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At least 19 records

Merger of the Dissolved Gas Method into RELAP5-3D

The Dissolved Gas Model (DGM) was developed for Bettis Atomic Power Laboratory in their own special version of RELAP5-3D known as NUPAC by a subcontractor to. Incorporation of this important code capability in RELAP5-3D was necessary for collaboration between INL and Bettis on future code development efforts. The changes necessary to implement DGM are fundamental, changing the very solver technology at the core of RELAP5-3D, and pervasive, requiring the addition of new subprograms and data, alteration of existing data structures, and modification of more than one hundred subprograms. Moreover, NUPAC and RELAP5-3D had evolved separately and in different directions for a decade and were significantly dissimilar, so the effort was both complex and time-consuming. To ensure its correctness, a large test set comprised thousands of input cases had been constructed and had to run correctly to prove DGM was implemented correctly. A novel method for transporting and adjusting the updates for DGM into RELAP5-3D was undertaken. Tens of thousands of lines of code were either changed or added resulting in a 100% successful implementation of DGM in RELAP5-3D.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Transformer Health Monitoring Using Dissolved Gas Analysis

As integral components of any power plant, transformers supply the generated electricity to the grid. However, a transformer’s cellulose-based paper insulation and the mineral oil in which it is immersed break down over time under standard operating conditions—or more rapidly due to potential faults within the system. As the transformer’s mineral oil breaks down, gases are released that can be measured and monitored. This technical brief exhibits a collection of diagnostic and prognostic techniques that utilities can adopt in lieu of labor-intensive periodic preventive maintenance routines. Furthermore, prognostic models have been incorporated using the latest version of the Institute of Electrical and Electronics Engineers (IEEE) standard (IEEE, 2019) for dissolved gas analysis (DGA), thus expanding it to include estimation of the time to maintenance. Overall, four different methodologies are explained, each of which aids in determining a transformer’s state of health. These methodologies include the Chendong model, the IEEE thermal life consumption model (IEEE, 2012), a diagnostic model for DGA, and a prognostic model for DGA that uses an autoregressive integrated moving average (ARIMA) model. An additional improvement for estimating missing system parameters by using monitoring data (i.e., a tool for parameter estimation utilizing Powell’s method) is presented, enabling the IEEE thermal life consumption model to benefit not only the collaborating power plant, but also the power industry at large.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Dissolved gas recovery from water using a sidestream hollow-fiber membrane module: First principles model synthesis and steady-state validation

This paper presents a first-principles model for the recovery of dissolved gases from liquids using a sidestream hollow-fiber membrane module. The model avoids the use of new empirical coefficients, thus providing a parametric understanding of the process behavior for future design and optimization of membrane modules. This type of first-principles model could be particularly useful when gas recovery is beneficial to biological or chemical reactions of interest, such as the acetogenesis reactions in two-stage anaerobic digesters. The steady-state behavior of the model was validated against both new experimental data for the recovery of H 2 , CH 4 and H 2 –CH 4 mixtures from pure water, as well as existing published data. The modeled gas recovery predictions agreed with experimental data to an absolute average error of 13%, and an average R value of 0.98. Parametric analysis of mixed-gas recovery suggests possible key transition points in the composition of the recovered gases. For example, at 40 °C, increasing trans-membrane pressure while keeping hydraulic residence time (HRT) under 0.5 s will result in an increase in the ratio of H 2 to CH 4 recovered. Otherwise, increasing trans-membrane pressure will instead decrease the ratio of H 2 to CH 4 recovered. The model has potential to be extended to transient analysis, but has yet to be validated with transient experimental data. Furthermore, this model was successfully implemented in both Python and MATLAB, and provides valuable insights for future net-energy optimization for anaerobic digestion systems with in-situ gas recovery.

Anaerobic Digestion↗

Transformer Health Monitoring Using Dissolved Gas Analysis

Power plants use transformers for supplying generated electricity to the grid. As these transformers age and degrade, they produce specific gases. These gases can be monitored and used to predict when maintenance should be completed. This code uses four complementary techniques to predict when maintenance should be performed based on gas concentrations within the transformer.

Walker, CodyM [Idaho National Laboratory (INL), Id↗

Depressurization and two-phase flow of water containing high levels of dissolved nitrogen gas

Depressurization of water containing various concentrations of dissolved nitrogen gas was studied. In a nonflow depressurization experiment, water with very high nitrogen content was depressurized at rates from 0.09 to 0.50 MPa per second and a metastable behavior which was a strong function of the depressurization rate was observed. Flow experiments were performed in an axisymmetric, converging diverging nozzle, a two dimensional, converging nozzle with glass sidewalls, and a sharp edge orifice. The converging diverging nozzle exhibited choked flow behavior even at nitrogen concentration levels as low as 4 percent of the saturation level. The flow rates were independent of concentration level. Flow in the two dimensional, converging, visual nozzle appeared to have a sufficient pressure drop at the throat to cause nitrogen to come out of solution, but choking occurred further downstream. The orifice flow motion pictures showed considerable oscillation downstream of the orifice and parallel to the flow. Nitrogen bubbles appeared in the flow at back pressures as high as 3.28 MPa, and the level at which bubbles were no longer visible was a function of nitrogen concentration.

Simoneau, R. J.↗

In Situ High-Temperature TEM Observation of Inconel Corrosion by Molten Chloride Salts with N 2 , O 2 , or H 2 O

Here, in situ transmission electron microscopy (TEM) diffraction and imaging techniques are used to monitor and quantify corrosion of Inconel-625 by pure molten chloride salts (MgCl 2 – NaCl – KCl) at 500 °C–800 °C in 1.0 atm inert N 2 or pure O2, or by salts which are controllably hydrated in a high vacuum chamber. The isothermal corrosion rate R in inert N 2 increases from 203 ± 30 μ m year –1 at 700 °C to 463 ± 30 μ m year –1 at 800 °C. An oxygen ambient causes a six-fold increase to R = 1261 ± 170 μ m year –1 at 700 °C. Salt hydration dramatically accelerates corrosion to R > 3 × 10 5 μ m year –1 at 700 °C while it leads to a more moderate R = 95 ± 20 and 486 ± 30 μ m year –1 at 500 °C and 600 °C, respectively. These isothermal corrosion rates indicate that the molten chloride corrosion is significantly accelerated by salt hydration at temperatures above 600 °C, where corrosion is aggravated by increased generation and solubility of corrosive HCl gases. Hence, to reduce rate of corrosion it is important to both avoid incorporation of H 2 O into the system at each stage and ensure proper flushing of the system before increasing the temperature beyond 600 °C. Compositional analysis of the corroded cells indicate that corrosion in O 2 ambient is dominated by oxidation of metals by O 2 gas dissolved in the chloride melt, but corrosion in H 2 O ambients is caused by chlorination of metals by dissolved HCl gas and MgOH + ions. So, to reduce rate of corrosion, steps should be taken to tailor chloride melt compositions that has low solubility for HCl and O 2 . All of our corroded samples exhibit passive-protective oxide layers of Cr, Mg, and Ni. In addition, distinct volatile compounds of Ni, Mo and Cr involving NiCl 2 , (Na,K) 2 MoO 4 and CrO 2 (OH) 2 are detected in N 2 , H 2 O, and O 2 ambients, respectively. We believe that corrosion acceleration can be minimized by minimizing formation of volatile by-products or promoting reactions that could convert these volatile compounds to solid phases, as these volatile compounds led to destruction of protective oxide layers.

14 SOLAR ENERGY↗

Hollow-Fiber Spacesuit Water Membrane Evaporator

The hollow-fiber spacesuit water membrane evaporator (HoFi SWME) is being developed to perform the thermal control function for advanced spacesuits and spacecraft to take advantage of recent advances in micropore membrane technology in providing a robust, heat-rejection device that is less sensitive to contamination than is the sublimator. After recent contamination tests, a commercial-off-the-shelf (COTS) micro porous hollow-fiber membrane was selected for prototype development as the most suitable candidate among commercial hollow-fiber evaporator alternatives. An innovative design that grouped the fiber layers into stacks, which were separated by small spaces and packaged into a cylindrical shape, was developed into a full-scale prototype for the spacesuit application. Vacuum chamber testing has been performed to characterize heat rejection as a function of inlet water temperature and water vapor back-pressure, and to show contamination resistance to the constituents expected to be found in potable water produced by the wastewater reclamation distillation processes. Other tests showed tolerance to freezing and suitability to reject heat in a Mars pressure environment. In summary, HoFi SWME is a lightweight, compact evaporator for heat rejection in the spacesuit that is robust, contamination- insensitive, freeze-tolerant, and able to reject the required heat of spacewalks in microgravity, lunar, and Martian environments. The HoFi is packaged to reject 810 W of heat through 800 hours of use in a vacuum environment, and 370 W in a Mars environment. The device also eliminates free gas and dissolved gas from the coolant loop.

Bue, Grant↗

Greenhouse gas and dissolved oxygen production and consumption rates associated with Regier et al. (2023)

Tidal inundation along the coastal terrestrial-aquatic interface controls soil and sediment biogeochemistry and gas dynamics. Although a rich literature exist on studies of the influence of tidal waters on the biogeochemistry of coastal ecosystem soils, few studies have experimentally addressed the reverse question: How do soils (or sediments) from different coastal ecosystems influence the biogeochemistry of the tidal waters that inundate them? We conducted short-term microcosm laboratory experiments where seawater was amended with sediments and soils collected across regional gradients of inundation exposure (i.e., frequently to rarely inundated) and measured changes in dissolved oxygen and greenhouse gas concentrations to calculate gas consumption or production rates occurring during seawater exposure to terrestrial materials. This data package contains dissolved oxygen and greenhouse gas data collected during incubation of soils and sediments collected at 18 sites, which were used in the publication Regier et al. (2023) entitled “Coastal inundation regime moderates the short-term effects of sediment and soil additions on seawater oxygen and greenhouse gas dynamics: a microcosm experiment” which is published in Frontiers in Marine Science (DOI: https://doi.org/10.3389/fmars.2023.1308590).---Acknowledging EXCHANGE: General Support and Data Product UseWe ask that users of EXCHANGE data add the following acknowledgement when publishing data in scholarly articles and data repositories:"This research is based on work supported by COMPASS-FME, a multi-institutional project supported by the U.S. Department of Energy, Office of Science, Biological and Environmental Research as part of the Environmental System Science Program."

54 ENVIRONMENTAL SCIENCES↗

Investigation of air solubility in jet A fuel at high pressures

The solubility and density properties of saturated mixtures of fuels and gases were measured. The fuels consisted of Jet A and dodecane, the gases were air and nitrogen. The test range included pressures of 1.03 to 10.34 MPa and temperatures of 298 to 373 K. The results were correlated successfully, using the Soave equation of state. Over this test range, dissolved gas concentrations were roughly proportional to pressure and increased slightly with increasing temperature. Mixture density was relatively independent of dissolved gas concentration.

Rupprecht, S. D.↗

Effect of CO 2 on the water slip flow at silica surfaces for nanometer slit pores of talc

In our previous study, Molecular Dynamics (MD) simulated water flow with no dissolved gas in nanometer slit pores of the hydrophobic talc surfaces revealed a slip length of about 0.5 nm, which is close to the size of “water exclusion zone” but much less than experimental slip length. Atomic Force Microscopy (AFM) imaging confirmed the presence of pancake shape nanobubbles at the hydrophobic talc (001) surface (size from tens to hundreds of nanometers). The effect of CO 2 on water slip flow in talc nanopores is reported to reveal the importance of dissolved gas for confined fluid flow. MD simulated 7 nm CO 2 nanobubbles were found to attach and spread at the talc (001) surface, consistent with the AFM observation. Simulated CO 2 saturated water flow in the slit pores of talc (001) surfaces predicted the generation of CO 2 nanobubbles at the end of the slit pore, due to the stabilization of a CO 2 film at the talc (001) surfaces and a water barrier at the edge surfaces of talc. A “critical thickness” of about 1.5 nm was found for CO 2 nanobubbles to be stabilized at the end of the talc (001) surface. With 1.5 nm CO 2 nanobubbles at the talc (001) surface of a 6 nm slit pore, a water slip length of 1.8 nm was determined. Furthermore, the nanometer slit pore simulations with dissolved CO 2 in water revealed an increased slip length. It is expected that an increased slip length value would be found with an increased CO 2 film thickness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Potential Fifty Percent Reduction in Saturation Diving Decompression Time Using a Combination of Intermittent Recompression and Exercise

Conventional saturation decompression protocols use linear decompression rates that become progressively slower at shallower depths, consistent with free gas phase control vs. dissolved gas elimination kinetics. If decompression is limited by control of free gas phase, linear decompression is an inefficient strategy. The NASA prebreathe reduction program demonstrated that exercise during O2 prebreathe resulted in a 50% reduction (2 h vs. 4 h) in the saturation decompression time from 14.7 to 4.3 psi and a significant reduction in decompression sickness (DCS: 0 vs. 23.7%). Combining exercise with intermittent recompression, which controls gas phase growth and eliminates supersaturation before exercising, may enable more efficient saturation decompression schedules. A tissue bubble dynamics model (TBDM) was used in conjunction with a NASA exercise prebreathe model (NEPM) that relates tissue inert gas exchange rate constants to exercise (ml O2/kg-min), to develop a schedule for decompression from helium saturation at 400 fsw. The models provide significant prediction (p < 0.001) and goodness of fit with 430 cases of DCS in 6437 laboratory dives for TBDM (p = 0.77) and with 22 cases of DCS in 159 altitude exposures for NEPM (p = 0.70). The models have also been used operationally in over 25,000 dives (TBDM) and 40 spacewalks (NEPM). The standard U.S. Navy (USN) linear saturation decompression schedule from saturation at 400 fsw required 114.5 h with a maximum Bubble Growth Index (BGI(sub max)) of 17.5. Decompression using intermittent recompression combined with two 10 min exercise periods (75% VO2 (sub peak)) per day required 54.25 h (BGI(sub max): 14.7). Combined intermittent recompression and exercise resulted in a theoretical 53% (2.5 day) reduction in decompression time and theoretically lower DCS risk compared to the standard USN decompression schedule. These results warrant future decompression trials to evaluate the efficacy of this approach.

Gernhardt, Michael I.↗

Gas-Liquid Flow Modeling for Renewable Fuels Production

Aerobic/anaerobic and gas fermentation pathways have emerged as promising new technologies for the generation of renewable fuels/chemicals from biomass derived sugars, and mixtures of greenhouse/energy rich gas streams (CO2/CH4/H2/CO) via microbial action. Example pathways include sugars-to-ethanol conversion, biomethanation (CO2/H2 to CH4), biogas upgrading, CO fermentation and wet-waste conversion. Gas and liquid phase transport, mass-transfer, and mixing physics at large length scales can significantly affect microbial conversion rates, particularly when the microbial reaction requires a narrow set of conditions. These phenomena are difficult to study in small-scale bench-top reactors that are typically well-mixed. Predictive computational fluid dynamics (CFD) based simulations can therefore aid in the scale-up, design and optimization of these reactors. This work presents multiphase Euler-Euler CFD simulations of at-scale (~500 m3) bioreactors. Our mathematical model treats the gas and liquid as interpenetrating phases. This approach reduces the computational complexity of tracking individual gas bubbles that are several orders of magnitude smaller than reactor dimensions. We solve the Reynolds averaged Navier-Stokes (RANS) multiphase equations that account for phase and chemical species transport, interphase mass and momentum transfer and uses a phenomenological model for gas uptake by microbes. We use a customized solver derived from open-source CFD toolbox, OpenFOAM [1], to perform these simulations, which has been validated against small-scale reactors in our previous work [2]. There is currently a knowledge-gap regarding bubble-size distributions when using gas mixtures with vastly different properties, which can have a significant impact overall mass-transfer. For example, hydrogen bubbles are more buoyant compared to other relatively heavier gases (CO2/CH4/CO), resulting in a large distribution of residence times and bubble sizes. This work therefore develops a deeper understanding of bubble dynamics and interphase mass transfer in such heterogenous gas mixtures through well-resolved computational models. We use a population balance model (PBM) for bubble-size-distribution modeling that is validated against small-scale experiments in our solver with an uncertainty quantification study for bubble coalescence and break-up model parameters. Results pertaining to multiple simulations of gas-fermentation reactors are presented where gas mixtures with varying compositions of CO2/CH4/CO/H2 are imposed at the sparger boundaries. The spatio-temporal variations in bubble-size distribution and mass transfer coefficient are analyzed for varying superficial velocities and gas-compositions for varying sizes of bubble-column and airlift reactors. This work will also examine the performance of different reactor designs, viz. bubble column reactor, airlift reactor with an internal draft tube, and a stirred-tank reactor with Rushton impellers. Reactor mass-transfer coefficient, gas hold-up, and dissolved gas distribution are critically analyzed among reactors, and sensitivity studies pertaining to gas flow rates and reactor geometry will be presented. [1] Weller, H., Tabor, G., Jasak, H. and Fureby, C., A tensorial approach to computational continuum mechanics using object-oriented techniques, Computers in physics, 12, 6, 620--631, 1998. [2] Rahimi, M., Sitaraman, H., Humbird, D. and Stickel, J., Computational fluid dynamics study of full-scale aerobic bioreactors: Evaluation of gas-liquid mass transfer, oxygen uptake, and dynamic oxygen distribution, Chemical Engineering Research and Design, 139: 283-295.

BIOMASS FUELS↗

Expedition UT-GOM2-2 Site H

Pressure and conventional cores were collected at Site H of the Walker Ridge Protracted Area Block 313 in the Terrebonne Basin, deepwater Gulf of America (Gulf of Mexico) during the University of Texas (UT) Deepwater Hydrate Coring Expedition (UT-GOM2-2). Pressure and conventional cores were collected continuously to a depth of 155.1 meters below the seafloor (mbsf). At deeper depths, cores were taken periodically from hydrate-bearing sands and their bounding muds to a total depth of 861.3 mbsf. 162.6 m of conventional core and 54.8 m of pressure core were recovered. Twelve temperature measurements were made between 27.1 and 144.5 mbsf to determine the geothermal gradient. At the seafloor, more than 4 m of sandy silt of unknown origin was encountered. Beneath this sand, to a depth of about 200 mbsf, the section was composed of interbedded mud and biogenic carbonate ooze. The ooze correlated to low density and high porosity intervals observed in the previously acquired logging while drilling (LWD) data and as measured. These ooze intervals also correspond to lighter sediment color, increased Ca content based on X-ray florescence (XRF) core scanning, and increased calcareous nannofossil abundance. Calcareous nannofossil biostratigraphy constrains the entire record to the Pleistocene (< 0.91 million years), with a pronounced increase in sedimentation rate with depth. Below 200 mbsf, the section was predominantly composed of mud with two thicker, hydrate-bearing coarse-grained intervals, which are commonly known as the Blue and Orange sands. The dissolved gas concentration was quantified from pressure cores. In the shallow section, dissolved methane concentration increased below the sulfate-methane transition zone (SMTZ) and reaches saturation (the limit of solubility for methane) at 147 mbsf. Gas expansion was very common in conventional and depressurized pressure (conventionalized) cores below the SMTZ. At deeper depths, the methane concentration within muds bounding the Blue and Orange reservoirs was generally found to be less than saturation. The dissolved and hydrate gas composition is consistent with a microbial source, containing greater than 99.99% methane and only trace concentrations of ethane, propane, and butane. The methane to ethane ratio (C1 /C2 ) and the methane to ethane plus propane (C1 /(C2 +C3 )) decrease with depth down to at least 678 mbsf, mainly driven by the increase in ethane with depth. It is unclear if this trend continues through the Orange sand interval. The δ13C isotopic signature of methane ranges between -69.9 and -78.5 ‰ relative to the Vienna Pee Dee Belemnite (VPDB) standard. Pressure core recovery in sandy intervals was poor. However, pressure core logs of the Orange sand show intervals of low density and high velocity, which are indicative of high hydrate saturation. One pressure core was degassed and the average hydrate saturation in the core was determined to be 24%. One core from within the Orange sand was composed of interbedded graded sandy silt and mud. The sandy silts from this core are composed of mainly quartz and feldspar with some lithics. Most of the recovered pressure core samples are maintained at near in-situ pressure and temperature (within the hydrate stability field) at the University of Texas Pressure Core Center awaiting analysis. In the shallow section, samples will be used to determine the flux of organic carbon through the basin system, find the rate at which that carbon was consumed, and understand the microbial population responsible for these processes. In the deeper section, samples from in and around the hydrate reservoirs will be used to determine the petrophysical properties of the reservoir and bounding seals in these systems.

03 NATURAL GAS↗

Backpack electrofishing does not contribute to external signs of gas bubble trauma in sculpins

Abstract We exposed prickly sculpin Cottus asper and reticulate sculpin Cottus perplexus to electroshock and sham treatments in a controlled laboratory setting to determine if backpack electrofishing contributed to or exacerbated external signs of gas bubble trauma (GBT) in fish exposed to elevated total dissolved gas (TDG) levels. Fish were exposed to 115, 120 and 125% TDG (measured as percent of saturation) for various amounts of time (24–144 h) then subjected to a 5‐s electroshock or sham treatment of no electroshock. Fish were examined to determine the incidence of GBT pre‐ and post‐treatment, and all aspects (i.e., dorsal, ventral, left and right sides) of each fish were photographed. Across all TDG levels in all trials, no sculpin showed any change in GBT incidence following treatment. Analysis of GBT signs evident in photographs of 68 fish found no evidence of change in mean pre‐ and post‐treatment gas bubble sizes in fish in any TDG trial, nor were any new gas bubbles found following treatment. We are aware of no physiological mechanism by which backpack electrofishing can cause GBT in sculpin, and as such, we believe using this gear should not increase GBT incidence rates in sculpin.

Tiffan, Kenneth F.↗

UT-GOM2-2 Preliminary Report: Terrebonne Basin Northern Gulf of Mexico, 30 July-28 September 2023

In the summer and fall of 2023, the Gulf of Mexico Deepwater Hydrate Coring Expedition (UT-GOM2-2) drilled, cored, made downhole measurements, and analyzed samples from the seafloor to the base of the gas hydrate stability zone in one location (Site H, WR313) in the Terrebonne basin, deepwater Gulf of Mexico. Analyses of data and samples from the expedition will inform biological, geochemical, and geomechanical models to constrain the role of gas hydrates in the carbon cycle and the potential for gas hydrates as an energy resource. Pressure and conventional cores were collected continuously to a depth of 155.1 meters below the seafloor (mbsf). At deeper depths, cores were taken periodically from hydrate-bearing sands and their bounding muds to a total depth of 861.3 mbsf. 162.6 m of conventional core and 54.8 m of pressure core were obtained. Twelve temperature measurements were made between 27.1 and 144.5 mbsf to determine the geothermal gradient. At the seafloor, more than 4 m of sandy silt of unknown origin was encountered. Beneath this sand, to a depth of ~200 mbsf, the section was composed of interbedded mud and biogenic carbonate ooze. The biogenic ooze correlated to low density and high porosity intervals observed in the previously acquired logging while drilling (LWD) data and as measured. Calcareous nannofossil biostratigraphy constrains the entire record to the Pleistocene (< 0.91 million years) with a pronounced increase in sedimentation rate with depth. Beneath 200 mbsf, the section was predominantly composed of mud with two thicker, hydrate-bearing coarse-grained intervals, which are commonly known as the Blue and Orange sands. The dissolved gas concentration was quantified from pressure cores. In the shallow section, dissolved methane concentration increased below the sulfate-methane transition zone (SMTZ) and reaches saturation (the limit of solubility for methane) at 147 mbsf. Gas expansion was very common in conventional and depressurized pressure (conventionalized) cores below the SMTZ. At deeper depths, the methane concentration within muds bounding the Blue and Orange reservoirs was generally found to be less than saturation. The dissolved and hydrate gas composition is consistent with a microbial source, containing greater than 99.99% methane and only trace concentrations of ethane, propane, and butane. The methane to ethane ratio (C 1 /C 2 ) and the methane to ethane plus propane (C 1 /(C 2 +C 3 )) decrease with depth down to at least 678 mbsf, mainly driven by the increase in ethane with depth. It is unclear if this trend continues through the Orange sand interval. The δ 13 C isotopic signature of methane ranges between -69.9 and -78.5 ‰ Vienna Pee Dee Belemnite (VPDB). Pressure core recovery of all sandy intervals was poor. However, pressure core logs of the Orange sand show intervals of low density and high velocity, which are indicative of high hydrate saturation. One core from within the Orange sand was composed of interbedded graded sandy silt and mud. The sandy silts from this core are composed of mainly quartz and feldspar with some lithics. Most of the recovered pressure core samples are maintained at near in-situ pressure and temperature (within the hydrate stability field) at the University of Texas Pressure Core Center awaiting analysis. In the shallow section, samples will be used to determine the flux of organic carbon through the basin system, find the rate at which that carbon was consumed, and understand the microbial population responsible for these processes. In the deeper section, samples from in and around the hydrate reservoirs will be used to determine the petrophysical properties of the reservoir and bounding seals in these systems.

03 NATURAL GAS↗

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↗