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DOE OSTI2024

Estimating Total Methane Emissions from the Denver-Julesburg Basin Using Bottom-Up Approaches

Methane is a powerful greenhouse gas with a 25 times higher 100-year warming potential than carbon dioxide and is a target for mitigation to achieve climate goals. To control and curb methane emissions, estimates are required from the sources and sectors which are typically generated using bottom-up methods. However, recent studies have shown that national and international bottom-up approaches can significantly underestimate emissions. In this study, we present three bottom-up approaches used to estimate methane emissions from all emission sectors in the Denver-Julesburg basin, CO, USA. Our data show emissions generated from all three methods are lower than historic measurements. A Tier 1/2 approach using IPCC emission factors estimated 2022 methane emissions of 358 Gg (0.8% of produced methane lost by the energy sector), while a Tier 3 EPA-based approach estimated emissions of 269 Gg (0.2%). Using emission factors informed by contemporary and region-specific measurement studies, emissions of 212 Gg (0.2%) were calculated. The largest difference in emissions estimates were a result of using the Mechanistic Air Emissions Simulator (MAES) for the production and transport of oil and gas in the DJ basin. The MAES accounts for changes to regulatory practice in the DJ basin, which include comprehensive requirements for compressors, pneumatics, equipment leaks, and fugitive emissions, which were implemented to reduce emissions starting in 2014. The measurement revealed that normalized gas loss is predicted to have been reduced by a factor of 20 when compared to 10-year-old normalization loss measurements and a factor of 10 less than a nearby oil and production area (Delaware basin, TX); however, we suggest that more measurements should be made to ensure that the long-tail emission distribution has been captured by the modeling. This study suggests that regulations implemented by the Colorado Department of Public Health and Environment could have reduced emissions by a factor of 20, but contemporary regional measurements should be made to ensure these bottom-up calculations are realistic.

03 NATURAL GAS↗

DOE OSTI2024

Quantifying Drivers of Methane Hydrobiogeochemistry in a Tidal River Floodplain System

The influence of coastal ecosystems on global greenhouse gas (GHG) budgets and their response to increasing inundation and salinization remains poorly constrained. In this study, we have integrated an uncertainty quantification (UQ) and ensemble machine learning (ML) framework to identify and rank the most influential processes, properties, and conditions controlling methane behavior in a freshwater floodplain responding to recently restored seawater inundation. Our unique multivariate, multiyear, and multi-site dataset comprises tidal creek and floodplain porewater observations encompassing water level, salinity, pH, temperature, dissolved oxygen (DO), dissolved organic carbon (DOC), total dissolved nitrogen (TDN), partial pressure of carbon dioxide (pCO 2 ), nitrous oxide (pN 2 O), methane (pCH 4 ), and the stable isotopic composition of methane (δ 13 CH 4 ). Additionally, we incorporated topographical data, soil porosity, hydraulic conductivity, and water retention parameters for UQ analysis using a previously developed 3D variably saturated flow and transport floodplain model for a physical mechanistic understanding of factors influencing groundwater levels and salinity and, therefore, CH 4 . Principal component analysis revealed that groundwater level and salinity are the most significant predictors of overall biogeochemical variability. The ensemble ML models and UQ analyses identified DO, water level, salinity, and temperature as the most influential factors for porewater methane levels and indicated that approximately 80% of the total variability in hourly water levels and around 60% of the total variability in hourly salinity can be explained by permeability, creek water level, and two van Genuchten water retention function parameters: the air-entry suction parameter α and the pore size distribution parameter m. These findings provide insights on the physicochemical factors in methane behavior in coastal ecosystems and their representation in local- to global-scale Earth system models.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2014

Performance Simulations for a Spaceborne Methane Lidar Mission

Future spaceborne lidar measurements of key anthropogenic greenhouse gases are expected to close current observational gaps particularly over remote, polar, and aerosol-contaminated regions, where actual in situ and passive remote sensing observation techniques have difficulties. For methane, a "Methane Remote Lidar Mission" was proposed by Deutsches Zentrum fuer Luft- und Raumfahrt and Centre National d'Etudes Spatiales in the frame of a German-French climate monitoring initiative. Simulations assess the performance of this mission with the help of Moderate Resolution Imaging Spectroradiometer and Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations of the earth's surface albedo and atmospheric optical depth. These are key environmental parameters for integrated path differential absorption lidar which uses the surface backscatter to measure the total atmospheric methane column. Results showthat a lidar with an average optical power of 0.45W at 1.6 μm wavelength and a telescope diameter of 0.55 m, installed on a low Earth orbit platform(506 km), will measure methane columns at precisions of 1.2%, 1.7%, and 2.1% over land, water, and snow or ice surfaces, respectively, for monthly aggregated measurement samples within areas of 50 × 50 km2. Globally, the mean precision for the simulated year 2007 is 1.6%, with a standard deviation of 0.7%. At high latitudes, a lower reflectance due to snow and ice is compensated by denser measurements, owing to the orbital pattern. Over key methane source regions such as densely populated areas, boreal and tropical wetlands, or permafrost, our simulations show that the measurement precision will be between 1 and 2%.

methane↗

NASA NTRS2017

Development of Augmented Spark Impinging Igniter System for Methane Engines

The Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) program is establishing multiple no-funds-exchanged Space Act Agreement (SAA) partnerships with U.S. private sector entities. The purpose of this program is to encourage the development of robotic lunar landers that can be integrated with U.S. commercial launch capabilities to deliver payloads to the lunar surface. As part of the efforts in Lander Technologies, NASA Marshall Space Flight Center (MSFC) is developing liquid oxygen (LOX) and liquid methane (LCH4) engine technology to share with the Lunar CATALYST partners. Liquid oxygen and liquid methane propellants are attractive owing to their relatively high specific impulse for chemical propulsion systems, modest storage requirements, and adaptability to NASA's Journey to Mars plans. Methane has also been viewed as a possible propellant choice for lunar missions, owing to the performance benefits and as a technology development stepping stone to Martian missions. However, in the development of methane propulsion, methane ignition has historically been viewed as a high risk area in the development of such an engine. A great deal of work has been conducted in the past decade devoted to risk reduction in LOX/CH4 ignition. This paper will review and summarize the history and results of LOX/CH4 ignition programs conducted at NASA. More recently, a NASA-developed Augmented Spark Impinging (ASI) igniter body, which utilizes a conventional spark exciter system, is being tested with LOX/CH4 to help support internal and commercial engine development programs, such as those in Lunar CATALYST. One challenge with spark exciter systems, especially at altitude conditions, is the ignition lead that transmits the high voltage pulse from the exciter to the spark igniter (spark plug). The ignition lead can be prone to corona discharge, reducing the energy delivered by the spark and potentially causing non-ignition events. For the current work, a commercial compact exciter system, which eliminates this high voltage cabling, was tested at altitude conditions. A modified, conventional exciter system with an improved ignition lead was also recently tested at altitude conditions. This test program demonstrated the capability of these exciter systems to operate at altitude. While more extensive testing may be required, these systems or similar ones may be used for future NASA and commercial engine programs.

methane↗

NASA NTRS2013

The Distribution of Methane in Titan's Stratosphere from Cassini/CIRS Observations

Cassini/CIRS spectra in the far- and mid-infrared region are used to determine the abundance of methanein Titans lower stratosphere and investigate its distribution with latitude. The CIRS spectra include emissionfrom both the CH4 v4 band at 7.7 micron and pure rotational lines longwards of 50 micron, which show differential sensitivities to thermal profile and methane mole fraction. We analyze nadir and limb data taken over the first part of the Cassini mission (August 2005 to June 2010), including a selection of 12 latitudes that provides a reasonably complete and regular sampling of both hemispheres. Unexpectedly, but in a consistent manner for limb and nadir geometries, large variations of the methane mole fraction near 15 mbar (approx. 85 km) are found, with values ranging from approx. 1.0% (at low latitudes and near +/-50-55 deg) to approx. 1.5% (at +/-30-35 deg and polar latitudes). Error bars on the retrieved methane mole fraction are 0.07-0.12% at low latitudes in the Southern hemisphere and 0.14-0.21% northward of 40 deg N. A 1.0% methanemole fraction at low latitudes permits us to reconcile the HASI-measured temperatures below 147 kmaltitude (2.7 mbar) with inferences from CIRS. The roughly hemispherically-symmetric distribution ofmethane gas is reminiscent of that observed or predicted for the tropospheric methane clouds, whichon a yearly-averaged basis, show preferential occurrences at tropical and polar latitudes. We speculatethat convective events at these latitudes result into local stratospheric methane enrichment, whichmay persist year-round due to dynamical mixing times in the lower stratosphere only moderately shorterthan a Titan year.

Methane↗

NASA NTRS2018

The Challenges of Measuring Methane from Space with a Lidar

The global and regional quantification of methane fluxes and identification of its sources and sinks has been highlighted as one of the goals of the NASA 2017 Earth Science Decadal Survey. Detecting methane from space and airborne platforms with an active (laser) remote sensing instrument presents several unique technology and measurement challenges. The instrument must have a single frequency, narrow-linewidth light source, and photon-sensitive detector at the right spectral region to make continuous measurements from orbit, day and night, all seasons and at all latitudes. It must have a high signal to noise ratio and must be relatively immune to biases from aerosol/cloud scattering, spectroscopic and meteorological data uncertainties, and instrument systematic errors. At Goddard Space Flight Center (GSFC), in collaboration with industry, we have developed an airborne instrument to measure methane. Our instrument is a nadir-viewing lidar that uses Integrated Path Differential Absorption (IPDA), to measure methane near 1.65 µm. We sample the absorption line using multiple wavelengths from a narrow linewidth laser source and a sensitive photodetector. This measurement approach provides maximum information content about the CH4 column, and minimizes biases in the XCH4 retrieval. In this paper, we will review our progress to date and discuss the technology challenges, options and tradeoffs to measure methane from space and airborne platforms.

airborne instruments↗

NASA NTRS2021

Using Satellite Data to Identify the Methane Emission Controls of South Sudan's Wetlands

The TROPOspheric Monitoring Instrument (TROPOMI) provides observations of atmospheric methane (CH4) at an unprecedented combination of high spatial resolution and daily global coverage. Hu et al. (2018) reported unexpectedly large methane enhancements over South Sudan in these observations. Here we assess methane emissions from the wetlands of South Sudan using 2 years (December 2017–November 2019) of TROPOMI total column methane observations. We estimate annual wetland emissions of 7.4 ± 3.2 Tg yr−1, which agrees with the multiyear GOSAT inversions of Lunt et al. (2019) but is an order of magnitude larger than estimates from wetland process models. This disagreement may be explained by the underestimation (by up to 4 times) of inundation extent by the hydrological schemes used in those models. We investigate the seasonal cycle of the emissions and find the lowest emissions during the June–August season when the process models show the largest emissions. Using satellite-altimetry-based river water height measurements, we infer that this seasonal mismatch is likely due to a seasonal mismatch in inundation extent. In models, inundation extent is controlled by regional precipitation scaled to static wetland extent maps, whereas the actual inundation extent is driven by water inflow from rivers like the White Nile and the Sobat. We find the lowest emissions in the highest precipitation and lowest temperature season (June–August, JJA) when models estimate large emissions. In general, our emission estimates show better agreement in terms of both seasonal cycle and annual mean with model estimates that use a stronger temperature dependence. This suggests that temperature might be a stronger control for the South Sudan wetlands emissions than currently assumed by models. Our findings demonstrate the use of satellite instruments for quantifying emissions from inaccessible and uncertain tropical wetlands, providing clues for the improvement of process models and thereby improving our understanding of the currently uncertain contribution of wetlands to the global methane budget.

methane emission↗

DOE OSTI2016

NREL Advancements in Methane Conversion Lead to Cleaner Air, Useful Products

Researchers at NREL leveraged the recent on-site development of gas fermentation capabilities and novel genetic tools to directly convert methane to lactic acid using an engineered methanotrophic bacterium. The results provide proof-of-concept data for a gas-to-liquids bioprocess that concurrently produces fuels and chemicals from methane. NREL researchers developed genetic tools to express heterologous genes in methanotrophic organisms, which have historically been difficult to genetically engineer. Using these tools, researchers demonstrated microbial conversion of methane to lactate, a high-volume biochemical precursor predominantly utilized for the production of bioplastics. Methane biocatalysis offers a means to concurrently liquefy and upgrade natural gas and renewable biogas, enabling their utilization in conventional transportation and industrial manufacturing infrastructure. Producing chemicals and fuels from methane expands the suite of products currently generated from biorefineries, municipalities, and agricultural operations, with the potential to increase revenue and significantly reduce greenhouse gas emissions.

09 BIOMASS FUELS↗

DOE OSTI2022

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↗

DOE OSTI2015

Modeling methane emissions from arctic lakes: Model development and site‐level study

Abstract To date, methane emissions from lakes in the pan‐arctic region are poorly quantified. In order to investigate the response of methane emissions from this region to global warming, a process‐based climate‐sensitive lake biogeochemical model was developed. The processes of methane production, oxidation, and transport were modeled within a one‐dimensional sediment and water column. The sizes of 14 C‐enriched and 14 C‐depleted carbon pools were explicitly parameterized. The model was validated using observational data from five lakes located in Siberia and Alaska, representing a large variety of environmental conditions in the arctic. The model simulations agreed well with the measured water temperature and dissolved CH 4 concentration (mean error less than 1°C and 0.2 μM, respectively). The modeled CH 4 fluxes were consistent with observations in these lakes. We found that bubbling‐rate‐controlling nitrogen (N 2 ) stripping was the most important factor in determining CH 4 fraction in bubbles. Lake depth and ice cover thickness in shallow waters were also controlling factors. This study demonstrated that the thawing of Pleistocene‐aged organic‐rich yedoma can fuel sediment methanogenesis by supplying a large quantity of labile organic carbon. Observations and modeling results both confirmed that methane emission rate at thermokarst margins of yedoma lakes was much larger (up to 538 mg CH 4 m −2 d −1 ) than that at nonthermokarst zones in the same lakes and a nonyedoma, nonthermokarst lake (less than 42 mg CH 4 m −2 d −1 ). The seasonal variability of methane emissions can be explained primarily by energy input and organic carbon availability.

Tan, Zeli↗

DOE OSTI2015

Rising methane emissions from northern wetlands associated with sea ice decline

Abstract The Arctic is rapidly transitioning toward a seasonal sea ice‐free state, perhaps one of the most apparent examples of climate change in the world. This dramatic change has numerous consequences, including a large increase in air temperatures, which in turn may affect terrestrial methane emissions. Nonetheless, terrestrial and marine environments are seldom jointly analyzed. By comparing satellite observations of Arctic sea ice concentrations to methane emissions simulated by three process‐based biogeochemical models, this study shows that rising wetland methane emissions are associated with sea ice retreat. Our analyses indicate that simulated high‐latitude emissions for 2005–2010 were, on average, 1.7 Tg CH 4 yr −1 higher compared to 1981–1990 due to a sea ice‐induced, autumn‐focused, warming. Since these results suggest a continued rise in methane emissions with future sea ice decline, observation programs need to include measurements during the autumn to further investigate the impact of this spatial connection on terrestrial methane emissions.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2016

Climatic drivers for multidecadal shifts in solute transport and methane production zones within a large peat basin

Abstract Northern peatlands are an important source for greenhouse gases, but their capacity to produce methane remains uncertain under changing climatic conditions. We therefore analyzed a 43 year time series of the pore‐water chemistry to determine if long‐term shifts in precipitation altered the vertical transport of solutes within a large peat basin in northern Minnesota. These data suggest that rates of methane production can be finely tuned to multidecadal shifts in precipitation that drive the vertical penetration of labile carbon substrates within the Glacial Lake Agassiz Peatlands. Tritium and cation profiles demonstrate that only the upper meter of these peat deposits was flushed by downwardly moving recharge from 1965 to 1983 during a Transitional Dry‐to‐Moist Period. However, a shift to a moister climate after 1984 drove surface waters much deeper, largely flushing the pore waters of all bogs and fens to depths of 2 m. Labile carbon compounds were transported downward from the rhizosphere to the basal peat at this time producing a substantial enrichment of methane in Δ 14 C with respect to the solid‐phase peat from 1991 to 2008. These data indicate that labile carbon substrates can fuel deep production zones of methanogenesis that more than doubled in thickness across this large peat basin after 1984. Moreover, the entire peat profile apparently has the capacity to produce methane from labile carbon substrates depending on climate‐driven modes of solute transport. Future changes in precipitation may therefore play a central role in determining the source strength of peatlands in the global methane cycle.

Glaser, Paul H.↗

DOE OSTI2026

A Global Methane Observation System to Reduce Uncertainty for Anthropogenic and Natural Sources and Sinks for Detecting and Attributing Climate Feedbacks

Atmospheric methane (CH4) concentrations are accelerating global warming as net emissions increase. Observing systems that quantify sources remain too sparse and fragmented to detect trends—especially in remote regions where climate‐driven natural emissions may be rising. We provide a framework for quantifying uncertainty reductions through the implementation of a global ecosystem‐methane observing system designed to: (i) substantially lower uncertainty in sectoral and regional emissions, (ii) separate co‐occurring anthropogenic and natural fluxes, and (iii) trend detection at regional scales to verify mitigation progress and provide early warning of natural feedbacks. Using bottom‐up inventories and process‐model ensembles for 2014–2023, we show that anthropogenic emissions remain uncertain by ∼32% globally, while natural sources—tropical and boreal‐arctic wetlands, fires, and inland waters—carry far larger uncertainties (+ 70%) and trend uncertainties reaching ∼200%. Additional observations must match spatial emission structure to increase observability of emissions: high‐resolution satellite constellations for point sources combined with expanded flux networks and wetland mapping for diffuse sources, and denser ground‐based atmospheric column measurements to restore observability in under‐sampled tropics and high latitudes. Notional analyses indicate that targeted additions of flux towers and ∼20 in situ atmospheric column concentration instruments per key tropical region could reduce continental‐scale uncertainties at modest cost. Conceptual illustration of a Global Ecosystem Methane Observing System (GEM‐OS) integrating satellites, aircraft, atmospheric networks, and ecosystem measurements to quantify methane emissions from anthropogenic and natural sources. The multi‐scale observing framework improves source attribution, reduces uncertainty in regional methane budgets, and enables early detection of climate‐driven feedbacks from wetlands, fires, permafrost, agriculture, and fossil‐fuel emissions.

Ciais, P↗

DOE OSTI2017

Unique phase identification of trimetallic copper iron manganese oxygen carrier using simultaneous differential scanning calorimetry/thermogravimetric analysis during chemical looping combustion reactions with methane

Chemical looping combustion (CLC) is a promising combustion technology that generates heat and sequestration-ready carbon dioxide that is undiluted by nitrogen from the combustion of carbonaceous fuels with an oxygen carrier, or metal oxide. This process is highly dependent on the reactivity and stability of the oxygen carrier. The development of oxygen carriers remains one of the major barriers for commercialization of CLC. Synthetic oxygen carriers, consisting of multiple metal components, have demonstrated enhanced performance and improved CLC operation compared to single metal oxides. However, identification of the complex mixed metal oxide phases that form after calcination or during CLC reactions has been challenging. Without an understanding of the dominant metal oxide phase, it is difficult to determine reaction parameters and the oxygen carrier reduction pathway, which are necessary for CLC reactor design. This is particularly challenging for complex multi-component oxygen carriers such as copper iron manganese oxide (CuFeMnO 4 ). This study aims to differentiate the unique phase formation of a highly reactive, complex trimetallic oxygen carrier, CuFeMnO 4 , from its single and bimetallic counterparts using thermochemical and reaction data obtained from simultaneous differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) during temperature programmed reductions (TPR) with methane. DSC/TGA experiments during TPR with methane provides heat flow data and corresponding reaction rate data that can be used to determine reaction routes and mechanisms during methane reduction. Furthermore, non-isothermal TPR data provides the advantage of distinguishing reactions that may not be observable in isothermal analysis. The detailed thermochemical and reaction data, obtained during TPR with methane, distinguished a unique reduction pathway for CuFeMnO 4 that differed from its single and bimetallic counterparts. This is remarkable since X-ray diffraction (XRD) data alone could not be used to distinguish the reactive trimetallic oxide phase due to overlapping peaks from various single and mixed metal oxides. The unique reduction pathway of CuFeMnO 4 was further characterized in this study using in-situ XRD TPR with methane to determine changes in the dominant trimetallic phase that influenced the thermochemical and reaction rate data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Role of redox-active biochar with distinctive electrochemical properties to promote methane production in anaerobic digestion of waste activated sludge

Biochar has been reported as an effective additive to improve methane production during anaerobic digestion (AD). However, the mechanism for such a stimulatory impact remains unclear. Here we investigated the capability of three pyrolytic biochars with distinctive electrochemical properties (BC300, BC500, BC700) to promote methanogenic performance of anaerobic digesters treating waste activated sludge (WAS). The cumulative methane production and the maximum methane production rate were increased by 46.9% and 181.6%, respectively, with BC300 amendment. By characterizing the electrochemical properties of biochar, our research team found out that methane production in AD of sludge was positively correlated to biochar’s electron-donating capacity (EDC) rather than its bulk electrical conductivity. These results indicate that the electron transfer mediated by the redox-active functional groups may prevail over the direct electron migration as the predominant mechanism to facilitate interspecies electron transfer in syntrophic communities for enhanced methanogenesis. Microbial community analysis suggests that biochar enriched Methanosarcina and Methanobacterium. Overall, this study shows that functional groups-mediated electron transfer contributes greatly to the improved methane production in WAS digester with biochar amendment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Numerical Analysis of Experiments on Thermally Induced Dissociation of Methane Hydrates in Porous Media

Numerical simulation is essential for the prediction and evaluation of hydrocarbon reservoir performance. Numerical simulators developed for the description of the behavior of hydrates under production and the corresponding flow of fluids and heat accounting for all known processes are powerful, but they need validation through comparison to field or experimental data in order to instill confidence in their predictions. In this study, we analyze by means of numerical simulation the results of an experiment of methane hydrate dissociation by thermal stimulation in unconsolidated porous media heated through the vessel walls. The physics captured by the model include multicomponent heat and mass transfer, multiphase flow through porous media, and the phase behavior of the CH 4 + H 2 O system involved in methane hydrate formation and dissociation. The set of governing equations consists of the mass and energy conservation equations coupled with constitutive relationships, i.e., the dissolution of gas in H 2 O, relative permeability and capillary pressure models, composite thermal conductivity models, and methane hydrate phase equilibria. The model geometry describes accurately the hydrate reactor used in a recent experimental study investigating methane hydrate dissociation behavior [Chong et. al. Appl. Energy 2016, 177, 409-421]. The cumulative gas production is estimated and validated against three tests of experimental data involving different boundary temperatures, showing a good agreement between observations and numerical predictions. The predicted evolution of the spatial distributions of different phases over time shows that hydrate dissociation progresses inward from the reactor boundary to the center, methane gas accumulates to the top of the reactor because of buoyancy, and water migrates down to the bottom of the reactor because of gravity. A sharp hydrate dissociation front is predicted, and the estimated location of hydrate dissociation front suggests a linear relationship with the square root of time. A sensitivity analysis on the thermal conductivity of sand under fully saturated conditions is conducted to elucidate its effect on the gas production behavior. In addition, the energy efficiency ratio computed from the simulation of this boundary-wall heating technique varies from 14.0 to 16.2. Deviations between observations and predictions of the evolution of the temperature profile are attributed to initial heterogeneous distribution of the hydrate phase in the hydrate reactor.

42 ENGINEERING↗

DOE OSTI2021

Methane Generation from CO 2 with a Molecular Rhenium Catalyst

The atomic-level tunability of molecular structures is a compelling reason to develop homogeneous catalysts for challenging reactions such as the electrochemical reduction of carbon dioxide to valuable C 1 –C n products. Of particular interest is methane, the largest component of natural gas. Herein, we report a series of three isomeric rhenium tricarbonyl complexes coordinated by the asymmetric diimine ligands 2-(isoquinolin-1-yl)-4,5-dihydrooxazole ( quin-1-oxa ), 2-(quinolin-2-yl)-4,5-dihydrooxazole ( quin-2-oxa ), and 2-(isoquinolin-3-yl)-4,5-dihydrooxazole ( quin-3-oxa ) that catalyze the reduction of CO 2 to carbon monoxide and methane, albeit the latter with a low efficiency. To our knowledge, these complexes are the first examples of rhenium(I) catalysts capable of converting carbon dioxide into methane. Re(quin-1-oxa)(CO) 3 Cl ( 1 ), Re(quin-2-oxa)(CO) 3 Cl ( 2 ), and Re(quin-3-oxa)(CO) 3 Cl ( 3 ) were characterized and studied using a variety of electrochemical and spectroscopic techniques. In bulk electrolysis experiments, the three complexes reduce CO 2 to CO and CH 4 . When the controlled-potential electrolysis experiments are performed at -2.5 V (vs Fc +/0 ) and in the presence of the Brønsted acid 2,2,2-trifluoroethanol, methane is produced with turnover numbers that range from 1.3 to 1.8. Isotope labeling experiments using 13 CO 2 atmosphere produce 13 CH 4 ( m / z = 17) confirming that methane originates from CO 2 reduction. Theoretical calculations are performed to investigate the mechanistic aspects of the 8e – /8H + reduction of CO 2 to CH 4 . Overall, a ligand-assisted pathway is proposed to be an efficient pathway in the formation of CH 4 . Delocalization of the electron density on the (iso)quinoline moiety upon reduction stabilizes the key carbonyl intermediate leading to additional reactivity of this ligand. These results should aid the development of more robust catalytic systems that produce CH 4 from CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Plasma-Assisted Chemical-Looping Combustion: Low-Temperature Methane and Ethylene Oxidation with Nickel Oxide

The chemical reaction network of low-temperature plasma-assisted oxidation of methane (CH 4 ) and ethylene (C 2 H 4 ) with nickel oxide (NiO) was investigated in a heated plasma reactor through time-dependent species measurements by electron-ionization molecular beam mass spectrometry (EI-MBMS). Methane (ethylene) oxidation by NiO was explored in temperature ranges from 300-700 °C (300-500 °C) and 300-800 °C (300-600°C) for the plasma and non-plasma conditions, respectively. Significant enhancement of methane oxidation was observed with plasma between 400 and 500 °C, where no oxidation was observed under non-plasma conditions. For the oxidation of methane at higher temperatures three different oxidation stages were observed: I) a period of complete oxidation, II) a period of incomplete CO oxidation, and III) a period of carbon buildup. For the C 2 H 4 experiments, and unlike the CH 4 experiments, the plasma resulted in a significant amount of new intermediate oxygenated species, such as CH 2 O, CH 3 OH, C 2 H 4 O, and C 2 H 6 O. Carbon deposits were observed under both methane and ethylene conditions and verified by X-ray photoelectron spectroscopy (XPS). ReaxFF simulations were performed for the oxidation of CH 4 and C 2 H 4 in a non-plasma environment. The simulated intermediates and products largely agree with the species measured in the experiments, though the predicted intermediate oxygenated species such as CH 2 O and C 2 H 6 O were not observed in experiments under non-plasma conditions. A reaction pathway analysis for CH 4 and C 2 H 4 reacting with NiO was created based on the observed species from the MBMS spectra, along with ReaxFF simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗