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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Advanced Alkaline Membrane H 2 /Air Fuel Cell System with Novel Technique for Air CO 2 Removal

Over the course of this project, significant progress was achieved in developing the hydroxide exchange membrane fuel cell (HEMFC) and the electrochemically-driven CO₂ separator (EDCS), with a focus on improving performance, durability, and scalability. Key milestones were met, and the technology demonstrated potential for a wide range of applications, including fuel cell vehicles, direct air capture (DAC), and life support systems.

08 HYDROGEN↗
DOE OSTI2021

Integration of Air Classification and Hydrothermal Carbonization to Enhance Energy Recovery of Corn Stover

Air classification (AC) is a cost-effective technology that separates the energy-dense light ash fraction (LAF) from the inorganic-rich high ash fraction (HAF) of corn stover. HAF could be upgraded into energy-dense solid fuel by hydrothermal carbonization (HTC). However, HTC is a high-temperature, high-pressure process, which requires additional energy to operate. In this study, three different scenarios (i.e., AC only, HTC only, and integrated AC–HTC) were investigated for the energy recovery of corn stover. AC was performed on corn stover at an 8 Hz fan speed, which yielded 84.4 wt. % LAF, 12.8 wt. % HAF, and 2.8 wt. % below screen particles. About 27 wt. % ash was reduced from LAF by the AC process. Furthermore, HTC was performed on raw corn stover and the HAF of corn stover at 200, 230, and 260 °C for 30 min. To evaluate energy recovery, solid products were characterized in terms of mass yield, ash yield, ultimate analysis, proximate analyses, and higher heating value (HHV). The results showed that the energy density was increased with the increase in HTC temperature, meanwhile the mass yield and ash yield were decreased with the increase in HTC temperature. Proximate analysis showed that fixed carbon increased 18 wt. % for original char and 27 wt. % for HAF char at 260 °C, compared to their respective feedstocks. Finally, the hydrochar resulting from HAF was mixed with LAF and pelletized at 180 bar and 90 °C to densify the energy content. An energy balance of the integrated AC–HTC process was performed, and the results shows that integrated AC with HTC performed at 230 °C resulted in an additional 800 MJ/ton of energy recovery compared to the AC-only scenario.

09 BIOMASS FUELS↗
DOE OSTI2024

Dual-module humidity pump for efficient air dehumidification: Demonstration and performance limitations

Condensation dehumidification in conventional air conditioning technologies is energy-intensive, accounting for up to 50% of building cooling energy used in some climates. Selective vacuum membrane dehumidification (VMD) is one of the leading alternative dehumidification technologies due to its potential for significant energy savings, and the “dual-module humidity pump” is one of the most promising VMD concepts. Here, this work is the first to provide experimental proof-of-concept for the dual-module humidity pump system and provides the first thermodynamic modeling framework that accounts for realistic steady-state operating limitations, both of which are lacking in the current literature. Additionally, this work is the first to provide a system design solution that overcomes practical challenges associated with air accumulation in the vacuum channels. The experimental results in this work show that the current prototype can remove up to 45% of the water vapor in the air stream, and the vapor pressure difference in the vapor rejection module needs to be approximately 2–4 times greater than that of the dehumidification module in order to maintain balanced mass transfer. The thermodynamic model applied to typical air conditioning conditions shows that the ideal dehumidification (latent) COPs can reach up to 40, but practical COPs are limited to approximately 10. Furthermore, the model shows that the overall energy efficiency increases as the membrane air selectivity increases, though this improvement gradually starts to diminish when the membrane selectivity is increased above 10,000.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Split HPWHs as an Efficient Solution for Multifamily Buildings with In-Unit Water Heaters

A quarter of all housing units in the United States are found in multifamily buildings, but few efficiency innovations have been made to improve electric water heating systems in this building type. Domestic hot water in multifamily buildings can either be provided by a large central water heater or smaller in-unit water heaters. Integrated heat pump water heaters that are installed in single-family homes are often a poor fit for individual multifamily units because the water heaters are often located in small internal closets. This confined space can limit the airflow to the heat pump, and the cold exhaust air can cause discomfort and reduced efficiency. Split CO2 HPWHs separate the tank from the heat pump, which allows for installation location flexibility. Further, CO2 heat pumps can operate under colder ambient conditions, making them a better fit for multifamily units across a wide range of climate regions. As part of a larger project to characterize split HPWH performance, we evaluated the feasibility of installing an additional, parallel tank that could provide hot water to a second housing unit using a single CO2 heat pump. This approach would reduce the first costs of these more expensive units. Based on the high draw volume that we imposed on both tanks, the same heat pump may be able to support more tanks, depending on hot water usage. This paper will describe the split CO2 HPWH technology, how the two-tank system was controlled, and results from our laboratory evaluation.

CO2 HPWH↗
DOE OSTI2022

Split HPWHs as an Efficient Solution for Multifamily Buildings with In-Unit Water Heaters: Preprint

A quarter of all housing units in the country are found in multifamily buildings but few efficiency innovations have been made to improve electric water heating systems in this building type. Domestic hot water in multifamily buildings can either be provided by a large central water heater or smaller in-unit water heaters. Integrated heat pump water heaters that are installed in single family homes are often a poor fit for individual multifamily units since the water heaters are often located in small internal closets. This confined space can limit the air flow to the heat pump and the cold exhaust air can cause discomfort and reduced efficiency. Split CO2 HPWHs separate the tank from the heat pump, which allows for installation location flexibility. Further, CO2 heat pumps can operate under colder ambient conditions, making them a better fit for multifamily units across a wide range of climate regions. As part of a larger project to characterize split HPWH performance, we evaluated the feasibility of installing an additional, parallel tank that could provide hot water to a second housing unit using a single CO2 heat pump. This approach would reduce the first costs of these more expensive units. Based on the high draw volume that we imposed on both tanks, the same heat pump may be able to support more tanks, depending on hot water usage. This paper will describe the split CO2 HPWH technology, how the two-tank system was controlled, and results from our laboratory evaluation.

CO2 HPWH↗
DOE OSTI2025

Polar Bear™ – Innovative Capture of Storage Tank Vapors

Polar Bear™ is a patented technology developed by the Energy & Environmental Research Center (EERC) to capture storage tank vapors and eliminate methane emissions from upstream oil- and gas-producing facilities. Sparked by early commercial investment, the EERC licensed the technology and extended the intellectual property to storage tanks. Polar Bear™ is uniquely engineered and adapted to individual lower-producing facilities where there is otherwise no economic alternative for capturing tank vapors. A high number of small producing oil and gas wells are distributed across the country. The aggregate contributes to a significant volume of emissions. Because of the lack of economy of scale, gas volumes from these facilities are typically not recovered and contribute to methane emissions. Polar Bear™ provides a fit-for-purpose compression solution that addresses cost by reducing complexity with respect to conventional vapor recovery units and eliminating oil changes. Unique to Polar Bear™ is the capability to separate oxygenated gas from storage tank vapors. Storage tanks are designed to “breathe,” allowing gas to enter and escape during internal level and temperature changes. This infiltration of air into the tank headspace imparts undesirable oxygen content with respect to pipeline gathering. Polar Bear™ separates the vapor stream, allowing oxygen-rich gas to be used as fuel on-site while recovering the liquids-rich portion of the gas where oxygen content is minimized. A prototype system was tested to verify process models, evaluate operational performance, and advance the technology readiness level from 5 to 6. Results provide a good match between experimental measurements and process models, indicating the models are useful for future scale-up and field design. Various mixtures of nitrogen and liquefied petroleum gas were tested to understand the mass balance of nitrogen and how it relates to the potential control of oxygen content. Findings indicate that less than 2000 ppm of oxygen is likely to remain in the liquid portion of the gas in field applications. The research and development prepare the technology for field implementation to eliminate routine and fugitive methane emissions from storage tanks.

02 PETROLEUM↗
DOE OSTI2022

Routes to roots: direct evidence of water transport by arbuscular mycorrhizal fungi to host plants

Summary Arbuscular mycorrhizal fungi (AMF) can help mitigate plant responses to water stress, but it is unclear whether AMF do so by indirect mechanisms, direct water transport to roots, or a combination of the two. Here, we investigated if and how the AMF Rhizophagus intraradices transported water to the host plant Avena barbata , wild oat. We used two‐compartment microcosms, isotopically labeled water, and a fluorescent dye to directly track and quantify water transport by AMF across an air gap to host plants. Plants grown with AMF that had access to a physically separated compartment containing 18 O‐labeled water transpired almost twice as much as plants with AMF excluded from that compartment. Using an isotopic mixing model, we estimated that water transported by AMF across the air gap accounted for 34.6% of the water transpired by host plants. In addition, a fluorescent dye indicated that hyphae were able to transport some water via an extracytoplasmic pathway. Our study provides direct evidence that AMF can act as extensions of the root system along the soil–plant–air continuum of water movement, with plant transpiration driving water flow along hyphae outside of the hyphal cell membrane.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Separation of volatile organic contaminants from water using a direct-contact dehumidifier: An experimental study and modeling

A packed-bed, direct-contact dehumidifier (PB-DCD) has been developed to selectively condense water from a gaseous mixture of organic contaminants. In this process, hot air is humidified by mixing with wastewater vapor in a static mixer and is dehumidified by subcooled fresh water passing through the PB-DCD in a counter-current configuration. The goal of this study is to understand the relationship between various operating parameters and how they affect separation of isopropyl alcohol (IPA) from the gaseous mixture with the purpose of expanding the investigation to other contaminants in the future. The process has been successfully used to separate IPA from wastewater. Different parameters including the concentration of IPA in water, feed temperature, air-to-vapor ratio, and cooling-water-to-vapor mass ratio, as well as residence time were examined to determine their influence on contaminant separation and clean water recovery rate. The Buckingham Pi theorem was applied to reduce the number of studying variables by generating non-dimensional groups. Experiments were performed to determine the relationship between the non-dimensional parameters and model mass transfer in the system. Mass transfer coefficients for multicomponent gaseous mixture condensation in a packed-bed direct contact condenser column are calculated and a modified correlation of mass transfer is developed. The parameters of the mass transfer model are obtained from operating conditions of the PB-DCD, stream conditions and thermodynamic properties. A modified Sherwood correlation is developed to predict IPA separation from a gaseous mixture consisting of air, water, and IPA. The modified Sherwood correlation is applied to successfully predict the Sherwood number with a mean absolute error equal to 6.6 %. According to the experimental results, the maximum IPA separation achieved was 76.3 %, which corresponds to a water recovery rate of 58.7 %.

42 ENGINEERING↗
DOE OSTI2025

Frontiers of Ionic Liquids in Carbon Dioxide Separation and Valorization

Ionic liquids (ILs) have emerged as highly tunable sorbents and membranes for gas separation, especially in the purification of CO 2 -containing gas streams such as air, natural gas, biogas, and syngas. Their negligible volatility, high thermal stability, and chemical versatility position them as promising alternatives to conventional amine and alkaline metal derivative-based systems, effectively addressing key challenges such as volatility, stability, and high regeneration energy. Here, this Review explores IL-derived systems for CO 2 -related gas separation across dense, porous, and supported categories. At the dense liquid level, we discuss strategies for tailoring IL properties to optimize CO 2 sorption, focusing on the correlation between IL-CO 2 interaction strength, uptake capacity, and regeneration energy. Key advancements in carbon capture, including amino-functionalized (AILs) and superbase-derived ILs (SILs), are highlighted, along with strategies such as chemical structure engineering, multiple binding site integration, alternative driving force exploration, and stability enhancement. Then, the porous liquids (PLs) scale focuses on the emerging field integrating IL properties with permanent porosity engineering, spanning ultramicropores (<5 Å) to macropores (around 100 nm). These innovations improve gas uptake capacity, accelerate transport kinetics, introduce the gating effect, and enable the coexistence of active sites with antagonistic properties within a single IL medium. At the supported IL scale, the discussion shifts to IL- and ionic pair-modified sorbents and membranes, emphasizing the modulation of cations and anions, confinement effects from porous supports, and the IL–interface interaction to enhance CO 2 separation performance, particularly in diluted gas streams. Beyond separation, this Review highlights IL-based integrated processes for CO 2 capture and conversion into value-added chemicals via thermocatalytic, electrocatalytic, and photocatalytic pathways. At each scale, advanced computational and experimental tools for IL design are also discussed, providing insights into stability enhancement, sorption efficiency, and process integration. The Review concludes by addressing existing challenges and outlining future directions for IL-driven innovations in gas separation technologies.

Qiu, Liqi [Univ. of Tennessee, Knoxville, TN (Unit↗
DOE OSTI2020

Predicting secondary organic aerosol phase state and viscosity and its effect on multiphase chemistry in a regional-scale air quality model

Atmospheric aerosols are a significant public health hazard and have substantial impacts on the climate. Secondary organic aerosols (SOAs) have been shown to phase separate into a highly viscous organic outer layer surrounding an aqueous core. This phase separation can decrease the partitioning of semi-volatile and low-volatile species to the organic phase and alter the extent of acid-catalyzed reactions in the aqueous core. A new algorithm that can determine SOA phase separation based on their glass transition temperature (T g ), oxygen to carbon (O:C) ratio and organic mass to sulfate ratio, and meteorological conditions was implemented into the Community Multiscale Air Quality Modeling (CMAQ) system version 5.2.1 and was used to simulate the conditions in the continental United States for the summer of 2013. SOA formed at the ground/surface level was predicted to be phase separated with core–shell morphology, i.e., aqueous inorganic core surrounded by organic coating 65.4 % of the time during the 2013 Southern Oxidant and Aerosol Study (SOAS) on average in the isoprene-rich southeastern United States. Our estimate is in proximity to the previously reported ~70 % in literature. The phase states of organic coatings switched between semi-solid and liquid states, depending on the environmental conditions. The semi-solid shell occurring with lower aerosol liquid water content (western United States and at higher altitudes) has a viscosity that was predicted to be 10 2 –10 12 Pa s, which resulted in organic mass being decreased due to diffusion limitation. Organic aerosol was primarily liquid where aerosol liquid water was dominant (eastern United States and at the surface), with a viscosity <10 2 Pa s. Phase separation while in a liquid phase state, i.e., liquid–liquid phase separation (LLPS), also reduces reactive uptake rates relative to homogeneous internally mixed liquid morphology but was lower than aerosols with a thick viscous organic shell. The sensitivity cases performed with different phase-separation parameterization and dissolution rate of isoprene epoxydiol (IEPOX) into the particle phase in CMAQ can have varying impact on fine particulate matter (PM 2.5 ) organic mass, in terms of bias and error compared to field data collected during the 2013 SOAS. This highlights the need to better constrain the parameters that govern phase state and morphology of SOA, as well as expand mechanistic representation of multiphase chemistry for non-IEPOX SOA formation in models aided by novel experimental insights.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Ultra-fast microwave regeneration of CO 2 solid sorbents for energy-efficient direct air capture

Large-scale deployment of direct air capture (DAC) technologies has become critical for mitigating climate change. Towards this end, energy-efficient regeneration of the sorbents used in the process of carbon capture from air is very important to significantly reduce the high operational cost of DAC. Guanidine compounds can be used with environmentally friendly aqueous amino acids (e.g., potassium sarcosinate) for fast and effective CO 2 capture from air, and have a strong potential for low-energy CO 2 release and sorbent regeneration. In this process, the amino acid absorbs the CO 2 from the air, and the guanidine compounds react with the CO 2 -rich amino acid solution and crystallize as an insoluble carbonate salt. Separation and thermal regeneration of the precipitated guanidine carbonate salt leads to an overall low-temperature and low-energy direct air capture process. Effective CO 2 release from the solid guanidine compound can be achieved by mild heating at 120 °C. Here, in this study, to overcome the relatively inefficient traditional conductive heating of the crystalline solid (i.e., Methylglyoxal-bis(iminoguanidine) carbonate, MGBIG carbonate), we evaluated the feasibility of microwave heating of MGBIG carbonate in terms of power requirement, radiation time, and solids mass for efficient CO 2 desorption. The energy consumption needed by a microwave oven and a conventional oven to regenerate the same mass of the sorbent was directly measured to compare the total energy required per unit mass of regenerated sample and provide an understanding of the potential benefits of microwave regeneration. We found that microwave heating effectively regenerates MGBIG carbonate, which may be facilitated by the water molecules that are co-crystallized with carbonate in the guanidine crystals. Microwave heating at 2.54 GHz with 1250 W is up to 17 times faster than conventional conductive heating at 160 °C, resulting in 40 % electrical energy reduction. These results indicate that microwave regeneration may be an energy-efficient method for fast regeneration of solid sorbents used for direct air capture.

42 ENGINEERING↗
DOE OSTI2023

Bipolar Membranes with an Electrospun 3D Junction

Freestanding bipolar membranes (BPMs) with an entirely new and transformative morphology were fabricated and characterized. The key disruptive design element was a water-splitting/water-generation junction layer of finite thickness composed of interwoven and interlocking electrospun anion-exchange polymer (AEP) fibers and cation-exchange polymer (CEP) fibers. Methods were developed to sandwich the 3D junction layer between two pre-formed dense AEP and CEP films., with the closure of all interfiber voids, where the processing steps are easily incorporated into a commercial roll-to-roll membrane manufacturing scheme. A series of membranes were made using different polymers and junction layers to identify the optimum morphology and composition for water-splitting and water-generation applications. For water splitting, the 3D junction BPMs worked remarkably well with operating current densities at/above 1.0 A/cm2 (10X greater than commercial BPMs) at a transmembrane voltage drop of only 1.1 V. In water generation mode, the 3D junction BPMs operated at 0.5 A/cm2, a world-record current density. The membranes were found to exhibit outstanding durability and can be manufactured at scale for low cost. The high operating current densities and stable long-term operation are due to the 3D junction layer design, where there is a high interfacial area for water splitting or water generation reactions and where the interlocking fibers prevent delamination of the outer films. These new BPMs are ideal candidate materials for both existing water-splitting electrodialysis separations and new electrochemical processes, such as large-scale direct air capture of CO 2 , reactors for CO 2 reduction, self-hydrating fuel cells, and redox flow batteries.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2022

Comparison of Irradiated and Unirradiated Graphite Oxidation Performance

This work examines the oxidation behavior of NBG-25 graphite using irradiated specimens and (not irradiated) companion specimens from the Advanced Graphite Creep (AGC) Experiment. Irradiated and companion specimens were quartered, split into four small samples, to enable four oxidation test runs for each (0.5 inch diameter by 0.25 inch tall) piggyback button obtained from the AGC Experiment inventory. These split samples were oxidized in air in a thermogravimetric analyzer (TGA) and benchmarked against observations with separately sourced same-grade specimens of three geometries oxidized either in the TGA or in a vertical furnace built and operated to satisfy the specifications of ASTM D7542. The study considers both irradiation damage and relief of damage by thermal annealing. A range of isothermal oxidation temperatures were tested for specimens exposed to a similar irradiation environment, nominally 6.5 dpa at 650°C. To assess the dose dependency of observed oxidation behavior, specimens with a range of irradiation exposures (up to 6.8 dpa) were tested at the single oxidation temperature of 650°C. In the conventional analysis (rate determined over the 5-10% mass loss range) any annealing effects appear to be negligible, while irradiation to ~6.5 dpa may double or triple the subsequent oxidation rate. However, examination of rate with extent of reaction (over incremental ranges from initial onset up to 5% mass loss) illustrates that (at least for ~6.5 dpa) irradiation initially inhibits oxidation. Slower rates of oxidation than companion split samples are clearly indicated across all oxidation temperatures tested up to ~0.5% mass loss. Over the range of 0.5-1% mass loss, regardless of normalization strategy, there is no statistically meaningful difference in oxidation rate. However, beyond 0.5% mass loss oxidation of the irradiated sample becomes progressively faster than the companion sample (up to the 10% mass loss level observed).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Spectrally filtered ps–ns emission dynamics of atmospheric-pressure nanosecond pulsed plasmas

The temporal dynamics of atmospheric-pressure nanosecond pulsed plasma discharges in a pin-to-pin electrode configuration are studied using streak-camera line imaging of the interelectrode gap with a time resolution as short as ~25 ps. Discharge emission initiates homogeneously throughout the interelectrode gap with no detectable streamer propagation and then temporally decays in two distinct phases. Plasma emission bands attributed to various electronic transitions are tracked for single discharges in air and N 2 . Spectral filtering of the excited molecular states reveals that the N 2 (C–B) and N 2 (B–A) emission bands evolve in distinct early and late phases, respectively, with a time separation of ~15–20 ns. Furthermore, significant differences in the temporal dynamics of plasma discharges in air and N2 are observed. High levels of excited-state atomic oxygen and NO appear after the initial decay of the N 2 (C) state and coincide primarily with the latter phases of plasma evolution in air environments. From temporal traces of discharge emission, the formation and relaxation timescales of the electronically excited states of N 2 are quantified in pure N2 and air environments with sub-nanosecond resolution. The streak-OES (optical emission spectroscopy) technique enables quantitative time-resolved studies of key chemical species for model validation in ultra-short-pulsed plasmas.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Air-breathing aqueous sulfur rechargeable batteries

An electrochemical apparatus includes a catholyte, an anolyte, and a separator disposed between the catholyte and the anolyte. The catholyte includes metal salt dissolved in water, thereby providing at least one metal ion. The anolyte includes a polysulfide solution. The separator is permeable to the at least one metal ion. During a charging process of the electrochemical apparatus, oxygen is generated in the catholyte, the polysulfide in the polysulfide solution undergoes a reduction reaction in the anolyte, and the at least one metal ion moves from the catholyte to the anolyte. During a discharging process of the apparatus, the oxygen is consumed in the catholyte, the polysulfide oxidizes in the anolyte, and the at least one metal ion moves from the anolyte to the catholyte.

Su, Liang↗
DOE OSTI2022

Hydrogen-powered Electrochemically-driven CO 2 Removal from Air Containing 400 to 5000 ppm CO 2

The performance of a hydrogen-powered, electrochemically-driven CO 2 separator (EDCS) was demonstrated at cathode inlet CO 2 concentrations from 400 ppm to 5,000 ppm. The impact of current density and CO 2 concentration were evaluated to predict operating windows for various applications. The single-cell data was used to scale a 100 cm 2 , multi-cell stack using a shorted-membrane design for four applications: direct air capture (DAC), hydroxide exchange membrane fuel cell (HEMFC) air pretreatment, submarine life support, and space habitation. For DAC, a 339-cell EDCS stack (7.7 L, 17 kg) was projected to remove 1 tonne CO 2 per year. The addition of the EDCS in HEMFC systems would result in nearly a 30% increase in volume, and therefore further improvements in performance would be necessary. A module containing five 338-cell EDCS stacks (38 L, 85 kg) in parallel can support a 150 person crew at 2.1% of the volume of the liquid amine system employed in submarines. For space habitation, a 109-cell EDCS stack (3.2 L, 10 kg) is adequate for 6 crewmembers, and is less than 1% the size and 5% the weight of the current CO 2 removal system installed on the International Space Station.

25 ENERGY STORAGE↗
DOE OSTI2024

An experimental and chemical kinetic modeling study of 4-butoxyheptane combustion

Here, the combustion kinetics of a novel oxygenated bioblendstock for diesel, 4-butoxyheptane (4-BH), was investigated experimentally using a flow reactor and a heated, high-pressure shock tube. The flow reactor experiments employed oxygen as the oxidizer and helium as the diluent with oxidation conducted at atmospheric pressure and 10 bar for temperatures from 400 to 1000 K at 20-K intervals. The fuel, oxidizer, and diluent flow rates were varied at different temperatures to maintain a constant initial fuel mole fraction of 1000 ppm, with stoichiometric equivalence ratio, and a residence time of 2.0 s. The reacted gas was fed to two separate GC systems that could qualitatively and quantitatively detect product species. Additionally, real fuel-air ignition delay time (IDT) data were collected using a heated, high-pressure shock-tube facility. Fuel lean (φ = 0.5) and stoichiometric (φ = 1.0) mixtures were investigated at 10 atm as well as at 30 atm for the fuel lean case for temperatures between 847 and 1259 K. A detailed chemical kinetics mechanism was developed to model the product distribution from the flow reactor and IDTs from the shock tube. The proposed model was able to predict the double NTC behavior in flow reactor experiments reasonably well. Model predictions at low temperatures were observed to be highly sensitive to the rate constants of ketohydroperoxide (KHP) decomposition in the case of the OOH group in α position which were modeled based on existing literature studies on ethers. It was noted that in the absence of theoretical or experimental studies, the rate constants for KHP decomposition used in the literature were empirically set. Additional studies are required to address the gap in model prediction obtained in this study and to reduce the uncertainty in kinetics models for ether oxidation. Predicted product concentrations and IDTs showed some quantitative agreement with experimental data, but the overall reactivity of the IDTs is underpredicted. Additionally, significant deviation is observed for the IDT results at 10 atm for the stoichiometric case with minor deviations for the other cases. The reaction pathways to the missing products were then further analyzed theoretically through quantum-mechanical calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Effect of Extended Aging and Oxidation on Linear Poly(propylenimine)-Mesoporous Silica Composites for CO 2 Capture from Simulated Air and Flue Gas Streams

Physical aging or degradation of amine-containing polymers and supported amine adsorbents is a critical issue that could limit practical application of such materials for CO 2 capture. However, to date, there is a scarcity of studies that evaluate the long-term stability of amine-based sorbents without the exclusive use of accelerated aging tests. Here, we demonstrate that extended aging (~2 years) of linear poly(propylenimine) (LPPI) confined in mesoporous silica (SBA-15) supports does not drastically impact the CO 2 adsorption performance under simulated flue gas (10% CO 2 ) and direct air capture (DAC, 400 ppm CO 2 ) conditions, although the behavior of the aged sorbents and polymers in the two CO 2 concentration regimes differs. Sorbents made with aged LPPI had modestly decreased CO 2 uptake performance (<~20% lower) compared to the fresh polymers, with overall good CO 2 cycling performance. The data indicate that only slow degradation occurs under the deployed ambient storage conditions. Even after extended aging, the LPPI-based sorbents preserved their ability to display stable temperature-swing cycling performance. In parallel, the impact of blending LPPI polymers of different number-average molecular weights, M n , is evaluated, seeking to understand its impact on adsorbent performance. We find that the results demonstrate that blends of two M n aged LPPI give similar CO 2 adsorption performance to adsorbents made from a single M n LPPI, suggesting that molecular weight will not negatively impact adsorbent performance in the studied M n range. After an accelerated oxidation experiment, the aged LPPI sorbents retained a larger portion of the samples’ original performance when cycling under simulated flue gas conditions than under DAC conditions. However, in each case, the oxidized sorbents could be cycled repeatedly with consistent uptake performance. Overall, these first of their kind extended aging tests suggest that LPPI-based amine adsorbents offer promise for long term, stable use in carbon capture applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗