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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Correlating Interlayer Spacing and Separation Capability of Graphene Oxide Membranes in Organic Solvents

Membranes synthesized by stacking two-dimensional graphene oxide (GO) hold great promise for applications in organic solvent nanofiltration. However, the performance of a layer-stacked GO membrane in organic solvent nanofiltration can be significantly affected by its swelling and interlayer spacing, which have not been systematically characterized. In this study, the interlayer spacing of the layer-stacked GO membrane in different organic solvents was experimentally characterized by liquid-phase ellipsometry. To understand the swelling mechanism, the solubility parameters of GO were experimentally determined and used to mathematically predict the Hansen solubility distance between GO and solvents, which is found to be a good predictor for GO swelling and interlayer spacing. Solvents with a small solubility distance (e.g., dimethylformamide, N-methyl-2-pyrrolidone) tend to cause significant GO swelling, resulting in an interlayer spacing of up to 2.7 nm. Solvents with a solubility distance larger than 9.5 (e.g., ethanol, acetone, hexane, and toluene) only cause minor swelling and are thus able to maintain an interlayer spacing of around 1 nm. Correspondingly, GO membranes in solvents with a large solubility distance exhibit good separation performance, for example, rejection of more than 90% of the small organic dye molecules (e.g., rhodamine B and methylene blue) in ethanol and acetone. Additionally, solvents with a large solubility distance result in a high slip velocity in GO channels and thus high solvent flux through the GO membrane. Finally, the GO membrane performs better in solvents that are unlike GO, i.e., solvents with large solubility distance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Bicarbonate-Carbonate Selectivity through Nanofiltration for Direct Air Capture of Carbon Dioxide

Direct air capture (DAC) of carbon dioxide is one approach among many proposed that is capable of offsetting hard-to-avoid emissions. In previous work, we developed the alkalinity concentration swing (ACS) method, which is driven through concentrating an alkaline solution that has been loaded with atmospheric CO 2 by desalination technologies, such as reverse osmosis or capacitive deionization. Though the ACS is promising in terms of energy usage and implementation, its absorption rate and water requirements are infeasible for a large-scale DAC process. Here, we propose an improvement on the ACS, the bicarbonate-enriched alkalinity concentration swing (BE-ACS), which selects bicarbonate ions from a stream of aqueous alkaline solution that has absorbed atmospheric CO 2 . The bicarbonate-rich stream is then concentrated, which greatly increases its CO 2 partial pressure, and then CO 2 is extracted from solution. We experimentally investigate the use of pressure-driven nanofiltration (NF) membrane-based separation to select bicarbonate ions over carbonate ions. We screen commercial membranes and select one high-performance membrane for detailed studies, quantifying its bicarbonate-carbonate selectivity factor and bicarbonate-passage factor. Feed pH, the combined concentration of aqueous CO 2 , bicarbonate, and carbonate species (or dissolved inorganic carbon), alkalinity, and permeation flux are systematically varied to study NF separation properties. We find that the selectivity factor, which exceeds 30 times in certain regimes, increases with higher feed pH and higher alkalinity. Lastly, the performance metrics of the selected NF membrane are input into a theoretical BE-ACS cycle analysis, and the required energy input and cycle capacity output are evaluated. Ideal cycle energy is found to be as low as around 250 kJ/mol, with opportunities identified for further decreases through process engineering and forward osmosis energy recovery.

animal feed↗
DOE OSTI2025

A computational investigation of high-flux, plate-and-frame membrane modules for industrial carbon capture

In this work, we study the application of membrane-based separation systems for carbon capture, considering plate-and-frame membrane modules. The successful deployment of membrane CO 2 capture system relies on high-performing membranes as well as effective membrane modules that can fully exploit the developed membranes. A plate-and-frame membrane module is especially attractive for CO 2 capture from industrial flue gas due to its lower pressure drop compared to its counterparts such as spiral wound modules and hollow fiber modules. To design better plate-and-frame modules, we investigate their basic unit - a single membrane stack through a combination of computational modeling and experimental investigations. The modeling approach is based on Computational Fluid Dynamics (CFD) to represent a multiphysics problem, including the fluid flow and diffusion processes within a membrane module. We use experimental data collected under different operating conditions to validate the CFD model. Numerical results suggest a good agreement between experiments and model outputs for the CO 2 recovery, CO 2 mole fraction in the retentate and permeate, and stage-cut. The CFD model is able to predict accurately the flow behavior, providing valuable insights on the effects of fluid dynamics on mass transfer of CO 2 . We also carry out a sensitivity analysis to identify the effect of key parameters on the CO 2 recovery and the CO 2 purity of the outlet streams.

CFD simulation↗
DOE OSTI2024

CFD modeling of high-flux plate-and-frame membrane modules for industrial carbon capture

In this work, we study the application of membrane-based separation systems for carbon capture, considering plate-and-frame membrane modules. The successful deployment of membrane CO2 capture system relies on high-performing membranes as well as effective membrane modules that can fully exploit the developed membranes. A plate-and-frame membrane module is especially attractive for CO2 capture from industrial flue gas due to its lower pressure drop compared to its counterparts such as spiral wound modules and hollow fiber modules. To design better plate-and-frame modules, we investigate their basic unit - a single membrane stack through a combination of computational modeling and experimental investigations. The modeling approach is based on Computational Fluid Dynamics (CFD) to represent a multiphysics problem, including the fluid flow and diffusion processes within a membrane module. We use experimental data collected under different operating conditions to validate the CFD model. Numerical results suggest a good agreement between experiments and model outputs for the CO2 recovery, CO2 mole fraction in the retentate and permeate, and stage-cut. The CFD model is able to predict accurately the flow behavior, providing valuable insights on the effects of fluid dynamics on mass transfer of CO2. We also carry out a sensitivity analysis to identify the effect of key parameters on the CO2 recovery and the CO2 purity of the outlet streams.

Dosso, Cheick↗
NASA NTRS2026

Highly Porous Polyimide Gel for Use as Battery Separator with Room Temperature Ionic Liquid Electrolytes

Advanced aerospace vehicular concepts require advances in many existing technologies, including space power and energy storage systems. Batteries represent one of the major areas in need of improvement, both in terms of energy density and safety, with growing concerns over the fire safety of commercial lithium-ion batteries. This has prompted efforts to develop nonflammable battery components, namely the electrolyte and separator. Existing commercial lithium-ion batteries utilize polyolefin microporous membranes as separators with an electrolyte consisting of a lithium salt dissolved in a mixture of cyclic carbonate solvents. This separator/electrolyte combination has ionic conductivities in the range of 10 −2 to 10 −3 S/cm. However, the cyclic carbonate solvents are inherently flammable. Room-temperature ionic liquids (RTILs) appear to be a safer alternative. They offer good ionic conductivities and are inherently nonvolatile and nonflammable, giving them a safety advantage. However, many promising RTILs for battery electrolytes are not compatible with commercial polyolefin separator materials. Alternative separator materials, such as polyimides, are non-flammable and are capable of accepting RTILs into their structure. Polyimide gels, with a composition of 4,4′-oxydianiline, 3,3′,4,4′-tetracarboxylic dianhydride and cross-linked with Desmodur N3300A, possess an open-porous, fibrillar network architecture which offers a high degree of porosity (typically greater than 85% porosity) for lithium-ion transport and conduction, as well as good mechanical properties. Furthermore, these polyimide gels are compatible with selected imidazolium-based RTILs. Nonflammable separator/electrolyte systems with room-temperature conductivities in the range of 10 −3 S/cm have been evaluated. It has been demonstrated that 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was the most promising among six RTILs screened, in terms of both ionic conductivity and constant current cycling.

Polyimide↗
DOE OSTI2021

Key Features of Polyimide‐Derived Carbon Molecular Sieves

Abstract Carbon molecular sieve (CMS) membranes have impressive separation properties; however, both chemical and morphology structures need to be understood better. Here we characterize CMS with the simplest polyimide (PI) PMDA/pPDA (PMDA=pyromellitic dianhydride, pPDA= p ‐phenylenediamine), using FTIR, solid‐state 15 N‐NMR and 13 C‐NMR, XPS, XRD, and Raman spectra to study chemical structure. We also compare gas separation properties for this CMS to a CMS derived from a more conventional PI precursor. The detailed characterization shows the presence of aromatic pyridinic, pyrrolic rings as well as graphitic, pyridonic components and a few other groups in both CMS types derived from the very different precursors. The CMS morphologies, while related to precursor and pyrolysis temperature details, show similarities consistent with a physical picture comprising distributed molecular sieving plate‐like structures. These results assist in understanding diverse CMS membrane separation performance.

Qiu, Wulin↗
DOE OSTI2021

Analysis of energetics and economics of sub-ambient hybrid post-combustion carbon dioxide capture

Adsorption of CO 2 from post-combustion flue gas is one of the leading candidates for globally impactful carbon capture systems. In this report, work focused on understanding the opportunities and limitations of sub-ambient CO 2 capture processes utilizing a multistage separation process. A hybrid process design using a combination of pressure-driven separation of CO 2 from flue gas (e.g., adsorption- or membrane-based separation) followed by CO 2 -rich product liquefaction to produce high-purity (>99%) CO 2 at pipeline conditions is considered. The operating pressure of the separation unit is a key cost parameter and also an important process variable that regulates the available heat removal necessary to reach the sub-ambient operating conditions. The economic viability of applying pressure swing adsorption (PSA) processes using fiber sorbent contactors with internal heat management was found to be most influenced by the productivity of the adsorption system, with productivities as high as 0.015 mol CO2 /kg sorb -1 sec -1 being required to reduce costs of capture below $60/ton CO 2 captured. This analysis was carried out using a simplified two-bed process, and thus there is opportunity for further cost reduction with exploration of more complex cycle designs. Three exemplar fiber sorbents (MIL-101(Cr), UiO-66, and zeolite 13X) were considered for application in the sub-ambient process of PSA unit. Among the considered sorbents, zeolite 13X fiber composites were found to perform better at ambient temperatures as compared to sub-ambient. MIL-101(Cr) and UiO-66 fiber composites had improved purity, recovery, and productivity at colder temperatures reducing costs of capture as low as $61/ton CO 2 . Future economic improvement could be achieved by reducing the required operating pressure of the PSA unit and pushing the Pareto frontier closer to the final pipeline requirement via a combination of PSA cycle design and material selection.

42 ENGINEERING↗
DOE OSTI2020

Facile Size-Selective Defect Sealing in Large-Area Atomically Thin Graphene Membranes for Sub-Nanometer Scale Separations

Atomically thin graphene with a high-density of precise subnanometer pores represents the ideal membrane for ionic and molecular separations. However, a single large-nanopore can severely compromise membrane performance and differential etching between pre-existing defects/grain boundaries in graphene and pristine regions presents fundamental limitations. Here, we show for the first time that size-selective interfacial polymerization after high-density nanopore formation in graphene not only seals larger defects (>0.5 nm) and macroscopic tears but also successfully preserves the smaller subnanometer pores. Low-temperature growth followed by mild UV/ozone oxidation allows for facile and scalable formation of high-density (4–5.5 $\times$ 10 12 cm –2 ) useful subnanometer pores in the graphene lattice. We demonstrate scalable synthesis of fully functional centimeter-scale nanoporous atomically thin membranes (NATMs) with water (~0.28 nm) permeance ~23$\times$ higher than commercially available membranes and excellent rejection to salt ions (~0.66 nm, >97% rejection) as well as small organic molecules (~0.7–1.5 nm, ~100% rejection) under forward osmosis. $\times$

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Above‐T g Annealing Benefits in Nanoparticle‐Stabilized Carbon Molecular Sieve Membrane Pyrolysis for Improved Gas Separation

Abstract Nanoparticles can suppress asymmetric precursor support collapse during pyrolysis to create carbon molecular sieve (CMS) membranes. This advance allows elimination of standard sol‐gel support stabilization steps. Here we report a simple but surprisingly important thermal soaking step at 400 °C in the pyrolysis process to obtain high performance CMS membranes. The composite CMS membranes show CO 2 /CH 4 (50 : 50) mixed gas feed with an attractive CO 2 /CH 4 selectivity of 134.2 and CO 2 permeance of 71 GPU at 35 °C. Furthermore, a H 2 /CH 4 selectivity of 663 with H 2 permeance of 240 GPU was achieved for promising green energy resource‐H 2 separation processes.

Cao, Yuhe↗
DOE OSTI2025

Supported ionic liquid membranes (SILMs) with exceptional selectivity and permeability for dilute CO 2 separations

Supported ionic liquid membranes (SILMs), containing phosphonium ionic liquids with aprotic N-heterocyclic anions (AHA ILs) in an inert inorganic support, were tested under both dry and humidified (40 % RH) mixed-gas conditions down to 420 ppm CO 2 in N 2 at 35 °C. In the dry case, the best performing IL, triethyl(octyl)phosphonium 4-bromopyrazolide ([P 2228 ][4-BrPyra]) exhibited mixed-gas CO 2 permeabilities and CO 2 /N 2 permeability selectivities as high as 26,800 barrer and 7,000, respectively. In the presence of humidity, the CO 2 permeability and CO 2 /N 2 selectivity increased to 49,100 barrer and 13,200, respectively, and these are the highest reported combination in the literature. Humidity amplifies CO 2 permeabilities and CO 2 /N 2 permeability selectivities through increases in CO 2 capacity due to bicarbonate formation and through faster mobility of the mobile carrier from decreased viscosity. Furthermore, N 2 permeability stayed roughly invariant in the presence of humidity, likely from competing effects of viscosity reduction and lower N 2 solubility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1975

The Research and Development of a Soluble Reactants and Products Secondary Battery System

A redox battery system which employs an aqueous dectrolyte is developed. Results are presented of the following experimental studies (1) measurement of the essential physical and chemical properties of the reactants and products; (2) evaluation of commerically available anion membranes as the cell separator, (3) determination of the composition and degradation mechanism of the anion membrane, and/or developing an anion membrane separator; and (4) evaluation of the performance of prototype secondary battery systems.

Liu, C. C.↗
DOE OSTI2021

Catalytic Reduction of Graphene Oxide Membranes and Water Selective Channel Formation in Water–Alcohol Separations

Graphene oxide (GO) is a promising membrane system for chemical separation applications due to its 2-D nanofluidics properties and an ability to control interplanar spacing for selectivity. The permeance of water, methanol (MeOH) and isopropyl alcohol (IPA) through 5 µm thick membranes was found to be 0.38 ± 0.15, 0.33 ± 0.16 and 0.42 ± 0.31 LMH/bar (liter/m2·h·bar), respectively. Interestingly, the permeance of a water–alcohol mixture was found to be dramatically lower (~0.01 LMH/bar) than any of its components. Upon removing the solvent mixture, the transmembrane flux of the pure solvent was recovered to near the original permeance. The interlayer space of a dried GO membrane was found to be 8.52 Å, which increased to 12.19 Å. 13.26 Å and 16.20 Å upon addition of water, MeOH and IPA. A decrease in d-space, about 2 Å, was consistently observed when adding alcohol to water wetted GO membrane and an optical color change and reduction in permeance. A newly proposed mechanism of a partial reduction of GO through a catalytic reaction with the water–alcohol mixture is consistent with experimental observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Regulating Gas Transport in Molecularly Engineered Polymer Membranes (Final Technical Report)

Energy-efficient separation processes are essential for a wide range of applications ranging from clean fuels (e.g., hydrogen purification) and petroleum refining (e.g., natural gas processing) to water purification and carbon capture. Membrane-mediated separations have shown tremendous promise in providing high productivity and high separation efficiency at significantly lower energy consumption, e.g., up to 90% less energy cost than traditional thermally driven processes such as distillation. Polymeric membranes–the dominant separation membrane materials–have yet to reach their full potential due to their limitations in long-term durability (e.g., productivity loss over the period of their lifetime due to physical aging) or insufficient stability under harsh conditions (e.g., high temperature, chemically complex feeds). This research seeks to establish a new paradigm in polymer membrane material design by harnessing crosslinked model networks with well-defined yet finely tailorable microstructure to facilitate fast and selective gas transport and simultaneously enhance membrane stability. Unlike traditional randomly crosslinked polymers, which suffer from structural inconsistencies and consequently suboptimal gas separation performance, crosslinked model network membranes prepared via a precisely controlled end-linking process enables the creation of previously unattainable microstructure tunability, which, in turn, results in versatile crosslinked membranes with high separation performance that meet the needs of various challenging gas separations. Using model network framework as a fundamental tool by applying this concept in diverse polymer categories, this work has led to the development of various innovative crosslinked membrane structures such as unimodal, bimodal and clustered model networks. These advanced crosslinked polymer membranes not only demonstrate exceptional gas separation performance that significantly outperform existing randomly crosslinked membranes, but also possess excellent long-term durability and robust stability under complex operating conditions. From a fundamental perspective, results from this research provide critical mechanistic insights into gas separation in crosslinked polymer membranes, addressing key knowledge gaps and opening new avenues for membrane design to meet various separation needs. The new membrane materials produced from this research enable the use of polymeric membranes for high temperature gas separations, offering substantial energy and cost savings by eliminating the need for repeated cooling-heating cycles in industrial processes.

02 PETROLEUM↗
DOE OSTI2026

Separation of Hydrogen Using Pd/Ag Membranes: Experimental and Modeling Results with Potential Application to Direct Internal Recycle

Implementation of fusion energy requires processing the deuterium-tritium (D-T) mixture used to fuel the reaction, and separation of hydrogen isotopes from other gases is imperative. Specifically, the separation of hydrogen isotopes from helium is a matter of importance to the fusion fuel cycle community. Initial testing with a palladium-silver (Pd-Ag) membrane indicates that even moderate vacuum (~100 torr permeate pressure) can provide a high degree of separation (>90%) at a high ratio of H 2 to He. Given the presence of He in many fusion systems, a high technology readiness level (TRL) for Q 2 /He (where Q represents any isotope of hydrogen) separations is needed. This study demonstrates the efficacy of H 2 removal from He via permeation and potential applications for direct internal recycle. Modeling will accompany the experimental campaign to generate a predictive capability and quantify the separation performance. Modeling from previous hydrogen permeation studies has demonstrated that the typical Sieverts’ law fails to predict the measured permeation rates at high hydrogen fluxes. Existing models are being refined to integrate the effects of surface phenomena into permeation predictions, which have been expanded to account for mixtures with large ranges of Q 2 concentrations. These data will improve the TRL of permeators as a separation technology for the fusion fuel cycle.

08 HYDROGEN↗
DOE OSTI2022

Processes for separation of aromatic compounds using a thin film composite membrane

This invention discloses a method for separation of an aromatic compound from a mixture comprising an alkane using an improved thin-film composite membrane. The membrane is particularly useful for separation of benzene from cyclohexane, which have similar boiling points. The membrane comprises a more mechanically durable and defect-free separation layer as a result of its fabrication from an ionomer solution that is substantially free of dissolved ionic species not associated with the ionomer.

Majumdar, Sudipto↗
DOE OSTI2024

Mapping TpPa-1 covalent organic framework (COF) molecular interactions in mixed solvents via atomistic modeling and experimental study

Complex solvent environments continue to limit the widespread adoption of organic solvent nanofiltration (OSN) in many chemical industry applications. In this paper we employ a commercially available covalent organic framework (COF), TpPa-1, and force field models to molecularly map separation performance of TpPa-1 membrane in mixed solvents. To minimize time and length scale mismatch between atomistic modeling and experiments, solvent permeance was normalized with water in modeling and experimental results to enable direct comparison. Model outputs, such as organic solvent permeance and solute rejection rate, matched well with filtration results. Since the atomistic models assume that all mass transfer is via through-pore transport, the discrepancies between modeling and experimental results provide insights on the effect of linear polymer defects, adsorption and interstitial mass transfer on polycrystalline COF membrane performance. In sum, force field models can serve as digital twins of COF membranes to simulate separation processes while capturing the effects of COF structure, chemistry, and crystallinity on membrane performance in complex organic solvent environments. Finally, this approach will provide insight into future COF design and synthesis for persisting separation challenges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2001

Buffer Gas Acquisition and Storage

The acquisition and storage of buffer gases (primarily argon and nitrogen) from the Mars atmosphere provides a valuable resource for blanketing and pressurizing fuel tanks and as a buffer gas for breathing air for manned missions. During the acquisition of carbon dioxide (CO2), whether by sorption bed or cryo-freezer, the accompanying buffer gases build up in the carbon dioxide acquisition system, reduce the flow of CO2 to the bed, and lower system efficiency. It is this build up of buffer gases that provide a convenient source, which must be removed, for efficient capture Of CO2 Removal of this buffer gas barrier greatly improves the charging rate of the CO2 acquisition bed and, thereby, maintains the fuel production rates required for a successful mission. Consequently, the acquisition, purification, and storage of these buffer gases are important goals of ISRU plans. Purity of the buffer gases is a concern e.g., if the CO, freezer operates at 140 K, the composition of the inert gas would be approximately 21 percent CO2, 50 percent nitrogen, and 29 percent argon. Although there are several approaches that could be used, this effort focused on a hollow-fiber membrane (HFM) separation method. This study measured the permeation rates of CO2, nitrogen (ND, and argon (Ar) through a multiple-membrane system and the individual membranes from room temperature to 193K and 10 kpa to 300 kPa. Concentrations were measured with a gas chromatograph that used a thermoconductivity (TCD) detector with helium (He) as the carrier gas. The general trend as the temperature was lowered was for the membranes to become more selective, In addition, the relative permeation rates between the three gases changed with temperature. The end result was to provide design parameters that could be used to separate CO2 from N2 and Ar.

Parrish, Clyde F.↗