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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Coupling plant litter quantity to a novel metric for litter quality explains C storage changes in a thawing permafrost peatland

Abstract Permafrost thaw is a major potential feedback source to climate change as it can drive the increased release of greenhouse gases carbon dioxide (CO 2 ) and methane (CH 4 ). This carbon release from the decomposition of thawing soil organic material can be mitigated by increased net primary productivity (NPP) caused by warming, increasing atmospheric CO 2 , and plant community transition. However, the net effect on C storage also depends on how these plant community changes alter plant litter quantity, quality, and decomposition rates. Predicting decomposition rates based on litter quality remains challenging, but a promising new way forward is to incorporate measures of the energetic favorability to soil microbes of plant biomass decomposition. We asked how the variation in one such measure, the nominal oxidation state of carbon (NOSC), interacts with changing quantities of plant material inputs to influence the net C balance of a thawing permafrost peatland. We found: (1) Plant productivity (NPP) increased post‐thaw, but instead of contributing to increased standing biomass, it increased plant biomass turnover via increased litter inputs to soil; (2) Plant litter thermodynamic favorability (NOSC) and decomposition rate both increased post‐thaw, despite limited changes in bulk C:N ratios; (3) these increases caused the higher NPP to cycle more rapidly through both plants and soil, contributing to higher CO 2 and CH 4 fluxes from decomposition. Thus, the increased C‐storage expected from higher productivity was limited and the high global warming potential of CH 4 contributed a net positive warming effect. Although post‐thaw peatlands are currently C sinks due to high NPP offsetting high CO 2 release, this status is very sensitive to the plant community's litter input rate and quality. Integration of novel bioavailability metrics based on litter chemistry, including NOSC, into studies of ecosystem dynamics, is needed to improve the understanding of controls on arctic C stocks under continued ecosystem transition.

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

Snowflake relocated Cu 2 O electrocatalyst on an Ag backbone template for the production of liquid C 2+ chemicals from CO 2

In this study, we performed the CO 2 reduction reaction (CO 2 RR) using a structural composite catalyst of cuprous oxide (Cu 2 O) and silver (Ag) that was simultaneously electrodeposited. While the underneath Ag electrodeposits maintained their spiky backbone structures even after the CO 2 RR, the Cu 2 O deposits were reduced to Cu(111) and relocated on the backbone template. Here, the structural changes in Cu 2 O to Cu increase the active area of the Cu–Ag interface, resulting in a remarkable production rate of 125.01 μmol h -1 of liquid C 2+ chemicals via the stabilization of the C–C coupling of the key intermediate species of acetaldehyde. This study provides new insights into designing a bimetallic catalyst for producing sustainable C 2+ products from CO 2 without any selectivity towards the production of methane.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Distinct microbiomes underlie divergent responses of methane emissions from diverse wetland soils to oxygen shifts

Abstract Hydrological shifts in wetlands, a globally important methane (CH4) source, are critical constraints on CH4 emissions and carbon-climate feedbacks. A limited understanding of how hydrologically driven oxygen (O2) variability affects microbial CH4 cycling in diverse wetlands makes wetland CH4 emissions uncertain. Transient O2 exposure significantly stimulated anoxic CH4 production in incubations of Sphagnum peat from a temperate bog by enriching for polyphenol oxidizers and polysaccharide degraders, enhancing substrate flow toward methanogenesis under subsequent anoxic conditions. To assess whether shifts in soil microbiome structure and function operate similarly across wetland types, here we examined the sensitivity of different wetland soils to transient oxygenation. In slurry incubations of Sphagnum peat from a minerotrophic fen, and sediments from a freshwater marsh and saltmarsh, we examined temporal shifts in microbiomes coupled with geochemical characterization of slurries and incubation headspaces. Oxygenation did not affect microbiome structure and anoxic CH4 production in mineral-rich fen-origin peat and freshwater marsh soils. Key taxa linked to O2-stimulated CH4 production in the bog-origin peat were notably rare in the fen-origin peat, supporting microbiome structure as a primary determinant of wetland response to O2 shifts. In contrast to freshwater wetland experiments, saltmarsh geochemistry—particularly pH—and microbiome structure were persistently and significantly altered postoxygenation, albeit with no significant impact on greenhouse gas emissions. These divergent responses suggest wetlands may be differentially resistant to O2 fluctuations. With climate change driving greater O2 variability in wetlands, our results inform mechanisms of wetland resistance and highlight microbiome structure as a potential resiliency biomarker.

Reji, Linta (ORCID:0000000213376782)↗
DOE OSTI2022

Reduced Precious Metal Catalysts for CH 4 and NO x Emission Control of Natural Gas Vehicles

The abundant domestic natural gas resources coupled with the desire for clean air and reduced greenhouse gas emissions motivates the accelerated development of natural gas vehicles (NGVs) and engine. Methane (CH 4 ), a potent greenhouse gas, is the major component of natural gas. The current emission catalysts fall short in meeting the desired exhaust CH 4 emission standards for NGVs. In this project we have developed a class of novel Platinum Group Metal (PGM) basedmonolith catalysts with enhanced activity.

03 NATURAL GAS↗
DOE OSTI2021

Production, fuel properties and combustion testing of an iso-olefins blendstock for modern vehicles

With the increasing pressure to decarbonize the transportation sector, exploring strategies that can reduce emissions from light-duty vehicles (LDV) has become critical. Bioblendstocks that allow for higher engine efficiency and fuel economy could complement vehicle electrification and help reach carbon neutrality by 2050. In this context, the potential of a mixture of iso-olefins as a bioblendstock was investigated for multimode boosted spark-ignition (SI)/advanced compression ignition (ACI) engine operation designed to achieve higher overall vehicle fuel economy. By establishing the relationship between the molecular structure of iso-olefins and research octane number (RON), octane sensitivity (S) (i.e., the difference between RON and motor octane number [MON]), and phi-sensitivity a dimethyl-hexenes rich olefins mixture (DMHROM) was identified as a preferred blendstock for SI/ACI combustion engines. Here, a pathway for DMHROM production from biomass-derived ethanol was developed and scaled up. More than 1 gallon of DMHROM blendstock was produced for fuel properties assessment including engine testing. Measurements in a Cooperative Fuel Research Engine showed that the DMHROM blendstock possesses a RON of 94 and S of 13.5, and blends synergistically. Rapid compression machine tests coupled with single-cylinder gasoline direct injection engine measurements demonstrated the 20 vol.% DMHROM blend has higher phi-sensitivity than an olefin-free gasoline base fuel and a typical California Reformulated Gasoline Blendstock for Oxygenate Blending (CARBOB) gasoline fuel. These results demonstrate the potential of DMHROM for improving gasoline fuel performance and quality for operation under ACI conditions. The effectiveness of the aftertreatment system in mitigating emissions was verified and showed that the pure DMHROM blendstock and 20 vol.% blend would not increase non-methane organic gases, NO x , and carbon monoxide (CO) emissions. The DMHROM blendstock was found to slightly decrease sooting tendency when added to a gasoline-base fuel (i.e., ~6% reduction at 20 vol.% blending level). Oxidation stability and lubricant compatibility were both confirmed for the 20 vol.% blend. Overall, these results demonstrate that dimethyl-hexenes have potential for improving engine efficiency and fuel economy while meeting emissions regulations and ASTM specifications for gasoline fuel.

09 BIOMASS FUELS↗
DOE OSTI2023

High methane concentrations in tidal salt marsh soils: Where does the methane go?

Abstract Tidal salt marshes produce and emit CH 4 . Therefore, it is critical to understand the biogeochemical controls that regulate CH 4 spatial and temporal dynamics in wetlands. The prevailing paradigm assumes that acetoclastic methanogenesis is the dominant pathway for CH 4 production, and higher salinity concentrations inhibit CH 4 production in salt marshes. Recent evidence shows that CH 4 is produced within salt marshes via methylotrophic methanogenesis, a process not inhibited by sulfate reduction. To further explore this conundrum, we performed measurements of soil–atmosphere CH 4 and CO 2 fluxes coupled with depth profiles of soil CH 4 and CO 2 pore water gas concentrations, stable and radioisotopes, pore water chemistry, and microbial community composition to assess CH 4 production and fate within a temperate tidal salt marsh. We found unexpectedly high CH 4 concentrations up to 145,000 μmol mol −1 positively correlated with S 2− (salinity range: 6.6–14.5 ppt). Despite large CH 4 production within the soil, soil–atmosphere CH 4 fluxes were low but with higher emissions and extreme variability during plant senescence (84.3 ± 684.4 nmol m −2 s −1 ). CH 4 and CO 2 within the soil pore water were produced from young carbon, with most Δ 14 C‐CH 4 and Δ 14 C‐CO 2 values at or above modern. We found evidence that CH 4 within soils was produced by methylotrophic and hydrogenotrophic methanogenesis. Several pathways exist after CH 4 is produced, including diffusion into the atmosphere, CH 4 oxidation, and lateral export to adjacent tidal creeks; the latter being the most likely dominant flux. Our findings demonstrate that CH 4 production and fluxes are biogeochemically heterogeneous, with multiple processes and pathways that can co‐occur and vary in importance over the year. This study highlights the potential for high CH 4 production, the need to understand the underlying biogeochemical controls, and the challenges of evaluating CH 4 budgets and blue carbon in salt marshes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Investigating the Impact of Absorbed Surface Impurities (CO, CO 2 , CH 4 , and H 2 O) on Getter Rate Performance

This report provides an overview of engineering and experimental efforts to establish a new capability for measuring H2 uptake rates for Tritium Producing Abosrber Rod (TPBAR) getter materials. This new system was used to gain a better understanding of the impact of contaminant species (CO 2 , CO, CH 4 , and H 2 O) on getter performance under relevant hydrogen uptake conditions (350 °C, 20 torr). Herein, we successfully established a high-resolution gravimetric sorption (HRGS) system in a flow through configuration that can measure sample mass changes with high resolution (1 µg or 10 µg) over long experiment times (days), high temperature, and varying pressures. We coupled this capability with an in-line universal gas analyzer (UGA) system to characterize potential surface chemistry side reactions occurring after contaminant gas exposure. The major findings of this study suggest that methane and CO have the most detrimental effects on getter H 2 uptake performance showing large changes in rate after exposure compared to CO 2 and water. The effect of these contaminant species did not influence getter sample capacity (~ 1.8 wt% H 2 ). After CO and methane exposure, changes in getter rate were accompanied by observable Ni-surface defects and pinholes via SEM imaging suggesting possible Ni- layer corrosion. Additionally, the increase in C and O signal in the zircaloy layer, observed via EDX, point to C and O species transport through the getter sample resulting in the formation of carbides and oxide species. Thus, co-exposure studies where mixed gases or water vapor are introduced together will be important to further understand what mechanisms are contributing to Ni-layer corrosion and changes in getter performance.

36 MATERIALS SCIENCE↗
NASA NTRS1993

Prediction of prompt NO(x) in hydrocarbon air flames

The gas turbine industry is directing particular attention to very low NOx combustors, whether for aircraft or land based CCGT systems. These low NOx combustors frequently use liquid fuels or natural gas burning under very lean premixed conditions with air or under rich-lean conditions, although only the first case is studied here. In land based systems, diluted steam or nitrogen are sometimes injected into the combustion chambers to reduce flame temperature. The NOx emissions from such systems are the product of three chemical mechanisms which are interrelated: the hydrocarbon prompt NO, the thermal NO (extended Zeldovich mechanism), and the nitrous oxide route to NO. Formation of NO2 from NO also occurs, as well as emission of carbon monoxide and unburnt hydrocarbons. When the fuel-oxidant proportion decreases towards leaner conditions, flame temperatures are lowered, resulting in the total NO being reduced and the thermal-NO contribution greatly diminished to the benefit of the remaining two mechanisms of NO formation. While knowledge of the elementary reactions and their chemical kinetics concerning methane and simple hydrocarbons combustion has existed for a number of years, its use for computer modeling is limited to simple flow dynamics configurations. Nevertheless, understanding of such combusting flows under a wide range of experimental conditions allows for analogies or speculations with more complex actual systems. Such understanding can be achieved by means of one dimensional laminar premixed flame modeling, with a full chemical mechanism which incorporates the three routes of NO formation. Complementary to this understanding is the modeling of the actual combustion system using a full description of the fluid dynamics coupled with a reduced chemical scheme, which is then compared against the first model. The objective of this investigation is to evaluate the relative importance of the three mechanisms of NO formation in lean premixed methane-air combustion with increasing pressure using the one dimensional plug flow package PREMIX, and to test the validity of a three dimensional model with a global chemical mechanism against the one dimensional model in the atmospheric pressure case. Methane is chosen because it is the only mechanism which is reasonably well known and is a good guide to the behavior of other hydrocarbons. The mixture ratio chosen is richer than that in lean gas turbines, but the combustion of this mixture with the low preheat gives realistic gas turbine final flame temperatures. Conditions of NO2 formation are also analyzed in the one dimensional model and results extrapolated to the case of gas turbines.

Valerie Dupont↗
DOE OSTI2023

Diverse electron carriers drive syntrophic interactions in an enriched anaerobic acetate-oxidizing consortium

Abstract In many anoxic environments, syntrophic acetate oxidation (SAO) is a key pathway mediating the conversion of acetate into methane through obligate cross-feeding interactions between SAO bacteria (SAOB) and methanogenic archaea. The SAO pathway is particularly important in engineered environments such as anaerobic digestion (AD) systems operating at thermophilic temperatures and/or with high ammonia. Despite the widespread importance of SAOB to the stability of the AD process, little is known about their in situ physiologies due to typically low biomass yields and resistance to isolation. Here, we performed a long-term (300-day) continuous enrichment of a thermophilic (55 °C) SAO community from a municipal AD system using acetate as the sole carbon source. Over 80% of the enriched bioreactor metagenome belonged to a three-member consortium, including an acetate-oxidizing bacterium affiliated with DTU068 encoding for carbon dioxide, hydrogen, and formate production, along with two methanogenic archaea affiliated with Methanothermobacter_A. Stable isotope probing was coupled with metaproteogenomics to quantify carbon flux into each community member during acetate conversion and inform metabolic reconstruction and genome-scale modeling. This effort revealed that the two Methanothermobacter_A species differed in their preferred electron donors, with one possessing the ability to grow on formate and the other only consuming hydrogen. A thermodynamic analysis suggested that the presence of the formate-consuming methanogen broadened the environmental conditions where ATP production from SAO was favorable. Collectively, these results highlight how flexibility in electron partitioning during SAO likely governs community structure and fitness through thermodynamic-driven mutualism, shedding valuable insights into the metabolic underpinnings of this key functional group within methanogenic ecosystems.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2015

Investigation of Benthic Foraminiferal Non-Traditional Stable Isotopes to Reconstruct Methane Fluxes in Sedimentary Environments

Methane (CH4) is an important greenhouse gas, with a global warming potential much higher than carbon dioxide (CO2) on a short time scale. Even if the residence time of CH4 in the atmosphere is relatively short (tens of years), one of the products of CH4 oxidation is CO2, a greenhouse gas with a much longer residence time in the atmosphere (tens to hundreds of years). CH4 has been proposed as one of the trigger mechanisms for rapid global climate change today and in the geological past. With regards to the geological past, numerous studies proposed the benthic foraminiferal carbon isotope ratio (Delta13C) as a tool to reconstruct the impact of marine CH4 on rapid climate changes; however, the investigation of modern benthic foraminiferal Delta13C have produced inconclusive results. CH4 has a distinctive hydrogen isotope (Delta(D)) and Delta13C signature compared to seawater, and sulfate reduction, often coupled to CH4 anaerobic oxidation in sediments, changes the sulfur isotope signature (Delta34S) of the remaining sulfate in porewater. Therefore, we hypothesize that the Delta(D) and Delta34S signature of infaunal benthic foraminiferal species can provide a complementary approach to Delta13C to study CH4 dynamics in sedimentary environments. Here, we present the preliminary results obtained analyzing Uvigerina peregrina Delta(D) and Delta34S from three different locations at Hydrate Ridge, offshore Oregon. Unfortunately, the lack of chemical data related to the moment of foraminiferal calcification makes difficult to build a robust relationship among the U. peregrina stable isotopes and the CH4 fluxes at the sampling sites. However, our results look very promising, as each site is characterized by a different Delta(D) and Delta34S signature. We emphasize that this study represents the first step in the development of new proxies (Delta(D)) and Delta34S), which may complement the more traditional benthic foraminiferal Delta13C values, to reconstruct marine CH4 fluxes in the geological past.

Borrelli, C.↗
DOE OSTI2024

Fluidized-Bed Gasification of Coal-Biomass-Plastics for Hydrogen Production

Coal is one of the most abundant fossil energy resources in the United States and in the world. The recoverable reserves in the United States are estimated to be about 252 billion tons – more than 350 years of supply at current rates of usage. However, the share of coal in total primary energy consumption in the US has been declining over the years. The decline of coal is mainly attributed to cheap natural gas and precipitous declines in the cost of electricity production from renewable technologies such as wind and solar. Coal can potentially be used if it is coupled with carbon-neutral feedstock such as biomass-agricultural residues, forest biomass, and forest residues. Co-gasification of coal and biomass can become a negative carbon emission technology if the carbon dioxide (CO 2 ) is captured and sequestered. Although the biomass gasification process has a lot of similarities to coal gasification, the large-scale adaptation of power production sourced from biomass has not come to fruition. The main reason is that the power production from biomass is still expensive when compared with natural gas or coal power technologies. To address the feedstock cost, one approach is to use low-cost feedstocks, such as municipal solid wastes (MSW) or plastics, for gasification. Gasification involves the partial oxidation of coal and/or biomass feedstocks to produce a combustible fuel called synthesis gas (syngas) which is composed of carbon monoxide (CO), hydrogen (H 2 ), CO 2 , methane (CH 4 ), nitrogen (N 2 ), water (H 2 O), and other compounds that might be considered as contaminants. Raw syngas from gasification must go through multiple steps to produce high-purity hydrogen. The specific steps depend upon the quality (gas composition, contaminants, and their concentration) and condition (pressure and temperature) of syngas. The long-term goal of the project was to utilize coal and plastics together with biomass to produce energy and fuels using a gasification platform while reducing greenhouse gas emissions. The main objective of this research was to examine gasification performance in a laboratory-scale fluidized-bed gasifier for hydrogen production. The specific objectives of the research were to: (i) study coal-plastic-biomass mixture flowability for consistent feeding in the gasifier; (ii) understand the gasification behavior of the mixture in steam and oxygen environments; (iii) perform thermal property characterization of ash and slag from the mixture feedstock and refractory-ash interface of the mixture under gasification conditions; and (iv) develop process models to determine the technology needed for syngas cleanup and contaminants. The study found that there was no apparent segregation when biomass, coal, and waste plastics were mixed together during feeding. Although there were differences in hydrogen production when individual feedstock were fed, the hydrogen concentration remained almost constant with various blends. Therefore, blending waste plastics with biomass and coal, which are all abundant, is a better approach for energy production. Results of the techno-economic analysis suggested that integration of advanced gasification (GTI’s R-GAS™) and syngas cleanup and conditioning technologies (RTI’s WDP and AFWGS) for clean hydrogen production resulted in substantial benefits, including significant capital cost and operating cost reductions. Advanced technologies resulted in 16% reduction in the hydrogen production cost (COH) from 2.94 $\$$/kg to 2.47 $\$$/g, with further scope for optimization and cost reduction. These advanced technologies also result in lower emissions, and improved energy efficiency.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS1991

Biospheric-atmospheric coupling on the early Earth

Theoretical calculations performed with a one-dimensional photochemical model have been performed to assess the biospheric-atmospheric transfer of gases. Ozone reached levels to shield the Earth from biologically lethal solar ultraviolet radiation (220-300 nm) when atmospheric oxygen reached about 1/10 of its present atmospheric level. In the present atmosphere, about 90 percent of atmospheric nitrous oxide is destroyed via solar photolysis in the stratosphere with about 10 percent destroyed via reaction with excited oxygen atoms. The reaction between nitrous oxide and excited oxygen atoms leads to the production of nitric oxide in the stratosphere, which is responsible for about 70 percent of the global destruction of oxygen in the stratosphere. In the oxygen/ozone deficient atmosphere, solar photolysis destroyed about 100 percent of the atmospheric nitrous oxide, relegating the production of nitric oxide via reaction with excited oxygen to zero. Our laboratory and field measurements indicate that atmospheric oxygen promotes the biogenic production of N2O and NO via denitrification and the biogenic production of methane by methanogenesis.

Levine, J. S.↗
NASA NTRS2001

Chemistry-Climate Interactions in the GISS GCM: Tropospheric Chemistry Model Description and Evaluation - Part 1

A tropospheric chemistry module has been developed for use within the Goddard Institute for Space Studies (GISS) general circulation model (GCM) to study interactions between chemistry and climate change. The model uses a simplified chemistry scheme based on CO-NOx-CH4 chemistry, and also includes a parameterization for emissions of isoprene, the most important non-methane hydrocarbon. The model reproduces present day annual cycles and mean distributions of key trace gases fairly well, based on extensive comparisons with available observations. Examining the simulated change between present day and pre-industrial conditions, we find that the model has a similar response to that seen in other simulations. It shows a 45% increase in the global tropospheric ozone burden, within the 25% - 57% range seen in other studies. Annual average zonal mean ozone increases by more than 125% at Northern Hemisphere middle latitudes near the surface. Comparison of model runs that allow the calculated ozone to interact with the GCM's radiation and meteorology with those that do not shows only minor differences for ozone. The common usage of ozone fields that are not calculated interactively seems to be adequate to simulate both the present day and the pre-industrial ozone distributions. However, use of coupled chemistry does alter the change in tropospheric oxidation capacity, enlarging the overall decrease in OH concentrations from the pre-industrial to the present by about 10% (-5.3% global annual average in uncoupled mode, -5.9% in coupled mode). This indicates that there may be systematic biases in the simulation of the pre-industrial to present day decrease in the oxidation capacity of the troposphere (though a 10% difference is well within the total uncertainty). Global annual average radiative forcing from pre-industrial to present day ozone change is 0.32 W/sq m. The forcing seems to be increased by about 10% when the chemistry is coupled to the GCM. Forcing values greater than 0.8 W/sq m are seen over large areas of the United States, Southern Europe, North Africa, the Middle East, Central Asia, and the Arctic. Radiative forcing is greater than 1.5 W/sq m over parts of these areas during Northern summer Though there are local differences, the radiative forcing is overall in good agreement with the results of other modeling studies in both its magnitude and spatial distribution, demonstrating that the simplified chemistry is adequate for climate studies.

Shindell, Drew T.↗
DOE OSTI2023

Electrochemical Reduction of Flue Gas Carbon Dioxide to Commercially Viable C2-C4 Products (Final Report)

This is the final scientific/technical report for a DOE project focused on the electrochemical conversion of CO 2 in non-aqueous solvents to novel products. Electrochemical reduction of CO 2 provides an attractive route to produce valuable fuels and chemicals that can simultaneously lower greenhouse gas emissions when powered by renewable electricity. While recent technological advances have shown the feasibility of industrial CO 2 electroreduction, many challenges remain to improve this technology and expand the list of economically viable products. The vast majority of electrochemical CO 2 reduction research has been conducted in aqueous media under neutral to alkaline conditions, leading to commonly reported products including carbon monoxide, formic acid, methane, methanol, ethylene, acetic acid, and ethanol. In comparison, non-aqueous media for CO 2 reduction has been underexplored but represents a possible avenue to yield new products and improved operating conditions. The aim of the project was to convert waste CO 2 in the form of flue gas to a multicarbon C2 - C4 chemical product in a reactor designed to achieve economically competitive values of current density and selectivity. The project strived to advance the technology readiness of an electrochemical CO 2 reduction process in alcohol solvents from the proof-of-concept stage to a device capable of meeting performance metrics for commercial viability. In the initial plan, the University of Louisville researchers were to focus on investigating the electrochemical process and improving the faradaic efficiency for novel C2 – C4 species, while also working on a parallel effort to build a practical electrolysis reactor to markedly increase the CO 2 reduction current density. The reactor development effort also aimed to engineer a dual-electrolyte feed strategy with non-aqueous catholyte and aqueous anolyte to promote water oxidation as the coupling anodic half-reaction to enable a sustainable and economical overall process. At the outset, the University of North Dakota was to investigate the feasibility of operating directly from coal-derived flue gas without separate capture and purification. The research team sought to determine impurity effects and test mitigation strategies, as well as engineer the gaseous feed system for high reactor tolerance to lower CO 2 concentration. In the last half year of the project, the focus was planned to shift to integrating the advances in the catalysis, electrochemical conditions, reactor design, and flue gas compatibility into a fully functional device and improve it for maximum current density and faradaic efficiency for C2 – C4 species. Knowledge of the full system components, constraints, and maximum performance was then to be used as the basis for a thorough technoeconomic analysis (TEA) and life cycle analysis (LCA) at the end of the project.

01 COAL, LIGNITE, AND PEAT↗
NASA NTRS1996

Chemical Characteristics of Continental Outflow Over the Tropical South Atlantic Ocean from Brazil and Africa

The chemical characteristics of air parcels over the tropical South Atlantic during September - October 1992 are summarized by analysis of aged marine and continental outflow classifications. Positive correlations between CO and CH3CL and minimal enhancements of C2CL40, and various ChloroFluoroCarbon (CFC) species in air parcels recently advected over the South Atlantic basin strongly suggest an impact on tropospheric chemistry from biomass burning on adjacent continental areas of Brazil and Africa. Comparison of the composition of aged Pacific air with aged marine air over the South Atlantic basin from 0.3 to 12.5 km altitude indicates potential accumulation of long-lived species during the local dry season. This may amount to enhancements of up to two-fold for C2H6, 30% for CO, and 10% for CH3Cl. Nitric oxide and NO(x) were significantly enhanced (up to approx. 1 part per billion by volume (ppbv)) above 10 km altitude and poorly correlated with CO and CH3Cl. In addition, median mixing ratios of NO and NO(x) were essentially identical in aged marine and continental outflow air masses. It appears that in addition to biomass burning, lightning or recycled reactive nitrogen may be an important source of NO(x) to the upper troposphere. Methane exhibited a monotonic increase with altitude from approx. 1690 to 1720 ppbv in both aged marine and continental outflow air masses. The largest mixing ratios in the upper troposphere were often anticorrelated with CO, CH3Cl, and CO2, suggesting CH, contributions from natural sources. We also argue, based on CH4/CO ratios and relationships with various hydrocarbon and CFC species, that inputs from biomass burning and the northern hemisphere are unlikely to be the dominant sources of CO, CH4 and C2H6 in aged marine air. Emissions from urban areas would seem to be necessary to account for the distribution of at least CH4 and C2H6. Over the African and South American continents an efficient mechanism of convective vertical transport coupled with large-scale circulations conveys biomass burning, urban, and natural emissions to the upper troposphere over the South Atlantic basin. Slow subsidence over the eastern South Atlantic basin may play an important role in establishing and maintaining the rather uniform vertical distribution of long-lived species over this region. The common occurrence of values greater than 1 for the ratio CH3OOH/H2O2 in the upper troposphere suggests that precipitation scavenging effectively removed highly water soluble gases (H2O2, HNO3, HCOOH, and CH3COOH) and aerosols during vertical convective transport over the continents. However, horizontal injection of biomass burning products over the South Atlantic, particularly water soluble species and aerosol particles, was frequent below 6 km altitude.

Talbot, R. W.↗
NASA NTRS2015

Microlith-Based Catalytic Reactor for Air Quality and Trace Contaminant Control Applications

Traditionally, gaseous compounds such as methane, carbon monoxide, and trace contaminants have posed challenges for maintaining clean air in enclosed spaces such as crewed spacecraft cabins as they are hazardous to humans and are often difficult to remove by conventional adsorption technology. Catalytic oxidizers have provided a reliable and robust means of disposing of even trace levels of these compounds by converting them into carbon dioxide and water. Precision Combustion, Inc. (PCI) and NASA - Marshall (MSFC) have been developing, characterizing, and optimizing high temperature catalytic oxidizers (HTCO) based on PCI's patented Microlith® technology to meet the requirements of future extended human spaceflight explorations. Current efforts have focused on integrating the HTCO unit with a compact, simple recuperative heat exchanger to reduce the overall system size and weight while also reducing its energy requirements. Previous efforts relied on external heat exchangers to recover the waste heat and recycle it to the oxidizer to minimize the system's power requirements; however, these units contribute weight and volume burdens to the overall system. They also result in excess heat loss due to the separation of the HTCO and the heat recuperator, resulting in lower overall efficiency. Improvements in the recuperative efficiency and close coupling of HTCO and heat recuperator lead to reductions in system energy requirements and startup time. Results from testing HTCO units integrated with heat recuperators at a variety of scales for cabin air quality control and heat melt compactor applications are reported and their benefits over previous iterations of the HTCO and heat recuperator assembly are quantified in this paper.

Vilekar, Saurabh↗
DOE OSTI2024

Experimental Combustion and Flame Characterization of a Chemical Looping-Based Oxidative Dehydrogenation Byproduct Fuel Mixture Containing High CO2 Dilution

Abstract This study investigates the combustion performance of a CO2-rich fuel mixture containing ethane and methane as active species using a constant volume combustion chamber. This fuel is obtained as a byproduct of a chemical looping-based oxidative dehydrogenation (Cl-ODH) process ethylene production. The byproduct gas mixture has 40.79% CO2, 39.49% ethane, and 4.88% methane by weight with other minor compounds. Using this fuel for energy extraction would improve the process efficiency of the ethane to ethylene conversion. After initial combustion modeling, the gas fuel mixture was reduced to just the major species: CO2, ethane, and methane. The mixture was then tested for flammability limits and combustion performance under spark-ignition conditions. Effects of ambient conditions like temperatures between 300 and 400 K with initial pressures from 1 to 10 bar were tested. The effects of stoichiometry were tested to understand flame velocities and heat release. The fuel mixture showed an overall reduced flame velocity compared to gasoline. Instability in combustion was believed to be caused by the dissociation of ethane under elevated conditions. At higher pressures, the flame produces lower cumulative heat release. Simulations were also performed using a model tuned to replicate the operations of the combustion chamber used in the experiments. Heat release and unburnt fuel mass data were calculated to identify the discrepancies in the combustion completeness at elevated pressures. The effects of CO2 quenching the flame coupled with the increased dissociation of the fuel species can lead to up to more than 75% of the fuel mixture being unburnt. Data from this study were used to modify a small-scale spark-ignition engine to use this fuel and produce usable energy.

Energy & Fuels↗
DOE OSTI2020

Coupled methane and NO x conversion on Pt + Pd/Al 2 O 3 monolith: Conversion enhancement through feed modulation and Mn 0.5 Fe 2.5 O 4 spinel addition

The performance of a dual-layer Pt-Pd/Al 2 O 3 washcoated monolith promoted by an Al 2 O 3 -supported Mn 0.5 Fe 2.5 O 4 spinel base layer was evaluated with the objective to develop a catalyst with a lower loading of Platinum group metal (PGM) for stoichiometric natural gas vehicle (NGV) emission control. Flow reactor results show that a combination of a lean/rich modulated feed and spinel addition gives enhanced methane and NO conversions compared to a steady-state feed having the same overall composition. Washcoated catalysts – PGM-only, spinel-only, PGM + spinel – were compared over a wide range of operating conditions. The results show a decrease in the methane conversion light-off temperature of up to 85 °C for an application-relevant feed (CH 4 + NO + H 2 + CO + O 2 + H 2 O + CO 2 ) while a moderate 40 °C decrease was observed for a simple feed (CH 4 + O 2 + H 2 O + CO 2 ). In the absence of spinel the modulation enhancement is negatively impacted at high methane conversion (> 80 %). The data show that the O 2 storage and release property of the spinel is needed to fully exploit the modulation enhancement. The mechanism responsible for the enhancement is linked to suppression of O 2 inhibition on the methane oxidation rate near the stoichiometric neutral point (λ = 1). Sufficiently fast cycling achieves a balance between a metallic and oxidic precious metal crystallites favorable for methane activation. The addition of spinel moves this balance closer to the λ = 1 feed, enabling a high oxidation efficiency with lower byproduct NH 3 selectivity. Enhancement in the NO conversion follows the methane conversion due to an easier NO reduction under the slightly rich of stoichiometric feed. Comparison of the PGM + spinel catalysts to PGM-only catalysts shows that the addition of spinel in combination with modulation can achieve the same activity with a lower PGM loading.

03 NATURAL GAS↗