Surpassing Robeson Upper Limit for CO2/N2 Separation with Fluorinated Carbon Molecular Sieve Membranes
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Recent Progress in the Engineering of Polymeric Membranes for CO2 Capture from Flue Gas
CO2 capture from coal- or natural gas-derived flue gas has been widely considered as the next opportunity for the large-scale deployment of gas separation membranes. Despite the tremendous progress made in the synthesis of polymeric membranes with high CO2/N2 separation performance, only a few membrane technologies were advanced to the bench-scale study or above from a highly idealized laboratory setting. Therefore, the recent progress in polymeric membranes is reviewed in the perspectives of capture system energetics, process synthesis, membrane scale-up, modular fabrication, and field tests. These engineering considerations can provide a holistic approach to better guide membrane research and accelerate the commercialization of gas separation membranes for post-combustion carbon capture.
20 FOSSIL-FUELED POWER PLANTS↗
Superior CO 2 /N 2 separation performance of highly branched Poly(1,3 dioxolane) plasticized by polyethylene glycol
With its high content of CO 2 -philic ether oxygen groups, poly(1,3-dioxolane) (PDXLA) has emerged as an attractive platform to achieve excellent CO 2 /N 2 separation properties for post-combustion carbon capture. Herein we demonstrate that the separation properties of PDXLA can be further enhanced by plasticizing with miscible polyethylene glycol (PEG)-based additives using an integrated experimentation and modeling approach. The effects of the chain end groups and loading level of the additives on the physical properties of the blends are thoroughly investigated, including glass transition temperature (T g ), fractional free volume, and gas transport properties, and the effects can be satisfactorily described using models available for homogeneous blends. Notably, a T g -integrated free volume model is adapted to successfully interpret the unified effect of the blend composition and temperature on gas diffusivity and permeability. A sample containing 45 mass% PEG dimethyl ether (PEGDME with a molecular mass of 240 g/mol) displays stable mixed-gas CO 2 permeability of 1540 Barrer and CO 2 /N 2 selectivity of 40 when challenged with a model flue gas at 60 °C, outperforming Robeson's 2008 upper bound. Elucidating how small plasticizers impact gas transport in homogeneous blends may unravel a facile way to design high-performance membranes for gas separations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Creation of Polymer Datasets with Targeted Backbones for Screening of High-Performance Membranes for Gas Separation
A simple approach was developed to computationally construct a polymer dataset by combining simplified molecular-input line-entry system (SMILES) strings of a targeted polymer backbone and a variety of molecular fragments. This method was used to create 14 polymer datasets by combining seven polymer backbones and molecules from two large molecular datasets (MOSES and QM9). Polymer backbones that were studied include four polydimethylsiloxane (PDMS) based backbones, poly(ethylene oxide) (PEO), poly(allyl glycidyl ether) (PAGE), and polyphosphazene (PPZ). The generated polymer datasets can be used for various cheminformatics tasks, including high-throughput screening for gas permeability and selectivity. This study utilized machine learning (ML) models to screen the polymers for CO2/CH4 and CO2/N2 gas separation using membranes. Several polymers of interest were identified. Here the results highlight that employing an ML model fitted to polymer selectivities leads to higher accuracy in predicting polymer selectivity compared to using the ratio of predicted permeabilities.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effect of Branch Length on the Structural and Separation Properties of Hyperbranched Poly(1,3-dioxolane)
Polymers containing poly(ethylene oxide) (PEO) demonstrate superior membrane CO 2 /N 2 separation properties owing to their polar ether oxygen groups exhibiting strong affinity toward CO2. Poly(1,3-dioxolane) (PDXL) shows an ether oxygen content higher than PEO and is expected to have higher CO 2 /N 2 solubility selectivity. However, similar to PEO, the high crystallinity of PDXL greatly reduces its gas permeability. Herein, amorphous PDXL-based hyperbranched polymers were synthesized by ring opening of 1,3-dioxolane (DXL) to form poly(1,3-dioxolane) acrylate (DXLAn) followed by photopolymerization. The repeating unit of DXL (n) or branch length was systematically varied from 4 to 12 to yield amorphous polymers. The chemical and physical properties of the obtained polymers (PDXLAn) were thoroughly evaluated and used to interpret pure- and mixed-gas transport characteristics. The polymers exhibit attractive CO 2 /N 2 and CO 2 /CH 4 separation properties. For example, PDXLA8 exhibits a CO 2 permeability of 220 Barrer and CO 2 /N 2 selectivity of 56 at 35 °C, surpassing Robeson’s 2008 upper bound, and it shows robust separation performance when evaluated with simulated flue gas at 60 °C. This study demonstrates that hyperbranched structures are an effective route to construct amorphous yet highly polar polymers and that chain end groups are instrumental in determining the structural and gas transport characteristics.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Mixed matrix membranes for post-combustion carbon capture: From materials design to membrane engineering
Mixed matrix materials (MMMs) containing nanofillers dispersed in continuous polymer matrices have emerged as an exciting and versatile platform to develop membranes with superior CO 2 /N 2 separation performance for post-combustion carbon capture. Both polymers and nanofillers can be vertically designed and engineered to combine the advantages of excellent processability (derived from polymers) and strong size-sieving ability or/and significant permanent porosity (originated from nanofillers). However, the MMMs face major challenges, such as interfacial incompatibility, particle agglomeration, and poor thin-film formability. This report provides a comprehensive yet critical review of various polymers and nanofillers (such as metal-organic frameworks, covalent organic frameworks, and two-dimensional materials) with promising CO 2 /N 2 separation properties. We exhaustively describe strategies to improve interfacial compatibility, such as in situ syntheses of polymers and nanofillers and functionalization of both components to improve adhesion. Moreover, we highlight various approaches to engineer the MMMs into thin-film composite (TFC) membranes. The review reveals the structure/property relationship in these MMMs and outlines the challenges and opportunities to realize their potential for practical applications.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Thin-film composite membranes based on hyperbranched poly(ethylene oxide) for CO 2 /N 2 separation
Cross-linked amorphous poly(ethylene oxide) (XLPEO) is one of the leading membrane materials for post-combustion CO 2 capture. For example, XLPEO prepared from poly(ethylene glycol) methyl ether acrylate (PEGMEA) exhibited CO 2 permeability of 570 Barrer and CO 2 /N 2 selectivity of 41 at 35 °C. However, these XLPEOs cannot be dissolved in coating solutions, making it impossible to be fabricated into thin-film composite (TFC) membranes using state-of-the-art manufacturing processes. In this study, we synthesized high molecular weight yet soluble HPEO via atom transfer radical polymerization (ATRP). These polymers were thoroughly characterized and compared with XLPEO, including thermal transitions, free volumes, and pure-gas sorption and permeation properties. A polymer with the best combination of CO 2 permeability (540 Barrer) and CO 2 /N 2 selectivity (43) was fabricated into defect-free TFC membranes with a thickness as thin as 506 ± 44 nm. When challenged with simulated flue gas containing water vapor at 35 °C for over 100 h, the membrane shows stable CO 2 permeance of 850 GPU and CO 2 /N 2 selectivity of 37, comparable to the leading commercial membranes for carbon capture.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Gas permeation properties of amorphous zeolitic imidazolate framework membranes made by atomic/molecular layer deposition
Amorphous metal-organic framework (MOF) membranes are desirable because they may retain some of the molecular sieving properties of their crystalline counterparts while being free of grain boundary defects, which often hinder the consistent achievement of high membrane performance. However, current methods, like melting and compression, for fabricating amorphous MOF membranes involve multi-step processes that require the formation of a crystalline membrane first, that is then amorphized, and therefore, could be challenging to scale. Here, we utilize atomic/molecular layer deposition (ALD/MLD) of diethylzinc (DEZ) and 2-methylimidazole (2mIm) to directly synthesize ultrathin amorphous zeolitic imidazolate framework (aZIF) deposits on γ-alumina-coated α-alumina supports. As the number of ALD/MLD cycles increased from 10 to 300, gas permeances decreased while ideal selectivities increased. Mixture separation factors for C3H6/C3H8, CO2/N2, and H2/C3H8 as high as 4, 37, and 194, respectively, were obtained. At 200 °C and 2.5 bar equimolar feed of H2 and C3H8, a H2/C3H8 mixture separation factor of 185 is obtained with an H2 permeance of ca. 4.15x10-8 mol/m2-s-Pa (124 GPU). Additionally, the membrane achieves a CO2/N2 mixture separation factor of 37 at 25 °C and 1 bar with a CO2 permeance of ca. 3.96x10-8 mol/m2-s-Pa (118 GPU). Considering the vast array of compositionally distinct aZIFs that can be potentially deposited by this approach, an enormously large parameter space for membrane design is emerging to be explored.
36 MATERIALS SCIENCE↗
Cross-Linked Polyphosphazene Blends as Robust CO2 Separation Membranes
An effective cross-linking technique allows a viscous, highly gas permeable hydrophilic polyphosphazene to be cast as solid membrane films. By judicious blending with other polyphosphazenes to improve mechanical properties, a membrane exhibiting the highest CO2 permeability (610 barrer) combined with good CO2/N2 selectivity (35) among polyphosphazenes is described here. The material demonstrates performance stability after 500 hours of exposure to a coal-fired power plant flue gas, making it attractive for use in carbon capture applications. Its CO2/N2 selectivity under conditions up to full humidity is also stable, and although the gas permeability does decline, the performance is fully recovered upon drying. The high molecular weight of these heteropolymers also allows them to be cast as a thin selective layer on an asymmetric porous membrane, yielding CO2 permeance of 1200 GPU, CO2/N2 pure gas selectivity of 31, which does not decline over 2000 hours due to physical aging. In addition to gas separation membranes, this cross-linked polyphosphazene can potentially be extended to other applications such as drug delivery or proton exchange membranes which take advantage of the polyphosphazene’s versatile chemistry.
Kusuma, Victor↗
Generalizable Porous Aromatic Framework‐Included Polymer Membranes for Diffusion‐Enhanced Gas Separations
Industrial separation processes account for 10-15% of global energy consumption. Membrane-based processes are less energy-intensive than traditional gas separation technologies; however, enhanced material separation performance and stability for numerous gas mixtures are needed for widespread industrial adoption. This work presents a generalizable strategy for preparing mixed-matrix gas separation membranes exceeding the performance upper bounds of existing polymer membranes for a wide variety of industrial gases. By incorporating robust porous aromatic framework (PAF) particles into various dense commercial polymer matrices, gas diffusivity and solubility can be enhanced. For diverse gas mixtures (e.g., CO2/N2, O2/N2, He/CH4, H2/N2, and C2H4/C2H6), the resulting composite membranes exhibit enhanced gas permeabilities-by as much as 520%-and largely unchanged selectivities even after 6 years of aging under simulated flue gas conditions. These improvements arise from the ultrahigh porosity, excellent chemical compatibility, and unique physicochemical properties of the embedded PAF particles. Functionalizing the PAFs with polyamines also enables composite membranes that achieve among the highest reported performances against plasticization, a common obstacle in commercializing gas separation membranes. Significantly, the PAF-1 particles are readily dispersible in various common membrane casting solvents, suggesting their broader utility as a filler for designing high-performance membranes for many industrial gas separations.
Uliana, Adam A↗
Membrane Development for CO2 Capture from Steel Manufacturing
The U.S. government is targeting a net-zero carbon-emission economy by 2050, offering an exciting opportunity for membrane-based CO2 capture from various industrial point sources. Given that industrial flue gas has low CO2 partial pressures and high volumetric flow rates, high-permeance membranes are needed to make membrane technology economically viable for large-scale deployment. Thin film composite (TFC) membranes are necessary for this implementation because they can provide high permeance by forming a thin selective layer on top of a porous support. This presentation will report the rational design and fabrication of NETL’s highly permeable non-aging TFCs achieved by: synthesizing a high-performance rubbery selective material; developing a high-porosity membrane support; optimizing coating methods to assemble the two materials into scalable membranes; and scaling up membrane supports and TFCs via a roll-to-roll process. The novel rubbery selective material shows mixed-gas CO2 permeability of 930 Barrer and CO2/N2 selectivity of 44, exceeding the 2008 Robeson upper bound. The resulting TFCs yield remarkably high CO2 permeance of 4,500 GPU and CO2/N2 selectivity of 34 at 23ºC. Moreover, the TFCs exhibit not only excellent performance stability (or non-aging behavior) for 1,000 hours in the lab, but also maintain their separation properties in a 700-hour field test at the U.S. DOE’s National Carbon Capture Center using real humid flue gas.
Tran, Thien↗
Poly(ionic liquid)s with Dicationic Pendants as Gas Separation Membranes
Poly(norbornene)s and poly(ionic liquid)s are two different classes of attractive materials, which are known for their structural tunability and thermal stabilities, and have been extensively studied as gas separation membranes. The incorporation of ionic liquids (ILs) into the poly(norbornene) through post-polymerization has resulted in unique materials with synergistic properties. However, direct polymerization of norbornene-containing IL monomers as gas separation membranes are limited. To this end, a series of norbornene-containing imidazolium-based mono- and di-cationic ILs (NBM-mIm and NBM-DILs) with different connectivity and spacer lengths were synthesized and characterized spectroscopically. Subsequently, the poly(NBM-mIm) with bistriflimide [Tf2N−] and poly([NBM-DILs][Tf2N]2) comprising homo-, random-, and block- (co)polymers were synthesized via ring-opening metathesis polymerization using the air-stable Grubbs second-generation catalyst. Block copolymers (BCPs), specifically, [NBM-mIM][Tf2N] and [NBM-ImCnmIm] [Tf2N]2 (n = 4 and 6) were synthesized at two different compositions, which generated high molecular weight polymers with decent solubility relative to homo- and random (co)polymers of [NBM-DILs] [Tf2N]2. The prepared BCPs were efficiently analyzed by a host of analytical tools, including 1H-NMR, GPC, and WAXD. The successfully BCPs were cast into thin membranes ranging from 47 to 125 μm and their gas (CO2, N2, CH4, and H2) permeations were measured at 20 °C using a time-lag apparatus. These membranes displayed modest CO2 permeability in a non-linear fashion with respect to composition and a reverse trend in CO2/N2 permselectivity was observed, as a usual trade-off behavior between permeability and permselectivity.
59 BASIC BIOLOGICAL SCIENCES↗