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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 307 records · Page 17

An Intensified Electro-Catalytic Process for Production of Formic Acid from Power Plant CO 2 Emissions (Final Technical Report)

The goal of this project was to develop and test a novel electro-catalytic method for the production of high-value formic acid from coal-derived CO 2 as a strategy to offset the cost of CO 2 capture. Formic acid is currently produced from the conversion of higher-order carbon products such as methane and/or methanol. This electro-catalytic CO 2 reduction process utilizes a highly selective catalyst in a flow-through reactor design to maximize the formic acid production rate. The specific objectives of this proposed study were to; 1) produce and screen highly selective engineered CO 2 reducing catalysts capable of exclusively producing formic acid; 2) immobilize the catalyst within a flow process to continually produce formic acid and increase catalyst lifetime; and 3) assess the stability of the electrocatalyst during long-term operation. The project involved the development and testing of an engineered catalyst to selectively reduce CO 2 directly and exclusively to formic acid. After the best-performing catalyst was selected, it was immobilized and tested inside a flow-through reactor at UK CAER using realistic conditions expected from CO 2 produced during coal combustion and separated by a CO 2 capture plant.

01 COAL, LIGNITE, AND PEAT↗

Signatures of Chemical Evolution in Protostellar Nebulae

A decade ago observers began to take serious notice of the presence of crystalline silicate grains in the dust flowing away from some comets. While crystallinity had been seen in such objects previously, starting with the recognitions by Campins and Ryan (1990) that the 10 micron feature of Comet Halley resembled that of the mineral forsterite, most such observations were either ignored or dismissed as no path to explain such crystalline grains was available in the literature. When it was first suggested that an outward flow must be present to carry annealed silicate grains from the innermost regions of the Solar Nebula out to the regions where comets could form (Nuth, 1999; 2001) this suggestion was also dismissed because no such transport mechanism was known at the time. Since then not only have new models of nebular dynamics demonstrated the reality of long distance outward transport (Ciesla, 2007; 2008; 2009) but examination of older models (Boss, 2004) showed that such transport had been present but had gone unrecognized for many years. The most unassailable evidence for outward nebular transport came with the return of the Stardust samples from Comet Wild2, a Kuiper-belt comet that contained micron-scale grains of high temperature minerals resembling the Calcium-Aluminum Inclusions found in primitive meteorites (Zolensky et aI., 2006) that formed at T > 1400K. Now that outward transport in protostellar nebulae has been firmly established, a re-examination of its consequences for nebular gas is in order that takes into account both the factors that regulate both the outward flow as well as those that likely control the chemical composition of the gas. Laboratory studies of surface catalyzed reactions suggest that a trend toward more highly reduced carbon and nitrogen compounds in the gas phase should be correlated with a general increase in the crystallinity of the dust (Nuth et aI., 2000), but is such a trend actually observable? Unlike the Fischer-Tropsch or the Haber-Bosch reactions used in industry, the surface catalyzed reactions seen in our laboratory do not produce a simple product stream of methane or ammonia, respectively. Instead, such reactions produce a wide range of both aliphatic and aromatic hydrocarbons, as well as reduced nitrogen compounds such as ammonia, amines, amides and imides, as gas phase products together with a heavy, macromolecular, kerogen-like surface coating that remains on the grains. While CO and N2 will certainly be depleted by conversion into more complex and less volatile species via reaction on grain surfaces, it may be very difficult to monitor such changes from outside the system.

Nuth, Joseph A., III↗

Scale and Regionality of Nonelectric Markets for U.S. Nuclear Light Water Reactors

This study assesses existing and potential industries that could conceivably be directly coupled to existing nuclear reactors. The goal is to identify the scale, location, and accessibility of the candidate industrial-product markets, as well as process feedstocks that are available near the plants to establish new industries. For example, CO 2 as a feedstock can be combined with H 2 to produce formic acid (FA), transportation fuels, and lubricants. These new plants can be entirely supported with the heat and electricity provided by a nearby NPP. The potential demand for nonelectric industrial products was assessed by documenting current and possible growth of nonelectricity product markets considered. This assessment used DOE- and industry-supported tools, data, and projections to capture regional industrial market opportunities. Electricity-capacity markets that reward large and reliable generators, such as NPPs, were considered because the electricity market will likely continue to be an important revenue source to NPPs. The key is to balance the needs of energy customers so as to optimize revenue for the affiliated energy customers or partners. In most cases, flexible plant energy delivery and power generation for the grid will require either energy storage or a stock of intermediate products to sustain the industrial customers when the NPP dispatches electricity to the grid. A diverse mix of temperate regions with operating NPPs around the U.S.—representing a variety of operating markets, local generation mix, and seasonal climates—were chosen for this market study. Both current and future market opportunities for candidate industrial-product markets surrounding these NPPs were studied. Figure 2 illustrates the regions chosen for this study. The success of developing nonelectric industrial-product markets as alternative revenue-generating sources for LWRs depends, not only on demand from growing existing markets, such as petroleum refining and NH 3 production, but also on the development of new markets such as light-duty (LD) and heavy-duty (HD) hydrogen FCEVs, synfuels, chemical production, biofuels, metal refining, injection of hydrogen into NG pipelines for gas power-generating units, FA, polymers, and close-coupled industrial heat applications, all of which can significantly increase demand relative to current levels while decarbonizing energy sectors. This study also presents a sample analysis of the economics of hydrogen production in an area of Minnesota, considering the capital and operating costs of a hydrogen plant as well as the local market demand for hydrogen. It includes some assumptions on electricity-grid pricing, showing how hydrogen could be integrated with an NPP and be competitive with the incumbent hydrogen-production process, steam methane reforming (SMR). The objectives of this study include: Provide U.S. NPP operators a robust sampling of the market demand location, scale, and accessibility (including storage and transportation) of the wide variety of industrial-product choices that can be produced using nuclear thermal energy and electricity proximate to a subset of U.S. NPPs to inform the industry of the potential opportunity; show examples and trade-off analyses of how U.S. LWR operators can access these markets, including storage and transportation of industrial products to their intended markets; and present a general analysis example for one industrial product (hydrogen) in one region (Minnesota area), including production, storage, and transportation, to show how nuclear-hybrid integrated energy systems (IESs) could access local markets and improve the profitability of an NPP.

03 NATURAL GAS↗

Assessment of advanced coal gasification processes

A technical assessment of the following advanced coal gasification processes is presented: high throughput gasification (HTG) process; single stage high mass flux (HMF) processes; (CS/R) hydrogasification process; and the catalytic coal gasification (CCG) process. Each process is evaluated for its potential to produce synthetic natural gas from a bituminous coal. Key similarities, differences, strengths, weaknesses, and potential improvements to each process are identified. The HTG and the HMF gasifiers share similarities with respect to: short residence time (SRT), high throughput rate, slagging, and syngas as the initial raw product gas. The CS/R hydrogasifier is also SRT, but is nonslagging and produces a raw gas high in methane content. The CCG gasifier is a long residence time, catalytic, fluidbed reactor producing all of the raw product methane in the gasifier.

Mccarthy, J.↗

Assessment of Advanced Coal Gasification Processes

This report represents a technical assessment of the following advanced coal gasification processes: AVCO High Throughput Gasification (HTG) Process; Bell Single-Stage High Mass Flux (HMF) Process; Cities Service/Rockwell (CS/R) Hydrogasification Process; Exxon Catalytic Coal Gasification (CCG) Process. Each process is evaluated for its potential to produce SNG from a bituminous coal. In addition to identifying the new technology these processes represent, key similarities/differences, strengths/weaknesses, and potential improvements to each process are identified. The AVCO HTG and the Bell HMF gasifiers share similarities with respect to: short residence time (SRT), high throughput rate, slagging and syngas as the initial raw product gas. The CS/R Hydrogasifier is also SRT but is non-slagging and produces a raw gas high in methane content. The Exxon CCG gasifier is a long residence time, catalytic, fluidbed reactor producing all of the raw product methane in the gasifier. The report makes the following assessments: 1) while each process has significant potential as coal gasifiers, the CS/R and Exxon processes are better suited for SNG production; 2) the Exxon process is the closest to a commercial level for near-term SNG production; and 3) the SRT processes require significant development including scale-up and turndown demonstration, char processing and/or utilization demonstration, and reactor control and safety features development.

coal gasification↗

Where old meets new: An ecosystem study of methanogenesis in a reflooded agricultural peatland

Reflooding formerly drained peatlands has been proposed as a means to reduce losses of organic matter and sequester soil carbon for climate change mitigation, but a renewal of high methane emissions has been reported for these ecosystems, offsetting mitigation potential. Our ability to interpret observed methane fluxes in reflooded peatlands and make predictions about future flux trends is limited due to a lack of detailed studies of methanogenic processes. In this study we investigate methanogenesis in a reflooded agricultural peatland in the Sacramento Delta, California. Furthermore, we use the stable-and radio-carbon isotopic signatures of wetland sediment methane, ecosystem-scale eddy covariance flux observations, and laboratory incubation experiments, to identify which carbon sources and methanogenic production pathways fuel methanogenesis and how these processes are affected by vegetation and seasonality. We found that the old peat contribution to annual methane emissions was large (~30%) compared to intact wetlands, indicating a biogeochemical legacy of drainage. However, fresh carbon and the acetoclastic pathway still accounted for the majority of methanogenesis throughout the year. Although temperature sensitivities for bulk peat methanogenesis were similar between open-water (Q 10 = 2.1) and vegetated (Q 10 = 2.3) soils, methane production from both fresh and old carbon sources showed pronounced seasonality in vegetated zones. We conclude that high methane emissions in restored wetlands constitute a biogeochemical trade-off with contemporary carbon uptake, given that methane efflux is fueled primarily by fresh carbon inputs.

54 ENVIRONMENTAL SCIENCES↗

Polymeric Membranes for H2S and CO2 Removal from Natural Gas for Hydrogen Production: A Review

Natural gas, an important source of hydrogen, is expected to be crucial in the transition to a hydrogen-based economy. The landscape of the gas processing industry is set to change in the near future with the development of highly acidic sour gas wells. Natural gas purification constitutes a major share of the gas separation membrane market, and the shift to low-quality sour gas wells has been mirrored in the trends of membrane material research. Purification also constitutes the major portion of the cost of natural gas, posing implications for the cost of hydrogen production. This review provides an update on the current state of research regarding polymeric membranes for H2S removal, along with CO2 separation, from natural gas that is used for hydrogen production via steam methane reforming. The challenges of adapting polymeric membranes to ternary H2S/CO2/CH4 separations are discussed in detail. Key polymeric materials are highlighted, and the prospects for their application in H2S removal from natural gas are evaluated. Finally, the growing interest in H2 production from H2S is discussed. Advances in the membrane industry and the emergence of new membrane materials may significantly improve the commercial viability of such processes.

Rao, Shraavya↗

Test evaluation of potential heat shield contamination of an Outer Planet Probe's atmospheric sampling system

An Outer Planets Probe which retains the charred heatshield during atmospheric descent must deploy a sampling tube through the heatshield to extract atmospheric samples for analysis. Once the sampling tube is deployed, the atmospheric samples ingested must be free of contaminant gases generated by the heatshield. Outgassing products such as methane and water vapor are present in planetary atmospheres and hence, ingestion of such species would result in gas analyzer measurement uncertainties. This paper evaluates the potential for, and design impact of, the extracted atmospheric samples being contaminated by heatshield outgassing products. Flight trajectory data for Jupiter, Saturn and Uranus entries are analyzed to define the conditions resulting in the greatest potential for outgassing products being ingested into the probe's sampling system. An experimental program is defined and described which simulates the key flow field features for a planetary flight in a ground-based test facility. The primary parameters varied in the test include: sampling tube length, injectant mass flow rate and angle of attack. Measured contaminant levels predict the critical sampling tube length for contamination avoidance. Thus, the study demonstrates the compatibility of a retained heatshield concept and high quality atmospheric trace species measurements.

Kessler, W. C.↗

A multiscale packed-bed reactor model for sustainable ethylene production via chemical looping oxidative coupling of methane

The rising global warming concerns and shale gas discovery have prompted research in the direction of greenhouse gas (GHG), such as methane, reduction and conversion. Oxidative coupling of methane (OCM) offers a pathway to low carbon-intense valorization of methane while producing ethylene, a chemical regarded as central to the petrochemical industry. Even after decades of OCM discovery, researchers keep understanding the process and underlying chemical reactions in a pursuit to achieve industrial viability for OCM. Here, in general, OCM suffers from low C 2 selectivity, yield and reactor temperature runaways due to highly exothermic nature of its reactions. Computational Fluid Dynamics (CFD) tools help analyze spatial gradients within the reactor to deeply understand the diffusion of species, mass and heat transfer phenomena. Furthermore, challenges associated with scaling up such as hot spot formation and parametric sensitivity can be addressed without having to expend on costly experiments. The current paper presents a multiscale packed-bed reactor CFD model coupled with a chemical kinetic model for the chemical looping OCM. The CFD model includes two scales i.e., macroscale for catalyst bed and microscale for individual pellets. Moreover, a chemical kinetic model based on 10 gas-phase reactions is integrated with the CFD model. An additional surface reaction for the formation of gas-phase oxygen from catalyst surface is added to account for the absence of feed oxygen. The model is calibrated against experimental results. The calibrated model captures trends in CH 4 conversion, C 2 selectivity and C 2 yield within a ± 4.35 % range across a temperature range of 700-900 °C. Moreover, model fidelity is evaluated by varying key computational parameters such as mesh resolution and time step size. The model is also verified by varying the inlet methane concentration and the gas hourly space velocity (GHSV) and comparing the results with literature. A sensitivity analysis and scale-up of the current model is undergoing.

Chemical looping↗

Production of nitrous oxide and consumption of methane by forest soils

Soils in an Amazonian rainforest are observed to release N2O at a rate larger than the global mean by about a factor of 20. Emissions from a New England hardwood forest are approximately 30 times smaller then Brazilian values. Atmospheric methane is consumed by soils in both systems. Tropical forests would provide a major source of atmospheric N2O if the Brazilian results are representative.

Keller, M.↗

Efficient CO2 and Natural Gas Refinery for Ethylene Production - Catalyst Development for Oxidative Coupling of Methane (OCM)

We designed a new electro-catalyst for oxidative coupling of methane (OCM) reaction, the structure of the Sc doped La0.3Sr0.7TiO3-d (LaSrTi) Sc doping to LaSrTi leading to lattice expansion and more distorted lattice, Investigated the effect of doping on the oxygen vacancy formation energy DFT calculations shows that Sc doping facilitate oxygen vacancy formation. Quantifying the surface basicity of the sample before and after Sc doping Sc doped sample exhibits high surface basicity.

catalysis↗

2D imaging of absolute methyl concentrations in nanosecond pulsed plasma by photo-fragmentation laser-induced fluorescence

The methyl radical plays a central role in plasma-assisted hydrocarbon chemistry but is challenging to detect due to its high reactivity and strongly pre-dissociative electronically excited states. In this work, we report the development of a photo-fragmentation laser-induced fluorescence (PF-LIF) diagnostic for quantitative 2D imaging of methyl profiles in a plasma. This technique provides temporally and spatially resolved measurements of local methyl distributions, including in near-surface regions that are important for plasma-surface interactions such as plasma-assisted catalysis. The technique relies on photo-dissociation of methyl by the fifth harmonic of a Nd:YAG laser at 212.8 nm to produce CH fragments. These photofragments are then detected with LIF imaging by exciting a transition in the B-X(0, 0) band of CH with a second laser at 390 nm. Fluorescence from the overlapping A-X(0, 0), A-X(1, 1), and B-X(0, 1) bands of CH is detected near 430 nm with the A-state populated by collisional B-A electronic energy transfer. This non-resonant detection scheme enables interrogation close to a surface. The PF-LIF diagnostic is calibrated by producing a known amount of methyl through photo-dissociation of acetone vapor in a calibration gas mixture. We demonstrate PF-LIF imaging of methyl production in methane-containing nanosecond pulsed plasmas impinging on dielectric surfaces. Absolute calibration of the diagnostic is demonstrated in a diffuse, plane-to-plane discharge. Measured profiles show a relatively uniform distribution of up to 30 ppm of methyl. Relative methyl measurements in a filamentary plane-to-plane discharge and a plasma jet reveal highly localized intense production of methyl. The utility of the PF-LIF technique is further demonstrated by combining methyl measurements with formaldehyde LIF imaging to capture spatiotemporal correlations between methyl and formaldehyde, which is an important intermediate species in plasma-assisted oxidative coupling of methane.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Substantial and overlooked greenhouse gas emissions from deep Arctic lake sediment

Thermokarst lakes cause abrupt and sustained permafrost degradation and have the potential to release large quantities of ancient carbon to the atmosphere. Despite concerns about how lakes will affect the permafrost carbon feedback, the magnitude of carbon dioxide and methane emissions from deep permafrost soils remains poorly understood. Here we incubated a very deep sediment core (20 m) to constrain the potential productivity of thawed Yedoma and underlying Quaternary sand and gravel deposits. Through radiocarbon dating, sediment incubations and sediment facies classifications, we show that extensive permafrost thaw can occur beneath lakes on timescales of decades to centuries. Although it has been assumed that shallow, aerobic carbon dioxide production will dominate the climate impact of permafrost thaw, we found that anaerobic carbon dioxide and methane production from deep sediments was commensurate with aerobic production on a per gram carbon basis, and had double the global warming potential at warmer temperatures. Carbon release from deep Arctic sediments may thus have a more substantial impact on a changing climate than currently anticipated. These environments are presently overlooked in estimates of the permafrost carbon feedback.

54 ENVIRONMENTAL SCIENCES↗

Overview of Diverse Methyl/Alkyl-Coenzyme M Reductases and Considerations for Their Potential Heterologous Expression

Methyl-coenzyme M reductase (MCR) is an archaeal enzyme that catalyzes the final step of methanogenesis and the first step in the anaerobic oxidation of methane, the energy metabolisms of methanogens and anaerobic methanotrophs (ANME), respectively. Variants of MCR, known as alkyl-coenzyme M reductases, are involved in the anaerobic oxidation of short-chain alkanes including ethane, propane, and butane as well as the catabolism of long-chain alkanes from oil reservoirs. MCR is a dimer of heterotrimers (encoded by mcrABG) and requires the nickel-containing tetrapyrrole prosthetic group known as coenzyme F430. MCR houses a series of unusual post-translational modifications within its active site whose identities vary depending on the organism and whose functions remain unclear. Methanogenic MCRs are encoded in a highly conserved mcrBDCGA gene cluster, which encodes two accessory proteins, McrD and McrC, that are believed to be involved in the assembly and activation of MCR, respectively. The requirement of a unique and complex coenzyme, various unusual post-translational modifications, and many remaining questions surrounding assembly and activation of MCR largely limit in vitro experiments to native enzymes with recombinant methods only recently appearing. Production of MCRs in a heterologous host is an important step toward developing optimized biocatalytic systems for methane production as well as for bioconversion of methane and other alkanes into value-added compounds. This review will first summarize MCR catalysis and structure, followed by a discussion of advances and challenges related to the production of diverse MCRs in a heterologous host.

59 BASIC BIOLOGICAL SCIENCES↗

Creating Accurate Methane Emission Inventories through Data-Driven Airborne Survey Strategies

Because natural gas emits less carbon than other fossil fuels, it holds promise as a green energy transition fuel. However, the overall carbon footprint of natural gas is significantly elevated by methane emissions that occur during its production and transmission (Cusworth et al. 2022). Methane “super-emitters,” while comprising only about 1% of sites, are responsible for the majority of oil- and gas-sourced methane emissions, making their detection and mitigation critical in reducing the climate impact of natural gas and in meeting national and global sustainability goals (Sherwin et al. 2024). Yet, despite advancements in detection, significant uncertainties remain regarding the size, frequency, and duration distributions of methane emissions (e.g., Frankenberg et al. 2016, Cusworth et al. 2022, Chen, Sherwin et al. 2022, Conrad et al. 2023, Johnson et al. 2023, Sherwin et al. 2024) underscoring the need for comprehensive emissions inventories segmented by basin across the US. Airborne surveys are well-suited for collecting data to build these comprehensive, basin-level inventories because they allow for extensive spatial coverage, and have the spatial resolution, and the sensitivity to pinpoint individual methane sources. As remote sensing technologies enable rapid basin-scale surveys, it is imperative to establish scientifically and statistically robust standards to generate reliable and actionable emissions inventories. Recent work has shown that differences in airborne sampling strategies, detection technologies, and analysis can lead to large differences between survey conclusions if not correctly accounted for (Chen et al. 2024). This elevates the importance of incorporating proper sampling and analysis techniques when designing a methane emissions monitoring campaign to produce accurate results and facilitate cross-study comparisons. In this paper, we describe a survey strategy designed using the latest conclusions from the literature to align results from different aerial surveys. We identify several sampling and analysis principles, including large sample sizes, balanced sampling across oil and gas production, careful survey area definition, and a unified protocol for analysis, to be vital to producing an unbiased estimate of basin-scale emissions. We present results from a Department of Energy-funded project that deployed this survey strategy in two understudied oil and gas- producing regions in the United States: the Haynesville Basin in Texas and Louisiana, and the Woodford Shale in the Anadarko Basin in Oklahoma.

03 NATURAL GAS↗

Development of Methane Emissions Model to Assess Fuel Recovery Potential at Gas Well Sites Using On Site Compression

The U.S. natural gas production and consumption has increased 85.5% since 2005 primarily due to the unconventional production methods of horizontal drilling and hydraulic fracturing. Natural gas used as a fuel has a lower greenhouse gas (GHG) footprint than coal and petroleum due to lower Carbon Dioxide (CO2) emissions when combusted. However, the “greener” benefit to natural gas may be negated by leaks in production and transmission systems. Methane (CH4), the primary hydrocarbon in natural gas, has an estimated Global Warming Potential (GWP) of 28-36 over 100 years, meaning it can absorb 28-36 more energy than CO2 which has a GWP of 1.0. Natural gas well sites are prone to methane emissions, or leaks and irregular gas releases, vented to atmosphere throughout production and transmission. The U.S. Department of Energy (DOE) and the National Energy Technology Laboratory (NETL) has recently granted West Virginia University (WVU) funding under agreement DE-FOA-0002005, to “Advance technologies to mitigate methane emissions and increase the efficiency of the natural gas transportation infrastructure”. As part of this funding WVU was tasked with identifying and quantifying sources of methane emissions at unconventional well sites, processing this data, and developing a system to recapture these emissions. A 0-D Simulink model was developed, utilizing standardized methodologies, data from previously conducted studies, as well as collected data from well sites in the Marcellus shale play region. The model was developed to predict emission rates from various components at natural gas well sites as well as the potential to utilize these emissions as fuel for the natural gas powered compressor engines on-site. This model was utilized to run high, medium, and low cases for four identified emission sources, engine size, pneumatic controller count, liquid level production which dictates tank emissions, and compressor packing vent emissions. Due to discrepancies in transient tank emission data, a high and low emission factor for tanks was used, resulting in two sets of 81 executed cases, and 162 unique cases of total site emissions and potential for fuel consumption. Each of the cases were run over 86,400 seconds at a 1 Hz, representative of a full 24 hour day of operation. The fuel consumption offset an average of 557% of fuel consumption on an energy density basis across all 81 cases with the high tank emission factor with a maximum offset of 2334%. The fuel consumption offset was an average of 82.9% for all 81 cases with the low tank emission factor with a maximum offset of 337%. This study highlights flaws in the use of publicly available methane number calculations to determine natural gas’s suitability as an engine fuel as well as the lack of public data for transient liquid storage tank emissions.

03 NATURAL GAS↗