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Membranes
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Membranes for Gas Separation
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Membranes for Gas Separation

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

Deadline for manuscript submissions: closed (31 July 2020) | Viewed by 77494

Special Issue Editors

Dr. Alessio Fuoco

E-Mail Website
Guest Editor
Institute on Membrane Technology, ITM-CNR, Via P. Bucci, Cubo 17/C, 87036 Rende (CS), Italy
Interests: polymeric and mixed matrix membranes; gas separation membranes; computational methods for membrane science; transport phenomena
Special Issues, Collections and Topics in MDPI journals
Dr. Guangwei He

E-Mail Website
Guest Editor
Department of Chemical Engineering, Massachusetts Institute of Technology (MIT), 77 Massachusetts Avenue, Room 66-580, Cambridge, MA 02139, USA
Interests: gas separation membranes; ion conducting membranes; nanoporous materials
Dr. Zhien Zhang

grade E-Mail Website
Guest Editor
William G. Lowrie Department of Chemical and Biomolecular Engineering, The Ohio State University, Columbus, OH 43210, USA
Interests: carbon capture utilization and storage (CCUS); gas separation; membrane; polymer; absorption; process modeling; mass transfer; heat transfer; fossil fuel; renewable energy; hydrate; wastewater treatment
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Generally, gas emissions can be removed using various methods, such as absorption, adsorption, cryogenic distillation, etc. Gas separation via the employment of membranes is noteworthy due to their high energy efficiency and productivity, and effective integration with the plants among the technologies for gas removal. However, there are still information gaps in the fields of membrane preparation and characterization, separation mechanisms, process optimization, and large-scale applications. Based on these ideas, we are inviting authors to submit original research and review papers in a broad range of topics for the Special Issue on “Membranes for Gas Separation”. Experimental and modeling works focused on gas separation using membrane approaches in a wide variety of application fields as well as reviews or technical notes in terms of the emerging and promising technologies on latest developments in gas separation membranes are highly welcome.

Dr. Zhien Zhang
Dr. Alessio Fuoco
Dr. Guangwei He
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Membranes is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2200 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

  • membrane
  • separation mechanism
  • gas separation
  • process intensification
  • membrane contactor
  • modeling

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Published Papers (12 papers)

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Editorial

Jump to: Research, Review

4 pages, 209 KiB  
Editorial
Membranes for Gas Separation
by Zhien Zhang, Alessio Fuoco and Guangwei He
Membranes 2021, 11(10), 755; https://doi.org/10.3390/membranes11100755 - 30 Sep 2021
Cited by 9 | Viewed by 4012
Abstract
Gas separation is of significant importance for many industrial processes including chemical purification, carbon capture, and fuel production [...] Full article
(This article belongs to the Special Issue Membranes for Gas Separation)

Research

Jump to: Editorial, Review

14 pages, 8821 KiB  
Article
Optical Analysis of the Internal Void Structure in Polymer Membranes for Gas Separation
by Chiara Muzzi, Alessio Fuoco, Marcello Monteleone, Elisa Esposito, Johannes C. Jansen and Elena Tocci
Membranes 2020, 10(11), 328; https://doi.org/10.3390/membranes10110328 - 5 Nov 2020
Cited by 6 | Viewed by 2852
Abstract
Global warming by greenhouse gas emissions is one of the main threats of our modern society, and efficient CO2 capture processes are needed to solve this problem. Membrane separation processes have been identified among the most promising technologies for CO2 capture, [...] Read more.
Global warming by greenhouse gas emissions is one of the main threats of our modern society, and efficient CO2 capture processes are needed to solve this problem. Membrane separation processes have been identified among the most promising technologies for CO2 capture, and these require the development of highly efficient membrane materials which, in turn, requires detailed understanding of their operation mechanism. In the last decades, molecular modeling studies have become an extremely powerful tool to understand and anticipate the gas transport properties of polymeric membranes. This work presents a study on the correlation of the structural features of different membrane materials, analyzed by means of molecular dynamics simulation, and their gas diffusivity/selectivity. We propose a simplified method to determine the void size distribution via an automatic image recognition tool, along with a consolidated Connolly probe sensing of space, without the need of demanding computational procedures. Based on a picture of the void shape and width, automatic image recognition tests the dimensions of the void elements, reducing them to ellipses. Comparison of the minor axis of the obtained ellipses with the diameters of the gases yields a qualitative estimation of non-accessible paths in the geometrical arrangement of polymeric chains. A second tool, the Connolly probe sensing of space, gives more details on the complexity of voids. The combination of the two proposed tools can be used for a qualitative and rapid screening of material models and for an estimation of the trend in their diffusivity selectivity. The main differences in the structural features of three different classes of polymers are investigated in this work (glassy polymers, superglassy perfluoropolymers and high free volume polymers of intrinsic microporosity), and the results show how the proposed computationally less demanding analysis can be linked with their selectivities. Full article
(This article belongs to the Special Issue Membranes for Gas Separation)
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13 pages, 1850 KiB  
Article
An Experimental Study of Membrane Contactor Modules for Recovering Cyanide through a Gas Membrane Process
by Michelle Quilaqueo, Gabriel Seriche, Sicely Valetto, Lorena Barros, Simón Díaz-Quezada, René Ruby-Figueroa, Elizabeth Troncoso and Humberto Estay
Membranes 2020, 10(5), 105; https://doi.org/10.3390/membranes10050105 - 19 May 2020
Cited by 7 | Viewed by 3766
Abstract
Cyanide is one of the main reagents used in gold mining that can be recovered to reduce operational costs. Gas membrane technology is an attractive method for intensifying both the stripping and absorption processes of valuable compounds, such as cyanide. However, scaling-up this [...] Read more.
Cyanide is one of the main reagents used in gold mining that can be recovered to reduce operational costs. Gas membrane technology is an attractive method for intensifying both the stripping and absorption processes of valuable compounds, such as cyanide. However, scaling-up this technology from laboratory to industry is an unsolved challenge because it requires the improvement of the experimental methodologies that replicate lab-scale results at a larger scale. With this purpose in mind, this study compares the performance of three different hollow fiber membrane contactor modules (1.7 × 5.5 Mini Module, 1.7 × 10 Mini Module, and 2.5 × 8 Extra Flow). These are used for recovering cyanide from aqueous solutions at laboratory scale, using identical operational conditions. For each experimental set-up, mass-transfer correlations at the ranges of feed flows assayed were determined. The modules with the smallest and largest area of mass transfer reached similar cyanide recoveries (>95% at 60 min), which demonstrate the impact of module configuration on their operating performance. The results obtained here are limited for scaling-up the membrane module performance only because operating modules with the largest area results in a low Re number. This fact limits the extrapolation of results from the mass-transfer correlation. Full article
(This article belongs to the Special Issue Membranes for Gas Separation)
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16 pages, 3125 KiB  
Article
Simple Flow-Based System with an In-Line Membrane Gas–Liquid Separation Unit and a Contactless Conductivity Detector for the Direct Determination of Sulfite in Clear and Turbid Food Samples
by Aulia Ayuning Tyas, Thitaporn Sonsa-ard, Kanchana Uraisin, Duangjai Nacapricha and Phoonthawee Saetear
Membranes 2020, 10(5), 104; https://doi.org/10.3390/membranes10050104 - 18 May 2020
Cited by 7 | Viewed by 4147
Abstract
This study presents a simple flow-based system for the determination of the preservative agent sulfite in food and beverages. The standard method of conversion of sulfite ions into SO2 gas by acidification is employed to separate the sulfite from sample matrices. The [...] Read more.
This study presents a simple flow-based system for the determination of the preservative agent sulfite in food and beverages. The standard method of conversion of sulfite ions into SO2 gas by acidification is employed to separate the sulfite from sample matrices. The sample is aspirated into a donor stream of sulfuric acid. A membrane gas–liquid separation unit, also called a ‘gas-diffusion (GD)’ unit, incorporating a polytetrafluoroethylene (PTFE) hydrophobic membrane allows the generated gas to diffuse into a stream of deionized water in the acceptor line. The dissolution of the SO2 gas leads to a change in the conductivity of water which is monitored by an in-line capacitively coupled contactless conductivity detector (C4D). The conductivity change is proportional to the concentration of sulfite in the sample. In this work, both clear (wine) and turbid (fruit juice and extracts of dried fruit) were selected to demonstrate the versatility of the developed method. The method can tolerate turbidity up to 60 Nephelometric Turbidity Units (NTUs). The linear range is 5–25 mg L−1 SO32− with precision <2% RSD. The flow system employs a peristaltic pump for propelling all liquid lines. Quantitative results of sulfite were statistically comparable to those obtained from iodimetric titration for the wine samples. Full article
(This article belongs to the Special Issue Membranes for Gas Separation)
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13 pages, 2118 KiB  
Article
Enhanced O2/N2 Separation of Mixed-Matrix Membrane Filled with Pluronic-Compatibilized Cobalt Phthalocyanine Particles
by S. A. S. C. Samarasinghe, Chong Yang Chuah, H. Enis Karahan, G. S. M. D. P. Sethunga and Tae-Hyun Bae
Membranes 2020, 10(4), 75; https://doi.org/10.3390/membranes10040075 - 18 Apr 2020
Cited by 26 | Viewed by 6490
Abstract
Membrane-based air separation (O2/N2) is of great importance owing to its energy efficiency as compared to conventional processes. Currently, dense polymeric membranes serve as the main pillar of industrial processes used for the generation of O2- and [...] Read more.
Membrane-based air separation (O2/N2) is of great importance owing to its energy efficiency as compared to conventional processes. Currently, dense polymeric membranes serve as the main pillar of industrial processes used for the generation of O2- and N2-enriched gas. However, conventional polymeric membranes often fail to meet the selectivity needs owing to the similarity in the effective diameters of O2 and N2 gases. Meanwhile, mixed-matrix membranes (MMMs) are convenient to produce high-performance membranes while keeping the advantages of polymeric materials. Here, we propose a novel MMM for O2/N2 separation, which is composed of Matrimid® 5218 (Matrimid) as the matrix, cobalt(II) phthalocyanine microparticles (CoPCMPs) as the filler, and Pluronic® F-127 (Pluronic) as the compatibilizer. By the incorporation of CoPCMPs to Matrimid, without Pluronic, interfacial defects were formed. Pluronic-treated CoPCMPs, on the other hand, enhanced O2 permeability and O2/N2 selectivity by 64% and 34%, respectively. We explain the enhancement achieved with the increase of both O2 diffusivity and O2/N2 solubility selectivity. Full article
(This article belongs to the Special Issue Membranes for Gas Separation)
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17 pages, 4494 KiB  
Article
Leveraging Nanocrystal HKUST-1 in Mixed-Matrix Membranes for Ethylene/Ethane Separation
by Chong Yang Chuah, S.A.S.C. Samarasinghe, Wen Li, Kunli Goh and Tae-Hyun Bae
Membranes 2020, 10(4), 74; https://doi.org/10.3390/membranes10040074 - 16 Apr 2020
Cited by 43 | Viewed by 6819
Abstract
The energy-intensive ethylene/ethane separation process is a key challenge to the petrochemical industry. HKUST-1, a metal–organic framework (MOF) which possesses high accessible surface area and porosity, is utilized in mixed-matrix membrane fabrication to investigate its potential for improving the performance for C2 [...] Read more.
The energy-intensive ethylene/ethane separation process is a key challenge to the petrochemical industry. HKUST-1, a metal–organic framework (MOF) which possesses high accessible surface area and porosity, is utilized in mixed-matrix membrane fabrication to investigate its potential for improving the performance for C2H4/C2H6 separation. Prior to membrane fabrication and gas permeation analysis, nanocrystal HKUST-1 was first synthesized. This step is critical in order to ensure that defect-free mixed-matrix membranes can be formed. Then, polyimide-based polymers, ODPA-TMPDA and 6FDA-TMPDA, were chosen as the matrices. Our findings revealed that 20 wt% loading of HKUST-1 was capable of improving C2H4 permeability (155% for ODPA-TMPDA and 69% for 6FDA-TMPDA) without excessively sacrificing the C2H4/C2H6 selectivity. The C2H4 and C2H6 diffusivity, as well as solubility, were also improved substantially as compared to the pure polymeric membranes. Overall, our results edge near the upper bound, confirming the effectiveness of leveraging nanocrystal HKUST-1 filler for performance enhancements in mixed-matrix membranes for C2H4/C2H6 separation. Full article
(This article belongs to the Special Issue Membranes for Gas Separation)
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12 pages, 1719 KiB  
Article
Effect of Bridgehead Methyl Substituents on the Gas Permeability of Tröger’s-Base Derived Polymers of Intrinsic Microporosity
by Richard Malpass-Evans, Ian Rose, Alessio Fuoco, Paola Bernardo, Gabriele Clarizia, Neil B. McKeown, Johannes C. Jansen and Mariolino Carta
Membranes 2020, 10(4), 62; https://doi.org/10.3390/membranes10040062 - 3 Apr 2020
Cited by 24 | Viewed by 5180
Abstract
A detailed comparison of the gas permeability of four Polymers of Intrinsic Microporosity containing Tröger’s base (TB-PIMs) is reported. In particular, we present the results of a systematic study of the differences between four related polymers, highlighting the importance of the role of [...] Read more.
A detailed comparison of the gas permeability of four Polymers of Intrinsic Microporosity containing Tröger’s base (TB-PIMs) is reported. In particular, we present the results of a systematic study of the differences between four related polymers, highlighting the importance of the role of methyl groups positioned at the bridgehead of ethanoanthracene (EA) and triptycene (Trip) components. The PIMs show BET surface areas between 845–1028 m2 g−1 and complete solubility in chloroform, which allowed for the casting of robust films that provided excellent permselectivities for O2/N2, CO2/N2, CO2/CH4 and H2/CH4 gas pairs so that some data surpass the 2008 Robeson upper bounds. Their interesting gas transport properties were mostly ascribed to a combination of high permeability and very strong size-selectivity of the polymers. Time lag measurements and determination of the gas diffusion coefficient of all polymers revealed that physical ageing strongly increased the size-selectivity, making them suitable for the preparation of thin film composite membranes. Full article
(This article belongs to the Special Issue Membranes for Gas Separation)
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15 pages, 3325 KiB  
Article
Fabrication of Defect-Free P84® Polyimide Hollow Fiber for Gas Separation: Pathway to Formation of Optimized Structure
by Miren Etxeberria-Benavides, Oguz Karvan, Freek Kapteijn, Jorge Gascon and Oana David
Membranes 2020, 10(1), 4; https://doi.org/10.3390/membranes10010004 - 25 Dec 2019
Cited by 17 | Viewed by 7963
Abstract
The elimination of the additional defect healing post-treatment step in asymmetric hollow fiber manufacturing would result in a significant reduction in membrane production cost. However, obtaining integrally skinned polymeric asymmetric hollow fiber membranes with an ultrathin and defect-free selective layer is quite challenging. [...] Read more.
The elimination of the additional defect healing post-treatment step in asymmetric hollow fiber manufacturing would result in a significant reduction in membrane production cost. However, obtaining integrally skinned polymeric asymmetric hollow fiber membranes with an ultrathin and defect-free selective layer is quite challenging. In this study, P84® asymmetric hollow fiber membranes with a highly thin (~56 nm) defect-free skin were successfully fabricated by fine tuning the dope composition and spinning parameters using volatile additive (tetrahydrofuran, THF) as key parameters. An extensive experimental and theoretical study of the influence of volatile THF addition on the solubility parameter of the N-methylpyrrolidone/THF solvent mixture was performed. Although THF itself is not a solvent for P84®, in a mixture with a good solvent for the polymer, like N-Methyl-2-pyrrolidone (NMP), it can be dissolved at high THF concentrations (NMP/THF ratio > 0.52). The as-spun fibers had a reproducible ideal CO2/N2 selectivity of 40, and a CO2 permeance of 23 GPU at 35 °C. The fiber production can be scaled-up with retention of the selectivity. Full article
(This article belongs to the Special Issue Membranes for Gas Separation)
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16 pages, 5342 KiB  
Article
Synthesis of Imidazolium based PILs and Investigation of Their Blend Membranes for Gas Separation
by Thanasis Chouliaras, Aristofanis Vollas, Theophilos Ioannides, Valadoula Deimede and Joannis Kallitsis
Membranes 2019, 9(12), 164; https://doi.org/10.3390/membranes9120164 - 3 Dec 2019
Cited by 16 | Viewed by 4645
Abstract
Polymeric (ionic liquid) (PIL) copolymers bearing cationic imidazolium pendants and polar acrylic acid groups (P(VBCImY-co-AAx)), which both favor the interaction with CO2 molecules, have been synthesized and blended with film forming, high glass transition temperature aromatic polyether-based pyridinium PILs (PILPyr). [...] Read more.
Polymeric (ionic liquid) (PIL) copolymers bearing cationic imidazolium pendants and polar acrylic acid groups (P(VBCImY-co-AAx)), which both favor the interaction with CO2 molecules, have been synthesized and blended with film forming, high glass transition temperature aromatic polyether-based pyridinium PILs (PILPyr). The blend membranes based on the above combination have been prepared and characterized in respect to their thermal and morphological behavior as well as to their gas separation properties. The used copolymers and blends showed a wide range of glass transition temperatures from 32 to 286 °C, while blends exhibited two phase morphology despite the presence of polar groups in the blend components that could participate in specific interactions. Finally, the membranes were studied in terms of their gas separation behavior. It revealed that blend composition, counter anion type and acrylic acid molar percentage affect the gas separation properties. In particular, PILPyr-TFSI/P(VBCImTFSI-co-AA20) blend with 80/20 composition shows CO2 permeability of 7.00 Barrer and quite high selectivity of 103 for the CO2/CH4 gas pair. Even higher CO2/CH4. selectivity of 154 was achieved for PILPyr-BF4/P(VBCImBF4-co-AA10) blend with composition 70/30. Full article
(This article belongs to the Special Issue Membranes for Gas Separation)
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16 pages, 3384 KiB  
Article
Chemical Absorption of CO2 Enhanced by Nanoparticles Using a Membrane Contactor: Modeling and Simulation
by Nayef Ghasem
Membranes 2019, 9(11), 150; https://doi.org/10.3390/membranes9110150 - 11 Nov 2019
Cited by 20 | Viewed by 4985
Abstract
In the present work, membrane resistance was estimated and analyzed, and the results showed that total membrane resistance increased sharply when membrane pores were wetted. For further study, a two-dimensional (2D) mathematical model was developed to predict the chemical absorption of CO2 [...] Read more.
In the present work, membrane resistance was estimated and analyzed, and the results showed that total membrane resistance increased sharply when membrane pores were wetted. For further study, a two-dimensional (2D) mathematical model was developed to predict the chemical absorption of CO2 in aqueous methyldiethanolamine (MDEA)-based carbon nanotubes (CNTs) in a hollow fiber membrane (HFM) contactor. The membrane was divided into wet and dry regions, and equations were developed and solved using finite element method in COSMOL. The results revealed that the existence of solid nanoparticles enhanced CO2 removal rate. The variables with more significant influence were liquid flow rate and concentration of nanoparticles. Furthermore, there was a good match between experimental and modeling results, with the modeling estimates almost coinciding with experimental data. Solvent enhanced by solid nanoparticles significantly improved the separation performance of the membrane contactor. There was around 20% increase in CO2 removal when 0.5 wt% CNT was added to 5 wt% aqueous MDEA. Full article
(This article belongs to the Special Issue Membranes for Gas Separation)
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Review

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20 pages, 2939 KiB  
Review
Research Progress in Gas Separation Using Hollow Fiber Membrane Contactors
by Linlin Li, Guiyang Ma, Zhen Pan, Na Zhang and Zhien Zhang
Membranes 2020, 10(12), 380; https://doi.org/10.3390/membranes10120380 - 29 Nov 2020
Cited by 45 | Viewed by 5963
Abstract
In recent years, gas–liquid membrane contactors have attracted increasing attention. A membrane contactor is a device that realizes gas–liquid or liquid–liquid mass transfer without being dispersed in another phase. The membrane gas absorption method combines the advantages of chemical absorption and membrane separation, [...] Read more.
In recent years, gas–liquid membrane contactors have attracted increasing attention. A membrane contactor is a device that realizes gas–liquid or liquid–liquid mass transfer without being dispersed in another phase. The membrane gas absorption method combines the advantages of chemical absorption and membrane separation, in addition to exhibiting high selectivity, modularity, and compactness. This paper introduces the operating principle and wetting mechanism of hollow membrane contactors, shows the latest research progress of membrane contactors in gas separation, especially for the removal of carbon dioxide from gas mixtures by membrane contactors, and summarizes the main aspects of membrane materials, absorbents, and membrane contactor structures. Furthermore, recommendations are provided for the existing deficiencies or unsolved problems (such as membrane wetting), and the status and progress of membrane contactors are discussed. Full article
(This article belongs to the Special Issue Membranes for Gas Separation)
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36 pages, 12213 KiB  
Review
Microscopy and Spectroscopy Techniques for Characterization of Polymeric Membranes
by Yousef Alqaheem and Abdulaziz A. Alomair
Membranes 2020, 10(2), 33; https://doi.org/10.3390/membranes10020033 - 24 Feb 2020
Cited by 98 | Viewed by 18252
Abstract
Polymeric membrane is a proven technology for water purification and wastewater treatment. The membrane is also commercialized for gas separation, mainly for carbon dioxide removal and hydrogen recovery. Characterization techniques are excellent tools for exploring the membrane structure and the chemical properties. This [...] Read more.
Polymeric membrane is a proven technology for water purification and wastewater treatment. The membrane is also commercialized for gas separation, mainly for carbon dioxide removal and hydrogen recovery. Characterization techniques are excellent tools for exploring the membrane structure and the chemical properties. This information can be then optimized to improve the membrane for better performance. In this paper, characterization techniques for studying the physical structure such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) are discussed. Techniques for investigating the crystal structure such as X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), and wide-angle X-ray scattering (WAXS) are also considered. Other tools for determining the functional groups such Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and nuclear magnetic resonance (NMR) are reviewed. Methods for determining the elemental composition such as energy-dispersion X-ray spectroscopy (EDS), X-ray fluorescent (XRF), and X-ray photoelectron spectroscopy (XPS) are explored. The paper also gives general guidelines for sample preparation and data interpretation for each characterization technique. Full article
(This article belongs to the Special Issue Membranes for Gas Separation)
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