 8 Dec 2020
Cited by 11 | Viewed by 2176
Abstract
Membrane technology is a simple and energy-conservative separation option that is considered to be a green alternative for CO2 capture processes. However, commercially available membranes still face challenges regarding water and chemical resistance. In this study, the effect of water and organic [...] Read more.
Membrane technology is a simple and energy-conservative separation option that is considered to be a green alternative for CO2 capture processes. However, commercially available membranes still face challenges regarding water and chemical resistance. In this study, the effect of water and organic contaminants in the feed stream on the CO2/CH4 separation performance is evaluated as a function of the hydrophilic and permselective features of the top layer of the membrane. The membranes were a commercial hydrophobic membrane with a polydimethylsiloxane (PDMS) top layer (Sulzer Chemtech) and a hydrophilic flat composite membrane with a hydrophilic [emim][ac] ionic liquid–chitosan (IL–CS) thin layer on a commercial polyethersulfone (PES) support developed in our laboratory. Both membranes were immersed in NaOH 1M solutions and washed thoroughly before characterization. The CO2 permeance was similar for both NaOH-treated membranes in the whole range of feed concentration (up to 250 GPU). The presence of water vapor and organic impurities of the feed gas largely affects the gas permeance through the hydrophobic PDMS membrane, while the behavior of the hydrophilic IL–CS/PES membranes is scarcely affected. The effects of the interaction of the contaminants in the membrane selective layer are being further evaluated. Full article
(This article belongs to the Special Issue Polymer Membranes for Gas Separation)
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23 pages, 5440 KiB  
Article
Analysis of CO2 Facilitation Transport Effect through a Hybrid Poly(Allyl Amine) Membrane: Pathways for Further Improvement
by Bouchra Belaissaoui, Elsa Lasseuguette, Saravanan Janakiram, Liyuan Deng and Maria-Chiara Ferrari
Membranes 2020, 10(12), 367; https://doi.org/10.3390/membranes10120367 - 25 Nov 2020
Cited by 22 | Viewed by 2710
Abstract
Numerous studies have been reported on CO2 facilitated transport membrane synthesis, but few works have dealt with the interaction between material synthesis and transport modelling aspects for optimization purposes. In this work, a hybrid fixed-site carrier membrane was prepared using polyallylamine with [...] Read more.
Numerous studies have been reported on CO2 facilitated transport membrane synthesis, but few works have dealt with the interaction between material synthesis and transport modelling aspects for optimization purposes. In this work, a hybrid fixed-site carrier membrane was prepared using polyallylamine with 10 wt% polyvinyl alcohol and 0.2 wt% graphene oxide. The membrane was tested using the feed gases with different relative humidity and at different CO2 partial pressures. Selected facilitated transport models reported in the literature were used to fit the experimental data with good agreement. The key dimensionless facilitated transport parameters were obtained from the modelling and data fitting. Based on the values of these parameters, it was shown that the diffusion of the amine-CO2 reaction product was the rate-controlling step of the overall CO2 transport through the membrane. It was shown theoretically that by decreasing the membrane selective layer thickness below the actual value of 1 µm to a value of 0.1 µm, a CO2 permeance as high as 2500 GPU can be attained while maintaining the selectivity at a value of about 19. Furthermore, improving the carrier concentration by a factor of two might shift the performances above the Robeson upper bound. These potential paths for membrane performance improvement have to be confirmed by targeted experimental work. Full article
(This article belongs to the Special Issue Polymer Membranes for Gas Separation)
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10 pages, 2979 KiB  
Article
The Impact of Various Natural Gas Contaminant Exposures on CO2/CH4 Separation by a Polyimide Membrane
by Nándor Nemestóthy, Péter Bakonyi, Piroska Lajtai-Szabó and Katalin Bélafi-Bakó
Membranes 2020, 10(11), 324; https://doi.org/10.3390/membranes10110324 - 31 Oct 2020
Cited by 20 | Viewed by 2267
Abstract
In this study, hollow fibers of commercial polyimide were arranged into membrane modules to test their capacity and performance towards natural gas processing. Particularly, the membranes were characterized for CO2/CH4 separation with and without exposure to some naturally occurring contaminants [...] Read more.
In this study, hollow fibers of commercial polyimide were arranged into membrane modules to test their capacity and performance towards natural gas processing. Particularly, the membranes were characterized for CO2/CH4 separation with and without exposure to some naturally occurring contaminants of natural gases, namely hydrogen sulfide, dodecane, and the mixture of aromatic hydrocarbons (benzene, toluene, xylene), referred to as BTX. Gas permeation experiments were conducted to assess the changes in the permeability of CO2 and CH4 and related separation selectivity. Compared to the properties determined for the pristine polyimide membranes, all the above pollutants (depending on their concentrations and the ensured contact time with the membrane) affected the permeability of gases, while the impact of various exposures on CO2/CH4 selectivity seemed to be complex and case-specific. Overall, it was found that the minor impurities in the natural gas could have a notable influence and should therefore be considered from an operational stability viewpoint of the membrane separation process. Full article
(This article belongs to the Special Issue Polymer Membranes for Gas Separation)
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11 pages, 7181 KiB  
Article
Enhanced Selective Hydrogen Permeation through Graphdiyne Membrane: A Theoretical Study
by Quan Liu, Long Cheng and Gongping Liu
Membranes 2020, 10(10), 286; https://doi.org/10.3390/membranes10100286 - 15 Oct 2020
Cited by 11 | Viewed by 2986
Abstract
Graphdiyne (GDY), with uniform pores and atomic thickness, is attracting widespread attention for application in H2 separation in recent years. However, the challenge lies in the rational design of GDYs for fast and selective H2 permeation. By MD and DFT calculations, [...] Read more.
Graphdiyne (GDY), with uniform pores and atomic thickness, is attracting widespread attention for application in H2 separation in recent years. However, the challenge lies in the rational design of GDYs for fast and selective H2 permeation. By MD and DFT calculations, several flexible GDYs were constructed to investigate the permeation properties of four pure gas (H2, N2, CO2, and CH4) and three equimolar binary mixtures (H2/N2, H2/CO2, and H2/CH4) in this study. When the pore size is smaller than 2.1 Å, the GDYs acted as an exceptional filter for H2 with an approximately infinite H2 selectivity. Beyond the size-sieving effect, in the separation process of binary mixtures, the blocking effect arising from the strong gas–membrane interaction was proven to greatly impede H2 permeation. After understanding the mechanism, the H2 permeance of the mixtures of H2/CO2 was further increased to 2.84 × 105 GPU by reducing the blocking effect with the addition of a tiny amount of surface charges, without sacrificing the selectivity. This theoretical study provides an additional atomic understanding of H2 permeation crossing GDYs, indicating that the GDY membrane could be a potential candidate for H2 purification. Full article
(This article belongs to the Special Issue Polymer Membranes for Gas Separation)
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14 pages, 1976 KiB  
Article
Synthesis of Cis-Cisoid or Cis-Transoid Poly(Phenyl-Acetylene)s Having One or Two Carbamate Groups as Oxygen Permeation Membrane Materials
by Yu Zang, Yinghui Lun, Masahiro Teraguchi, Takashi Kaneko, Hongge Jia, Fengjuan Miao, Xunhai Zhang and Toshiki Aoki
Membranes 2020, 10(9), 199; https://doi.org/10.3390/membranes10090199 - 25 Aug 2020
Cited by 3 | Viewed by 2216
Abstract
Three new phenylacetylene monomers having one or two carbamate groups were synthesized and polymerized by using (Rh(norbornadiene)Cl)2 as an initiator. The resulting polymers had very high average molecular weights (Mw) of 1.4–4.8 × 106, with different solubility and [...] Read more.
Three new phenylacetylene monomers having one or two carbamate groups were synthesized and polymerized by using (Rh(norbornadiene)Cl)2 as an initiator. The resulting polymers had very high average molecular weights (Mw) of 1.4–4.8 × 106, with different solubility and membrane-forming abilities. The polymer having two carbamate groups and no hydroxy groups in the monomer unit showed the best solubility and membrane-forming ability among the three polymers. In addition, the oxygen permeability coefficient of the membrane was more than 135 times higher than that of a polymer having no carbamate groups and two hydroxy groups in the monomer unit with maintaining similar oxygen permselectivity. A better performance in membrane-forming ability and oxygen permeability may be caused by a more extended and flexible cis-transoid conformation and lower polarity. On the other hand, the other two new polymers having one carbamate group and two hydroxy groups in the monomer unit showed lower performances in membrane-forming abilities and oxygen permeabilities. It may be caused by a very tight cis-cisoid conformation, which was maintained by intramolecular hydrogen bonds. Full article
(This article belongs to the Special Issue Polymer Membranes for Gas Separation)
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18 pages, 4802 KiB  
Article
New Poly(imide)s Bearing Alkyl Side-Chains: A Study on the Impact of Size and Shape of Lateral Groups on Thermal, Mechanical, and Gas Transport Properties
by Fidel E. Rodríguez-González, Germán Pérez, Vladimir Niebla, Ignacio Jessop, Rudy Martin-Trasanco, Deysma Coll, Pablo Ortiz, Manuel Aguilar-Vega, Luis H. Tagle, Claudio A. Terraza and Alain Tundidor-Camba
Membranes 2020, 10(7), 141; https://doi.org/10.3390/membranes10070141 - 4 Jul 2020
Cited by 6 | Viewed by 2865
Abstract
A set of five new aromatic poly(imide)s (PIs) incorporating pendant acyclic alkyl moieties were synthesized. The difference among them was the length and bulkiness of the pendant group, which comprises of linear alkyl chains from three to six carbon atoms, and a tert [...] Read more.
A set of five new aromatic poly(imide)s (PIs) incorporating pendant acyclic alkyl moieties were synthesized. The difference among them was the length and bulkiness of the pendant group, which comprises of linear alkyl chains from three to six carbon atoms, and a tert-butyl moiety. The effect of the side group length on the physical, thermal, mechanical, and gas transport properties was analyzed. All PIs exhibited low to moderate molecular weights (Mn ranged between 27.930–58.970 Da, and Mw ranged between 41.760–81.310 Da), good solubility in aprotic polar solvents, except for PI-t-4, which had a tert-butyl moiety and was soluble even in chloroform. This behaviour was probably due to the most significant bulkiness of the side group that increased the interchain distance, which was corroborated by the X-ray technique (PI-t-4 showed two d-spacing values: 5.1 and 14.3 Å). Pure gas permeabilities for several gases were reported (PI-3 (Barrer): He(52); H2(46); O2(5.4); N2(1.2); CH4(1.1); CO2(23); PI-t-4 (Barrer): He(139); H2(136); O2(16.7); N2(3.3); CH4(2.3); CO2(75); PI-5 (Barrer): He(44); H2(42); O2(5.9); N2(1.4); CH4(1.2); CO2(27); PI-6 (Barrer): He(45); H2(43); O2(6.7); N2(1.7); CH4(1.7); CO2(32)). Consistent higher volume in the side group was shown to yield the highest gas permeability. All poly(imide)s exhibited high thermal stability with 10% weight loss degradation temperature between 448–468 °C and glass transition temperature between 240–270 °C. The values associated to the tensile strength (45–87 MPa), elongation at break (3.2–11.98%), and tensile modulus (1.43–2.19 GPa) were those expected for aromatic poly(imide)s. Full article
(This article belongs to the Special Issue Polymer Membranes for Gas Separation)
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34 pages, 11392 KiB  
Article
Enhancing the Separation Performance of Glassy PPO with the Addition of a Molecular Sieve (ZIF-8): Gas Transport at Various Temperatures
by Francesco M. Benedetti, Maria Grazia De Angelis, Micaela Degli Esposti, Paola Fabbri, Alice Masili, Alessandro Orsini and Alberto Pettinau
Membranes 2020, 10(4), 56; https://doi.org/10.3390/membranes10040056 - 27 Mar 2020
Cited by 16 | Viewed by 4826
Abstract
In this study, we prepared and characterized composite films formed by amorphous poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and particles of the size-selective Zeolitic Imidazolate Framework 8 (ZIF-8). The aim was to increase the permselectivity properties of pure PPO using readily available materials to enable the [...] Read more.
In this study, we prepared and characterized composite films formed by amorphous poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and particles of the size-selective Zeolitic Imidazolate Framework 8 (ZIF-8). The aim was to increase the permselectivity properties of pure PPO using readily available materials to enable the possibility to scale-up the technology developed in this work. The preparation protocol established allowed robust membranes with filler loadings as high as 45 wt% to be obtained. The thermal, morphological, and structural properties of the membranes were analyzed via DSC, SEM, TGA, and densitometry. The gas permeability and diffusivity of He, CO2, CH4, and N2 were measured at 35, 50, and 65 °C. The inclusion of ZIF-8 led to a remarkable increase of the gas permeability for all gases, and to a significant decrease of the activation energy of diffusion and permeation. The permeability increased up to +800% at 45 wt% of filler, reaching values of 621 Barrer for He and 449 for CO2 at 35 °C. The ideal size selectivity of the PPO membrane also increased, albeit to a lower extent, and the maximum was reached at a filler loading of 35 wt% (1.5 for He/CO2, 18 for CO2/N2, 17 for CO2/CH4, 27 for He/N2, and 24 for He/CH4). The density of the composite materials followed an additive behavior based on the pure values of PPO and ZIF-8, which indicates good adhesion between the two phases. The permeability and He/CO2 selectivity increased with temperature, which indicates that applications at higher temperatures than those inspected should be encouraged. Full article
(This article belongs to the Special Issue Polymer Membranes for Gas Separation)
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Review

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31 pages, 1744 KiB  
Review
Recent Advances in Membrane-Based Electrochemical Hydrogen Separation: A Review
by Leandri Vermaak, Hein W. J. P. Neomagus and Dmitri G. Bessarabov
Membranes 2021, 11(2), 127; https://doi.org/10.3390/membranes11020127 - 13 Feb 2021
Cited by 50 | Viewed by 8383
Abstract
In this paper an overview of commercial hydrogen separation technologies is given. These technologies are discussed and compared—with a detailed discussion on membrane-based technologies. An emerging and promising novel hydrogen separation technology, namely, electrochemical hydrogen separation (EHS) is reviewed in detail. EHS has [...] Read more.
In this paper an overview of commercial hydrogen separation technologies is given. These technologies are discussed and compared—with a detailed discussion on membrane-based technologies. An emerging and promising novel hydrogen separation technology, namely, electrochemical hydrogen separation (EHS) is reviewed in detail. EHS has many advantages over conventional separation systems (e.g., it is not energy intensive, it is environmentally-friendly with near-zero pollutants, it is known for its silent operation, and, the greatest advantage, simultaneous compression and purification can be achieved in a one-step operation). Therefore, the focus of this review is to survey open literature and research conducted to date on EHS. Current technological advances in the field of EHS that have been made are highlighted. In the conclusion, literature gaps and aspects of electrochemical hydrogen separation, that require further research, are also highlighted. Currently, the cost factor, lack of adequate understanding of the degradation mechanisms related to this technology, and the fact that certain aspects of this technology are as yet unexplored (e.g., simultaneous hydrogen separation and compression) all hinder its widespread application. In future research, some attention could be given to the aforementioned factors and emerging technologies, such as ceramic proton conductors and solid acids. Full article
(This article belongs to the Special Issue Polymer Membranes for Gas Separation)
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