Gas Separation Membrane Applications Research Articles

Fabrication of high-performance biochar incorporated Pebax®1657 membranes for CO2 separation

This study highlights the utilization of biobased material for developing high-performance membranes for gas separation applications. Biochar was synthesized by the pyrolysis of pine needles and further modified by silane functionalization. Thus obtained biochar was incorporated into a rubbery polymer, poly(ether-blockamide) (Pebax-1657), to synthesize mixed matrix membranes (MMMs). Morphologies of membranes and physio-chemical interactions of the biochar and polymer were evaluated using SEM, FTIR, DSC, and XRD. MMMs exhibit higher gas adsorption properties compared to the neat Pebax-1657 membrane. The effect of biochar incorporation on gas permeation properties was conducted in an indigenously designed setup using pure CH4, CO2, and N2 gases in the pressure range of 5–30 kg/cm2. 20 wt% Biochar loaded MMM achieved a higher CO2 permeability of 114 Barrer, signifying 79% higher permeability over the pristine Pebax membrane. Correspondingly, the highest selectivity values for CO2/CH4 and CO2/N2 achieved were 32 and 94, respectively, with increasing pressure. A regression model was developed to estimate the relation between biochar loading and gas permeability. The data revealed a strong positive correlation (0.7–0.9) between gas permeability and the percentage of biochar loaded. The developed MMMs are stable and exhibit superior performance for CO2 removal from natural gas and power plant off-gases. Pine needles derived MMMs represent a promising new approach for developing high-performance and environmentally sustainable membranes for gas separation applications.

Enhanced gas separation performance for H2 purification using MIL-68(ln)-nh2/PES mixed-matrix membranes

The growing demand for sustainable and efficient gas separation technologies has prompted the exploration of advanced materials to enhance the gas permeability and selectivity. Polyethersulfone (PES) membranes are widely used in gas separation, gas upgrading, and clean energy production owing to their environmental friendliness and low cost. However, their gas permeability and selectivity can be further improved for commercial application. This study explored the incorporation of 10 wt % of MIL-68(ln)-NH2 into PES membranes using a phase-inversion approach to enhance gas permeability and selectivity. The morphological, structural, and thermal properties of the resulting MOF/PES membrane were characterized using SEM, AFM, BET, XRD, FTIR, and TGA-DTG. Gas permeation experiments were conducted using different gases (CO2, N2, CH4, and H2) under different heating conditions (20–60 °C) to evaluate the gas permeability and selectivity of the MOF/PES membrane. The results showed that the incorporation of MOF into the mixed matrix membrane (MMMs) led to a 9% increase in porosity, 87% reduction in roughness, and 32% decrease in pore size compared to neat PES membranes. Significant changes in the morphology, crystallinity, and thermal stability were observed, with notable improvements of up to 22%. Moreover, the MOF/PES membrane exhibited high gas permeability (CO2 = 124656, N2 = 83650, CH4 = 159298, and H2 = 427075 Barrer) and selectivity (H2/N2 = 5.7, H2/CO2 = 4, CH4/N2 = 2, and CH4/CO2 = 1.7) for flammable gases. The optimal gas separation performance was observed at 20 °C and 60 °C for H2/N2 and H2/CO2 separation, respectively. These findings demonstrate the potential of MOF-based PES membranes for gas separation applications, particularly in H2 purification.

A semi-rigid co-poly(imide) derived from an isomeric mixture of monomers. Assessing gas transport properties in self-standing polymer membrane

Chemical structure and morphology of polymers are directly related with the membrane separation performance. Poly(imide)s (PIs) are the most widely used polymers in the preparation of membranes for gas separation applications; thus, research on the structural design of polymers is of great interest to develop new membranes. In the present work, we reported the synthesis, characterization, and measurement of the gas transport properties of a new co-poly(imide)s (PI-D2a-D2b-6FDA) prepared from a mixture of isomeric diamines. The co-poly(imide) synthetic route involved several steps, starting by a bromination reaction, followed by a double nucleophilic aromatic substitution giving an isomeric mixture of precursors, which suffered a Suzuki-Miyaura C–C cross-coupling reaction followed by the reduction of nitro groups to give two new isomeric diamines. Finally, diamines simultaneously reacted with the dianhydride 6FDA to obtain PI-D2a-D2b-6FDA. The co-poly(imide) had a Mn of 47.7 kDa and a Mw of 74.0 kDa with a PDI of 1.6. The sample exhibited a 10% weight loss at 540 °C, Tg of 280 °C, BET surface area of 110 m2 g−1, and wide-angle X-ray diffraction (WAXD) interchain d-spacing at 9.5 Å and 6.3 Å. Tensile strength, elongation at break and Young's modulus were 109.6 MPa, 6.66% and 2.18 GPa, respectively. co-Poly(imide) was soluble in various polar aprotic organic solvents such as DMSO, NMP, DMF, DMAc, THF, and chloroform, forming a self-standing dense film whose gas transport properties were measured. Pure gas permeability coefficients for H2, CO2, O2, N2, and CH4, were 47.28, 24.04, 4.35, 1.02, and 0.76 (Barrer), respectively, which follows a decreasing order by the increasing kinetic diameters of the respective gases. Ideal gas selectivities H2/N2, O2/N2, CO2/CH4, and CO2/N2 were 46.4, 4.3, 31.6, and 23.6, respectively. These gas transport properties were compared with the commercial polymer Matrimid®, showing higher gas permeability coefficients than Matrimid®.

Controlling Microstructure-Transport Interplay in Poly(ether-block-amide) Multiblock Copolymer Gas Separation Membranes.

In this study, we investigated the effect of morphology on the gas-transport properties of a poly(ether-block-amide) (PEBA) multiblock copolymer. We annealed the copolymer samples and varied the annealing temperature to evaluate the influence of changes in the microstructure on the gas transport properties of PEBA. In addition, we used time-resolved attenuated total reflection Fourier transform infrared spectroscopy to evaluate the diffusion coefficient of CO2 in PEBA based on the Fickian model. The effect of the annealing temperature on the microphase-separated structure of the multiblock copolymer is discussed in detail. Furthermore, the gas diffusivity was significantly affected by the purity of the soft domains. The annealed sample demonstrated a 38% increase in CO2 permeability while maintaining a high CO2/N2 permselectivity of approximately 53. The findings of this study provide valuable insight into the design and optimization of PEBA membranes for gas separation applications.

Simultaneously enhanced gas separation and anti-aging performance of intrinsic microporous polyimide by dibromo substitution

Physical aging is a huge challenge hindering the practical gas separation application of high-performance intrinsic microporous polyimides (PIM-PIs). Herein, through precise molecular design, bromine was introduced into the PIM-PI chain to both improve its separation and anti-aging properties. To clarify the anti-aging effect of bromo groups in PIM-PIs, two fluorene-based diamine isomer monomers, 9,9-bis(3-bromo-4-aminophenyl)-fluorene (BBAPF), 2,7-dibromo-9,9-bis(4-aminophenyl)-fluorene (DBBAPF), and their corresponding PIM-PIs (BAPI, BBPI, DBPI) were synthesized. Compared with pristine BAPI membrane, the permeability of BBPI is improved about 50%, which can be attributed to the bromo groups near the amino group suppressing chain densification packing and providing more free volume element (FVE). In addition, the substituted bromo group increased the chain rigidity of the polymer and hindered its rotation, resulting in a lower release of fractional free volume (FFV) during aging process. Particularly, the permeability of the BBPI was maintained at approximately ∼70% with slightly increased selectivity after 250 days, while the pristine BAPI only retained about 50% permeability of N2 (CH4). Our findings proposed an effective strategy for designing microporous polymers with improved permeability and anti-aging properties for practical applications in gas separation membranes.

Interdependent factors influencing the carbon yield, structure, and CO_{2} adsorption capacity of lignocellulose-derived carbon fibers using multiple linear regression

Cellulose has experienced a renaissance as a precursor for carbon fibers (CFs). However, cellulose possesses intrinsic challenges as precursor substrate such as typically low carbon yield. This study examines the interplay of strategies to increase the carbonization yield of (ligno-) cellulosic fibers manufactured via a coagulation process. Using Design of Experiments, this article assesses the individual and combined effects of diammonium hydrogen phosphate (DAP), lignin, and CO_{2} activation on the carbonization yield and properties of cellulose-based carbon fibers. Synergistic effects are identified using the response surface methodology. This paper evidences that DAP and lignin could affect cellulose pyrolysis positively in terms of carbonization yield. Nevertheless, DAP and lignin do not have an additive effect on increasing the yield. In fact, combined DAP and lignin can affect negatively the carbonization yield within a certain composition range. Further, the thermogravimetric CO_{2} adsorption of the respective CFs was measured, showing relatively high values (ca. 2 mmol/g) at unsaturated pressure conditions. The CFs were microporous materials with potential applications in gas separation membranes and CO_{2} storage systems.Graphical abstract

Utilization and Comparison of Different Food Wastes for the Synthesis of Two-Stage Activated Carbon-Based Mixed Matrix Membranes for Gas Separation Applications

Utilization and Comparison of Different Food Wastes for the Synthesis of Two-Stage Activated Carbon-Based Mixed Matrix Membranes for Gas Separation Applications

Curvature Effect in Polydimethylsiloxane Interaction with CO2. Insights from Theory

In this study we employ density functional theory to investigate the binding interaction between polydimethylsiloxane and CO2 for application in gas separation membranes. The binding strength has been studied systematically as a function of the monomer conformational rotations in the polymer chain. Our work identified major differences between the CO2 interaction with the helical conformation and the linear conformation of polydimethylsiloxane polymer chains. We have further estimated dependence between the CO2 binding strength and the polydimethylsiloxane polymer chain curvature by systematically evaluating the CO2 binding to cyclic polydimethylsiloxane oligomers. The enhanced CO2 interaction with helical chains and cyclic oligomers was attributed to cooperative, confinement effects, and local electron density distribution at the Si-O-Si fragments. The binding modes were identified using vibration frequency analysis.

Synthesis and characterization of a high-performance bio-based Pebax membrane for gas separation applications

Synthesis of biobased membranes for gas separation applications. The Pebax® Rnew® 30R51 membrane holds potential for CO2 separation. Increasing the polymer concentration enhanced the gas selectivity to 91 and 26 for CO2/N2 and CO2/CH4, respectively.

Poly(vinyl alcohol) mediated bifunctional ZIF-BN nanocomposite for the high-selectivity H2 separation membrane

We combined the advantages of the 2-methylimidazole zinc salt (ZIF-8) and hydroxylated boron nitride (OH-BN) materials to prepare a new bifunctional separation material, namely ZIF-BN. In this, spherical ZIF-8 materials fill the macroporous structure of OH-BN sheets by coordination bonds due to the edge effect. Furthermore, a series of ZIF-BN/PVA membranes were prepared using the vacuum-assisted filtration of the layer-by-layer for the gas separation study. The trace amounts of PVA connect adjacent ZIF-BN sheets through hydrogen bonds, without covering the pore structures of ZIF-8 materials. Based on this exclusive strategy for preparing membranes, the obtained membranes exhibit superior H2 separation performances. Compared with the pure PVA membrane, the H2 permeability, H2/CO2 selectivity, and H2/N2 selectivity of the ZIF-BN/PVA-8 membrane have increased (54, 13, & 12)-fold, to (600 Barrer, 97.2, & 173.6), respectively. This strategy provides a facile way to design new bifunctional membranes for gas separation applications.

The effect of chain rigidity and microstructure on gas separation performance of the cardo-based polyimides

A series of aromatic polyimides were synthesized from three Cardo-based diamines, BAF, DDA, BAP, with different building blocks (ether linkage, dioxane linkage and C–C linkage), and commercially available dianhydride 6FDA. All polyimides were readily soluble in conventional aprotic and protic solvents, which guaranted the fabrication of self-standing membranes for gas separation applications. The Cardo-based polyimides also exhibited excellent thermal stability, with weight loss temperatures (T 5 %) of over 538 °C, and good mechanical properties, with tensile strength in the range of 41–64 MPa. Compared to 6FDA-BAF, the substitution of dioxane linkage for ether linkage resulted in increased chain rigidity, looser polymer chain packing, and larger fractional free volume. Consequently, as displayed by single gas permeation tests, 6FDA-DDA showed higher permeability coefficients without significantly sacrificing selectivity. In addition, the CO 2 permeability of 6FDA-BAP was around 2 times as high as that of 6FDA-BAF, while the CO 2 /CH 4 selectivity increased by 11%. This can be explained by the lower rotational mobility and the relatively higher imide content caused by the absence of the flexible ether linkage and dioxane linkage in polymer backbone. In short, fundamental insights into structure-property relationships of the Cardo-based polyimides observed in this study provided guidance for the molecular structure design of the gas separation membranes. • Three Cardo-based polyimides containing different building blocks were successfully synthesized. • The effect of rigidity and microstructure on gas separation performance of the Cardo-based polyimides was elucidate. • The substitution of dioxane for ether linkage led to the increased chain rigidity and the looser chain packing. • The polyimide containing C–C linkage showed better combination of permeability and gas-pair selectivity.

Graphene nanoplatelets based polyimide/Pebax dual-layer mixed matrix hollow fiber membranes for CO2/CH4 and He/N2 separations

Mixed matrix membranes are key in the preparation of stable, stretchy, durable and efficient membranes for gas separation applications. To this aim, the perfect filler nanomaterials’ dispersion is needed. At the same time the replacement of toxic solvents with green ones is also a priority in science, including the membrane technology. Herein, we present the development steps, their structural characteristics and the gas selectivity properties of graphene nanoplatelets (GNPs) based mixed matrix hollow fiber (HF) membranes. In specific, dual-layer composite polymeric hollow fiber membranes, for CO2/CH4 and He/N2 gas separations, were prepared by directly dip-coating a single selective layer on prepared porous HF supports without the use of any gutter layer. Asymmetric BTDA-TDI/MDI (P84) co-polyimide-based HFs that acted as porous supports, were fabricated via the dry-wet phase inversion process and the commercial poly(ether-block-amide) Pebax-1657 was chosen as a high CO2-selective separation layer material, dip-coated on the HF supports. The positive influence of the incorporation of GNPs as promising nanofiller in both, the polymeric matrix (support) and the selective layer, in parallel with the partial replacement of toxic NMP by GBL -a "green" solvent- in the support's spinning process, were all evaluated and confirmed. CO2/CH4 and He/N2 selectivities up to 82 and 20, respectively with CO2 and He permeances of 3 and 2.7 GPU, respectively were measured under real binary gas mixture conditions at 1.3 bar(a) transmembrane pressure at 298 K for dual-layer composite, with GNPs filler, HF (DL-HF) membranes.

Gas processing with intrinsically porous 2D membranes

The importance of membranes for the processing of gases with significant technological as well as environmental impact is rapidly increasing given their advantages in operation, low energy consumption, and efficiencies. In this work we employ density functional theory calculations to investigate the performance of a number of intrinsically porous two-dimensional (2D) membranes for gas separation applications. Our results indicate that gases with small kinetic diameters such as He, H2O, Ne, H2, and CO2 present low energy barriers and high permeability through these membranes, in contrast to other components of natural and atmospheric gases. Additionally, we show that some of the studied membranes present high selectivities for a number of permeating gases. Our results indicate that these materials are promising candidates for applications in gas processing such as natural gas dehydration and sweetening, He recovery, O2 and N2 production from air, H2 purification, and CO2 capturing.

Modulating Polymer Dynamics via Supramolecular Interaction with Ultrasmall Nanocages for Recyclable Gas Separation Membranes with Intrinsic Microporosity.

The engineering of mixed-matrix membranes is severely hindered by the trade-off between mechanical performance and effective utilization of inorganic fillers' microporosity. Herein, we report a feasible approach for optimal gas separation membranes through the fabrication of coordination nanocages with poly(4-vinylpyridine) (P4VP) via strong supramolecular interactions, enabling the homogeneous dispersion of nanocages in polymer matrixes with long-term structural stability. Meanwhile, suggested from dynamics studies, the strong attraction between P4VP and nanocages slows down polymer dynamics and rigidifies the polymer chains, leading to frustrated packing and lowered densities of the polymer matrix. This effect allows the micropores of nanocages to be accessible to external gas molecules, contributing to the intrinsic microporosity of the nanocomposites and the simultaneous enhancement of permselectivities. The facile strategy for supramolecular synthesis and polymer dynamics attenuation paves avenues to rational design of functional hybrid membranes for gas separation applications.

Conjugate polymer-based membranes for gas separation applications: current status and future prospects

Conjugate polymers provide the possibility of exploiting both the chemical and physical attributes of the polymers for membrane-based gas separation. The presence of delocalized π electrons provides high chain stiffness with low packing density, thus making the membrane a rigid structure that favors facilitated transport. Historically, the polymeric membranes were constrained by the tradeoff relationship between gas permeability and gas selectivity. So, different methods were investigated to prepare the membranes that can overcome the limitation. In recent years, electroconductive polymeric membranes have gained attention with their enhanced transportation properties combining the separation behavior depending on both molecular size discrimination as well as the facilitated transport. They offer better selectivity toward polar gases such as CO2 because of the increased solubility. This review is aimed to provide a literature survey on gas separation using conjugate polymers such as polyaniline, polypyrrole, and some derivatives of polythiophenes. It contains various methods used by different researchers to enhance the gas separation properties of the membranes with improved mechanical and thermal stability such as changing the morphology and membrane preparation methods. In addition, it provides the pros and cons of various factors affecting the conjugate polymer membrane performance. The major challenges and future work that can be done in improving the transportation properties through the membrane to achieve viable membranes are also discussed so that they can be used for commercial and practical applications in the future.

2D boron nitride nanosheets in PIM-1 membranes for CO2/CH4 separation

Physical aging represents one of the major obstacles towards adoption of polymer of intrinsic microporosity (PIM) membranes for gas separation applications. In this work, mixed matrix membranes (MMMs) of 2D boron nitride nanosheets (BNNS) and PIM-1 were prepared and applied in the separation of a CO2/CH4 (1:1, v:v) binary gas mixture. The membranes were tested over a period of more than one year to evaluate their anti-aging properties as compared to neat PIM-1. The results show that introducing BNNS into PIM-1 leads to a significant reduction in the physical aging of PIM-1, as demonstrated by the values of reduction in CO2 permeability after 414 days (22% for the MMMs as compared to 58% for neat PIM-1). This work paves the way to using PIM-based membranes in industry.

Tosoh reports Speciality Group results for fiscal 2021

Three titanosilicate zeolites were used as fillers for Mixed Matrix Membranes: (i) ETS-10, (ii) TS-1 having Si/Ti=100 and (iii) TS-1 using Si/Ti=25. Zeolite samples were characterized by X-Ray Diffraction, Scanning Electron Microscopy, Atomic Emission Spectroscopy, X-Ray Photoelectron Spectroscopy, and CO2 and CH4 adsorption isotherms. TS-1 particles showed a narrow size distribution ranging from 200 nm to 400 nm. In the case of ETS-10, the size distribution was broader ranging from 400 nm to 800 nm. Mixed Matrix Membranes were prepared using Matrimid® polyimide as continuous phase and filler loadings of 10, 20, and 30 wt%. Membranes were characterized by Thermogravimetric Analysis, Differential Scanning Calorimetry, and Scanning Electron Microscopy. The performances was measured at 8 bars of transmembrane pressure for CO2/CH4 mixed gases system at 50/50 vol/vol. concentration.Membranes using TS-1 (Si/Ti=25) as filler showed a maximum increase of 89.1% of CO2 permeability and 23.9% increase in separation factor. In the case of TS-1 (Si/Ti=100) only permeability increased significantly, with a maximum increase of 90.1%. Regarding the ETS-10 membranes, both permeability and separation factor increased slightly with respect to the reference polymeric membrane (22.5% in CO2 permeability and 7.8% in the separation factor). In conclusion, TS-1 (Si/Ti=25) is the most suitable filler for the use in Mixed Matrix Membranes for gas separation applications among the titanosilicate studied in this work.

Recent development of polyimides: Synthesis, processing, and application in gas separation

AbstractHigh‐performance polymers have been concomitant with advanced technology for half a century. With the advancement of synthetic chemistry, the recent development of high‐performance polymers has provided superior properties and enabled wide applications. This article reviews recent research progress in aromatic high‐performance polymers. Particularly, we focus on the synthesis and processing of polyimides, as well as the application in gas separation membranes. We begin with a brief introduction to highlight important history and physiochemical characteristics of polyimides. Then, we review the various synthesis methods, followed by recent advances for improving processability. Finally, we evaluate the use of high‐performance polymers in gas separation membranes with focus given to the key issues of plasticization and aging. Overall, the information presented herein provides an up‐to‐date overview of high‐performance polymers, polyimides particularly, and serves as a guide for further research involving the applications in membrane technologies.

Mitigating the Agglomeration of Nanofiller in a Mixed Matrix Membrane by Incorporating an Interface Agent.

Nanodiamonds (ND) have recently emerged as excellent candidates for various applications including membrane technology due to their nanoscale size, non-toxic nature, excellent mechanical and thermal properties, high surface areas and tuneable surface structures with functional groups. However, their non-porous structure and strong tendency to aggregate are hindering their potential in gas separation membrane applications. To overcome those issues, this study proposes an efficient approach by decorating the ND surface with polyethyleneimine (PEI) before embedding it into the polymer matrix to fabricate MMMs for CO2/N2 separation. Acting as both interfacial binder and gas carrier agent, the PEI layer enhances the polymer/filler interfacial interaction, minimising the agglomeration of ND in the polymer matrix, which is evidenced by the focus ion beam scanning electron microscopy (FIB-SEM). The incorporation of PEI into the membrane matrix effectively improves the CO2/N2 selectivity compared to the pristine polymer membranes. The improvement in CO2/N2 selectivity is also modelled by calculating the interfacial permeabilities with the Felske model using the gas permeabilities in the MMM. This study proposes a simple and effective modification method to address both the interface and gas selectivity in the application of nanoscale and non-porous fillers in gas separation membranes.

Current Trends in Metal-Organic and Covalent Organic Framework Membrane Materials.

Metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) have been thoroughly investigated with regards to applications in gas separation membranes in the past years. More recently, new preparation methods for MOFs and COFs as particles and thin‐film membranes, as well as for mixed‐matrix membranes (MMMs) have been developed. We will highlight novel processes and highly functional materials: Zeolitic imidazolate frameworks (ZIFs) can be transformed into glasses and we will give an insight into their use for membranes. In addition, liquids with permanent porosity offer solution processability for the manufacture of extremely potent MMMs. Also, MOF materials influenced by external stimuli give new directions for the enhancement of performance by in situ techniques. Presently, COFs with their large pores are useful in quantum sieving applications, and by exploiting the stacking behavior also molecular sieving COF membranes are possible. Similarly, porous polymers can be constructed using MOF templates, which then find use in gas separation membranes.