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At least 325 records · Page 18

Insights into Controls of Mineralogy and Pore Structure on the Density of Methane Adsorption Phase in Shales under Supercritical Conditions

With gradually increasing enhancing population and industrialization, exploitation of shale gas is enhancing in the world to satisfy the growing demand for energy worldwide. To exploit shale gas efficiently, accurate assessment of shale gas in place (GIP) is necessary for determining production strategies. Unlike free and dissolved gas, adsorbed gas contributes to the shale GIP up to 85% due to the well-developed surface area and micropores. Measured excess adsorption of methane (up to over 95% of subsurface shale gas) is often corrected to absolute adsorption to obtain the actual amount of adsorption under supercritical (or geological) conditions. During the correction, adsorption phase density (APD) is critical. However, the APD of subsurface shale gas and the effects of shale properties (e.g., mineralogy and pore structure) on APD remain poorly understood. A series of high-pressure methane adsorption isotherms (HPMAI) on Caney Shales were collected and analyzed in conjunction with other United States and Chinese shales from the literature at 35–125 °C and up to 15 MPa. Here, a three-layer Ono–Kondo (OK3) model is utilized to derive the temperature- and pressure-dependent APD coupling low-pressure nitrogen adsorption isotherms (LPNAI) and HPMAI. X-ray diffraction and organic geochemistry are combined to reveal the mineralogy. Brunauer–Emmett–Teller, Barrett–Joyner–Halenda, and Horvath–Kawazoe analyses via LPNAI are used to investigate the pore structures. Results show that APD increases with organic matter (OM) proxied by total organic carbon and decreases with clay minerals and the sum of quartz and feldspar. OM dramatically contributes to the APD as multiple-layer adsorption exists, and the APD for OM could be 1.4–8.5 times that for clay minerals. Other inorganic minerals contribute less to APD. The properties and constitution of the surface area instead of the volume fraction contribute to the APD in shales. APD does not show an obvious correlation with micropore volume, likely related to the ratio of micropore volume to the total pore volume. Here, we provide a significant and comprehensive study of petrological factors that impact the APD of subsurface shale gas, which will improve the estimation of supercritical adsorption and shale GIP under reservoir conditions. Also, the findings in this work can provide applications for subsurface carbon dioxide adsorption and storage.

58 GEOSCIENCES↗

Development of prechamber enabled mixing-controlled combustion strategy for ultra-low methane emissions from lean burn natural gas engines

This numerical study explores the optimization of Prechamber Enabled Mixing-Controlled Combustion (PC-MCC) using natural gas in heavy-duty engines, aiming to enhance combustion efficiency to minimize methane slip and NOx emissions. The approach involves a prechamber ignition system, distinct from conventional spark ignition (SI) systems, to initiate combustion of direct injected natural gas. By leveraging the robust ignition characteristics of the prechamber, the PC-MCC method demonstrates significant potential in achieving efficient combustion akin to diesel engines but with lower greenhouse gas emissions. The research evaluates the effects of various geometric and operational parameters on the combustion process and emissions, including prechamber volume, nozzle diameter, direct injector (DI) geometry, and engine operating strategies. Computational Fluid Dynamics (CFD) simulations are utilized, focusing on a heavy-duty, single-cylinder engine modeled after the Caterpillar C9.3B engine. Key findings indicate that a prechamber volume of 3 cc, coupled with a nozzle diameter of 2.75 mm for two prechamber holes, strikes an optimal balance between combustion efficiency and emissions reduction. This configuration ensures robust combustion across a range of operating conditions while maintaining methane slip within targeted limits. Further investigation into DI geometry shows the significance of the injector umbrella angle and nozzle diameter in shaping the fuel-air mixing and combustion dynamics. An umbrella angle of 130° and a nozzle diameter of 300 microns are identified as optimal, promoting rapid and efficient combustion with minimized methane and NOx emissions. The study also investigates the impact of injection timing and pressure, highlighting their roles in controlling combustion timing and influencing emissions levels. Advanced injection timing is found to be crucial in achieving the desired low methane slip, whereas retarded injection timing assists to reduce NOx emissions while having a slight increase in methane emissions. Operating strategies incorporating various levels of Exhaust Gas Recirculation (EGR) are assessed for their effectiveness in further reducing emissions. The research demonstrates that a judicious combination of internal hot EGR and careful calibration of DI pressure and SOI timing can achieve significant reductions in NOx emissions while keeping methane slip under control. Specifically, an internal EGR level of 15%–25%, combined with DI pressures of 200–300 bar and injection timings at or after top dead center, is recommended. These findings contribute valuable insights into the development of advanced combustion techniques for natural gas engines, offering a viable pathway to reduce methane slip without compromising engine efficiency or performance. The PC-MCC system presents a promising solution for the future of heavy-duty natural gas engine technology to reduce methane emissions.

Nsaif, Osama↗

An ISRU Propellant Production System to Fully Fuel a Mars Ascent Vehicle

In-Situ Resource Utilization (ISRU) will enable the long term presence of humans beyond low earth orbit. Since 2009, oxygen production from the Mars atmosphere has been baselined as an enabling technology for Mars human exploration by NASA. However, using water from the Martian regolith in addition to the atmospheric CO2 would enable the production of both liquid Methane and liquid Oxygen, thus fully fueling a Mars return vehicle. A case study was performed to show how ISRU can support NASA's Evolvable Mars Campaign (EMC) using methane and oxygen production from Mars resources. A model was built and used to generate mass and power estimates of an end-to-end ISRU system including excavation and extraction water from Mars regolith, processing the Mars atmosphere, and liquefying the propellants. Even using the lowest yield regolith, a full ISRU system would weigh 1.7 mT while eliminating the need to transport 30 mT of ascent propellants from earth.

Mars Surface↗

Lunar base CELSS: A bioregenerative approach

During the twenty-first century, human habitation of a self-sustaining lunar base could become a reality. To achieve this goal, the occupants will have to have food, water, and an adequate atmosphere within a carefully designed environment. Advanced technology will be employed to support terrestrial life-sustaining processes on the Moon. One approach to a life support system based on food production, waste management and utilization, and product synthesis is outlined. Inputs include an atmosphere, water, plants, biodegradable substrates, and manufacutured materials such as fiberglass containment vessels from lunar resources. Outputs include purification of air and water, food, and hydrogen (H2) generated from methane (CH4). Important criteria are as follows: (1) minimize resupply from Earth; and (2) recycle as efficiently as possible.

Easterwood, G. W.↗

CO2 Acquisition Membrane (CAM)

The objective of CAM is to develop, test, and analyze thin film membrane materials for separation and purification of carbon dioxide (CO2) from mixtures of gases, such as those found in the Martian atmosphere. The membranes are targeted toward In Situ Resource Utilization (ISRU) applications that will operate in extraterrestrial environments and support future unmanned and human space missions. A primary application is the Sabatier Electrolysis process that uses Mars atmosphere CO2 as raw material for producing water, oxygen, and methane for rocket fuel and habitat support. Other applications include use as an inlet filter to collect and concentrate Mars atmospheric argon and nitrogen gases for habitat pressurization, and to remove CO2 from breathing gases in Closed Environment Life Support Systems (CELSS). CAM membrane materials include crystalline faujasite (FAU) zeolite and rubbery polymers such as silicone rubber (PDMS) that have been shown in the literature and via molecular simulation to favor adsorption and permeation of CO2 over nitrogen and argon. Pure gas permeation tests using commercial PDMS membranes have shown that both CO2 permeance and the separation factor relative to other gases increase as the temperature decreases, and low (Delta)P(Sub CO2) favors higher separation factors. The ideal CO2/N2 separation factor increases from 7.5 to 17.5 as temperature decreases from 22 C to -30 C. For gas mixtures containing CO2, N2, and Ar, plasticization decreased the separation factors from 4.5 to 6 over the same temperature range. We currently synthesize and test our own Na(+) FAU zeolite membranes using standard formulations and secondary growth methods on porous alumina. Preliminary tests with a Na(+) FAU membrane at 22 C show a He/SF6 ideal separation factor of 62, exceeding the Knudsen diffusion selectivity by an order of magnitude. This shows that the membrane is relatively free from large defects and associated non-selective (viscous flow) transport mechanisms. The Membrane Test Facility (MTF) has been developed to measure membrane permeance over a wide range of temperature and pressure. The facility uses two volume compartments separated by the membrane that are instrumented to measure temperature, delta pressure across the membrane, and gas composition. A thermal shroud supports and encloses the membrane, and provides temperature control. Methods were developed to determine membrane permeance using the first order decay of the pressure difference between the sealed compartments, using the total pressure for pure gases, and partial pressure of each species in gas mixtures. The technique provides an end-to-end measurement of gas permeance that includes concentration polarization effects. Experiments have shown that in addition to membrane permeance properties, the geometry and design of associated structures play an important role in how membrane systems will function on Mars.

Mason, Larry W.↗

Theoretical assessments of CO 2 activation and hydrogenation pathways on transition-metal surfaces

Carbon dioxide (CO 2 ) hydrogenation on transition-metal active sites offers a promising carbon utilization route toward mitigating greenhouse gas emissions. C 1 products are often formed in parallel during CO 2 hydrogenation, prompting investigations into the intrinsic properties of transition metals that drive activity and product selectivity. Here, in this work, close-packed surfaces of a selection of transition-metal catalysts (Ni, Co, Rh, Ru, Pd, and Pt) were studied with density functional theory (DFT) calculations to understand their fundamental reactivities for CO 2 transformation reactions. Results indicate that CO 2 conversion proceeds through CO* formation and hydrogenation to form C 1 products (* denotes an adsorbed species). Ni, Co, Rh, and Ru favor CO/CH 4 formation, while Pd and Pt favor CO/CH 3 OH formation. The ability of a metal to dissociate C-O bonds drives selectivity between CH 4 and CH 3 OH, while competition between CO* desorption and surface hydrogenation describes CO selectivities. The C-O bond dissociation steps often impose the highest barrier along CH 4 formation reaction profiles, suggesting their kinetic relevance for CH 4 formation rates. The provided DFT-derived data sets detail a comprehensive reaction network of elementary steps relevant to C 1 chemistries, ultimately offering a benchmark for insights into design strategies for materials that exploit transition-metal active sites in carbon capture or utilization processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nonthermal hydrogen plasma-enabled ambient, fast lignin hydrogenolysis to valuable chemicals and bio-oils

The reduction of fossil fuel resources and the ongoing surge in global energy demand have captured the interest of researchers worldwide, prompting a focus on developing renewable energy sources. For this reason, biomass conversion has emerged as a crucial pathway for renewable fuel production. Lignin, constituting 10–35% of woody biomass, represents a significant and largely untapped sustainable feedstock. Despite the potential of lignin, a substantial portion of this lignocellulosic residue remains unused, with approximately 60% considered waste. This study addresses the challenge of underutilized lignin by introducing an innovative approach to its hydrogenolysis. Despite their potential, existing hydrogenolysis methods face obstacles such as complexity, high cost, and the need for high temperatures or pressures. Herein we report a noncatalytic nonthermal hydrogen plasma method for lignin hydrogenolysis, conducted under ambient temperature and pressure conditions. Our method proves to be highly effective in breaking lignin bonds, achieving complete conversion, and generating valuable gaseous and bio-oil products including methane and aromatic dimers and monomers obtained from guaiacyl and syringyl units within the lignin structure. Our results showed an increase in gaseous products, especially methane, and aromatic monomer yields, as well as a reduction in total bio-oil and biochar yields and lignin functional groups by increasing reaction time, input power, and H2 partial pressure. This research confirms the considerable promise of utilizing noncatalytic nonthermal hydrogen plasma-assisted hydrogenolysis as an effective technique for producing gaseous and liquid fuels from lignin.

Pishva, Parsa↗

Compact Hydrogen Generator

GTI Energy (GTI) is developing a One-Step Hydrogen Generation through Sorption Enhanced Reforming (SER) process that provides significant improvements in energy productivity (18% efficiency improvement), environmental performance (90% CO 2 capture and up to 98%), product yield (30% reduction in natural gas consumption), and economic benefit (reduce Levelized Cost of Hydrogen by 28%) as compared to the Steam Methane Reforming process. A 20,000 Standard Cubic Feet per Day pilot plant (or Feasibility Demonstration Unit, FDU) located at the Energy and Environmental Research Center (EERC) was moved to GTI’s Des Plaines, IL facility and reconfigured to utilize an atmospheric calciner which enables CO 2 capture as a high purity product. Between operations at EERC and GTI’s facility, the pilot plant has demonstrated over 110 hours of sorbent enhanced hydrogen production at 80% or higher purity. The primary objective of this project is to advance the development of GTI’s Sorption Enhanced Reforming (SER) hydrogen production technology, known as the Compact Hydrogen Generator (CHG), to allow for a future commercial demonstration. This effort was performed over the course of 51 months. The previous effort demonstrated that previously observed catalyst deactivation can be mitigated with different catalyst substrates and operating conditions. This follow-on effort will improve both the system operational reliability, and system efficiency. Additionally, a novel approach for the calcination process will be demonstrated which can reduce the cost of carbon dioxide capture by up to 60% compared to equivalent commercial approaches.

03 NATURAL GAS↗

Hot hydrogen atoms reactions of interest in molecular evolution and interstellar chemistry

Hot hydrogen atoms which are photochemically generated initiate reactions among mixtures of methane, ethane, water and ammonia, to produce ethanol, organic amines, organic acids, and amino acids. Both ethanol and ethyl amine can also act as substrates for formation of amino acids. The one carbon substrate methane is sufficient as a carbon source to produce amino acids. Typical quantum yields for formation of amino acids are approximately 0.00002 to 0.00004. In one experiment, 6 protein amino acids were identified and 8 nonprotein amino acids verified utilizing gas chromatography-mass spectroscopy. We propose that hot atoms, especially hydrogen, initiate reactions in the thermodynamic nonequilibrium environment of interstellar space as well as in the atmospheres of planets.

Becker, R. S.↗

PRIMO - The P&A Project Optimizer

In support of the Methane Emissions Reduction Program (MERP) and under the National Methane Emissions Reduction Initiative (NEMRI), the National Energy Technology Laboratory (NETL) and NETL site support contractors are developing and releasing an open-source decision-support tool (“PRIMO”) to help organizations determine which marginal conventional wells (MCWs) or other low-producing wells make the best candidates for plugging utilizing MERP funds, while also optimizing subsequent plugging and abandonment (P&A) campaigns for both program impact and efficiency. The framework—which is fully customizable—provides three main capabilities: 1. Ranking candidate wells (based on user preferences) 2. Identifying high-impact, high-efficiency P&A project candidates (with transparently computed scores for relevant metrics) 3. Comparing competing P&A projects quantitatively (through transparently computed project impact and efficiency scores) As such, PRIMO is a versatile, fully customizable tool that is meant to support organizations in making data-based, transparent, and defensible well selection and P&A project design decisions. For questions, comments or feedback, please contact primo@netl.doe.gov.

MERP↗

Harnessing photoautotroph-methanotroph interactions for biogas conversion to fuels and chemicals using binary consortia (Project Final Technical Report)

Industrial, municipal, and agricultural waste streams containing stranded organic carbon represent a significant and underutilized feedstock to produce fuels and chemicals. With anaerobic digestion deployed at large scales to capture organic waste streams, over 6 million tons of biogas are available today. However, the utilization of biogas represents a significant challenge due to its low pressure and presence of contaminants such as H 2 S, ammonia, and volatile organic carbon compounds. To tap into this immense potential, effective biotechnologies that co-utilize both CO 2 and CH 4 are needed. Recent studies demonstrated that, in nature, microbial communities have developed a highly efficient way to recover energy and capture carbon from both CH 4 and CO 2 through metabolic coupling of methane oxidation to oxygenic photosynthesis. Using two synthetic methanotroph – photoautotroph (M-P) co-cultures that exhibit stable growth under a broad range of cultivation conditions, in this project we proposed to harness the interspecies interactions within these cocultures for biogas conversion to fuels and chemicals. To facilitate this overarching objective, we aim to develop experimental and computational tools to gain qualitative and quantitative understandings on the interactions and dynamics of the coculture at both systems and molecular levels, and to validate our findings through experiments and mutant development. The fundamental understanding on the interactions and dynamics of the photoautotroph-methanotroph will lay the foundation for the design and optimization of synthetic binary consortia for production of fuels and chemicals from biogas. We expect the knowledge gained from this project may be generally applicable to other cross-feeding binary consortium, and the tools developed can be adapted to study the interactions and dynamics of other multi-organism platforms.

09 BIOMASS FUELS↗

Soldier-Warfighter Operationally Responsive Deployer for Space

The Soldier-Warfighter Operationally Responsive Deployer for Space (SWORDS) project was a joint project between the U.S. Army Space & Missile Defense Command (SMDC) and NASA. The effort, lead by SMDC, was intended to develop a three-stage liquid bipropellant (liquid oxygen/liquid methane), pressure-fed launch vehicle capable of inserting a payload of at least 25 kg to a 750-km circular orbit. The vehicle design was driven by low cost instead of high performance. SWORDS leveraged commercial industry standards to utilize standard hardware and technologies over customized unique aerospace designs. SWORDS identified broadly based global industries that have achieved adequate levels of quality control and reliability in their products and then designed around their expertise and business motivations.

Davis, Benny↗

Martian Environment Electrostatic Precipitator

As part of the planned manned mission to Mars, NASA has noticed that shipping oxygen as a part of life support to keep the astronauts alive continuously is overly expensive, and impractical. As such, noting that the Martian atmosphere is 95.37% CO2, NASA chemists noted that one could obtain oxygen from the Martian atmosphere. The plan, as part of a larger ISRU (in-situ resource utilization) initiative, would extract water from the regolith, or the Martian soil which can be electrolyzed by solar panel produced voltage into hydrogen and oxygen. The hydrogen can then be used in the Sabatier reaction with carbon dioxide to produce methane and water producing a net reaction that does not lose water and outputs methane and oxygen for use as rocket fuel and breathing.

Dust↗

Integrating Solar Energy, Desalination, and Electrolysis

Solar electricity enables the advancement and deployment of technologies that are strongly influenced by clean energy availability and cost. The economics of both desalination and hydrogen production from water electrolysis are dominated by the cost of energy, and the availability of inexpensive solar energy creates markets and offers incentives to the desalination and electrolyzer industries. In this report the production of high-purity water and hydrogen from seawater is focused on. Current electrolyzers require deionized water so they need to be coupled with desalination units. It is shown that such coupling is cost effective in hydrogen generation, and it also offers benefits to thermal desalination, which can utilize waste heat from electrolysis. Furthermore, such coupling can be optimized when electrolyzers operate at high current density, using low-cost solar and/or wind electricity, as such operation increases both hydrogen production and heat generation. Results of technoeconomic modeling of polymer electrolyte membrane electrolyzers define thresholds of electricity pricing, current density, and operating temperature that make clean electrolytic hydrogen cost competitive with hydrogen from steam methane reforming (SMR). By using 2020 hourly electricity pricing in California and Texas, it is estimated that hydrogen can be produced from seawater in coupled desalination-electrolyzer systems at prices near $2 kg -1 H 2 , reaching cost parity with hydrogen produced from SMR.

14 SOLAR ENERGY↗

Methane Emissions from Gathering Compressor Stations in the U.S.

Using results from a nationally representative measurement campaign at 180 gathering compressor stations conducted with nine industry partners, this study estimated emissions for the U.S. gathering sector, where sector-specific emission factors have not been previously available. The study drew from a partner station population of 1705 stations—a significantly larger pool than was available for prior studies. Data indicated that whole gas emission rates from components on gathering stations were comparable to or higher than emission factors utilized by the EPA’s greenhouse gas reporting program (GHGRP) but less than emission factors used for similar components on transmission compressor stations. Field data also indicated that the national population of stations likely has a higher fraction of smaller stations, operating at lower throughput per station, than the data used to develop the per-station emission factor used in EPA’s greenhouse gas inventory (GHGI). This was the first national study to incorporate extensive activity data reported to the GHGRP, including 319 basin-level reports, covering 15,895 reported compressors. Further, combining study emission data with 2017 GHGRP activity data, the study indicated statistically lower national emissions of 1290 [1246–1342] Gg methane per year or 66% [64–69%] of current GHGI estimates, despite estimating 17% [12–22%] more stations than the 2017 GHGI (95% confidence interval). Finally, we propose a replicable method that uses GHGRP activity data to annually update GHGI gathering and boost sector emissions.

03 NATURAL GAS↗

Mars Atmospheric In Situ Resource Utilization Projects at the Kennedy Space Center

The atmosphere of Mars, which is 96 percent carbon dioxide (CO2), is a rich resource for the human exploration of the red planet, primarily by the production of rocket propellants and oxygen for life support. Three recent projects led by NASAs Kennedy Space Center have been investigating the processing of CO2. The first project successfully demonstrated the Mars Atmospheric Processing Module (APM), which freezes CO2 with cryocoolers and combines sublimated CO2 with hydrogen to make methane and water. The second project absorbs CO2 with Ionic Liquids and electrolyzes it with water to make methane and oxygen, but with limited success so far. A third project plans to recover up to 100 of the oxygen in spacecraft respiratory CO2. A combination of the Reverse Water Gas Shift reaction and the Boudouard reaction eventually fill the reactor up with carbon, stopping the process. A system to continuously remove and collect carbon has been tested with encouraging results.

oxygen production and recovery↗

Mars Atmospheric In Situ Resource Utilization Projects at the Kennedy Space Center

The atmosphere of Mars, which is approximately 95% carbon dioxide (CO2), is a rich resource for the human exploration of the red planet, primarily by the production of rocket propellants and oxygen for life support. Three recent projects led by NASA's Kennedy Space Center have been investigating the processing of CO2. The first project successfully demonstrated the Mars Atmospheric Processing Module (APM), which freezes CO2 with cryocoolers and combines sublimated CO2 with hydrogen to make methane and water. The second project absorbs CO2 with Ionic Liquids and electrolyzes it with water to make methane and oxygen, but with limited success so far. A third project plans to recover up to 100% of the oxygen in spacecraft respiratory CO2. A combination of the Reverse Water Gas Shift reaction and the Boudouard reaction eventually fill the reactor up with carbon, stopping the process. A system to continuously remove and collect carbon is under construction.

in situ resource utilization↗