Multi-species sensing using multi-mode absorption spectroscopy with mid-infrared interband cascade lasers

NASA Astrophysics Data System (ADS)

O'Hagan, S.; Northern, J. H.; Gras, B.; Ewart, P.; Kim, C. S.; Kim, M.; Merritt, C. D.; Bewley, W. W.; Canedy, C. L.; Vurgaftman, I.; Meyer, J. R.

2016-06-01

The application of an interband cascade laser, ICL, to multi-mode absorption spectroscopy, MUMAS, in the mid-infrared region is reported. Measurements of individual mode linewidths of the ICL, derived from the pressure dependence of lineshapes in MUMAS signatures of single, isolated, lines in the spectrum of HCl, were found to be in the range 10-80 MHz. Multi-line spectra of methane were recorded using spectrally limited bandwidths, of approximate width 27 cm-1, defined by an interference filter, and consist of approximately 80 modes at spectral locations spanning the 100 cm-1 bandwidth of the ICL output. Calibration of the methane pressures derived from MUMAS data using a capacitance manometer provided measurements with an uncertainty of 1.1 %. Multi-species sensing is demonstrated by the simultaneous detection of methane, acetylene and formaldehyde in a gas mixture. Individual partial pressures of the three gases are derived from best fits of model MUMAS signatures to the data with an experimental error of 10 %. Using an ICL, with an inter-mode interval of ~10 GHz, MUMAS spectra were recorded at pressures in the range 1-10 mbar, and, based on the data, a potential minimum detection limit of the order of 100 ppmv is estimated for MUMAS at atmospheric pressure using an inter-mode interval of 80 GHz.

Coupling between geochemical reactions and multicomponent gas and solute transport in unsaturated media: A reactive transport modeling study

USGS Publications Warehouse

Molins, S.; Mayer, K.U.

2007-01-01

The two‐way coupling that exists between biogeochemical reactions and vadose zone transport processes, in particular gas phase transport, determines the composition of soil gas. To explore these feedback processes quantitatively, multicomponent gas diffusion and advection are implemented into an existing reactive transport model that includes a full suite of geochemical reactions. Multicomponent gas diffusion is described on the basis of the dusty gas model, which accounts for all relevant gas diffusion mechanisms. The simulation of gas attenuation in partially saturated landfill soil covers, methane production, and oxidation in aquifers contaminated by organic compounds (e.g., an oil spill site) and pyrite oxidation in mine tailings demonstrate that both diffusive and advective gas transport can be affected by geochemical reactions. Methane oxidation in landfill covers reduces the existing upward pressure gradient, thereby decreasing the contribution of advective methane emissions to the atmosphere and enhancing the net flux of atmospheric oxygen into the soil column. At an oil spill site, methane oxidation causes a reversal in the direction of gas advection, which results in advective transport toward the zone of oxidation both from the ground surface and the deeper zone of methane production. Both diffusion and advection contribute to supply atmospheric oxygen into the subsurface, and methane emissions to the atmosphere are averted. During pyrite oxidation in mine tailings, pressure reduction in the reaction zone drives advective gas flow into the sediment column, enhancing the oxidation process. In carbonate‐rich mine tailings, calcite dissolution releases carbon dioxide, which partly offsets the pressure reduction caused by O2 consumption.

Method and apparatus for the selective separation of gaseous coal gasification products by pressure swing adsorption

DOEpatents

Ghate, Madhav R.; Yang, Ralph T.

1987-01-01

Bulk separation of the gaseous components of multi-component gases provided by the gasification of coal including hydrogen, carbon monoxide, methane, and acid gases (carbon dioxide plus hydrogen sulfide) are selectively adsorbed by a pressure swing adsorption technique using activated carbon, zeolite or a combination thereof as the adsorbent. By charging a column containing the adsorbent with a gas mixture and pressurizing the column to a pressure sufficient to cause the adsorption of the gases and then reducing the partial pressure of the contents of the column, the gases are selectively and sequentially desorbed. Hydrogen, the least absorbable gas of the gaseous mixture, is the first gas to be desorbed and is removed from the column in a co-current direction followed by the carbon monoxide, hydrogen and methane. With the pressure in the column reduced to about atmospheric pressure the column is evacuated in a countercurrent direction to remove the acid gases from the column. The present invention is particularly advantageous as a producer of high parity hydrogen from gaseous products of coal gasification and as an acid gas scrubber.

Dry reforming of methane on a highly-active Ni-CeO 2 catalyst: Effects of metal-support interactions on C–H bond breaking

DOE PAGES

Liu, Zongyuan; Grinter, David C.; Lustemberg, Pablo G.; ...

2016-05-04

Ni-CeO 2 is a highly efficient, stable and non-expensive catalyst for methane dry reforming at relative low temperatures (700 K). The active phase of the catalyst consists of small nanoparticles of nickel dispersed on partially reduced ceria. Experiments of ambient pressure XPS indicate that methane dissociates on Ni/CeO 2 at temperatures as low as 300 K, generating CH x and CO x species on the surface of the catalyst. Strong metal–support interactions activate Ni for the dissociation of methane. The results of density-functional calculations show a drop in the effective barrier for methane activation from 0.9 eV on Ni(111) tomore » only 0.15 eV on Ni/CeO 2–x(111). At 700 K, under methane dry reforming conditions, no signals for adsorbed CH x or C species are detected in the C1s XPS region. As a result, the reforming of methane proceeds in a clean and efficient way.« less

Adsorption of Natural Gas Mixtures in Nanoporos Carbon

NASA Astrophysics Data System (ADS)

Wexler, Carlos; Crawford-Goss, Ian; Lemke, Drew; Roth, Michael

Natural gas (NG) is promising fuel due to its smaller CO2 emissions per unit energy compared to other hydrocarbons. Storage via adsorption into carbon nanostructures permits the operation of storage tanks at significantly reduced pressures, resulting in cost savings, added safety and smaller loss of cargo volume. Since NG is mostly comprised of methane (87-99%), other components are often ignored, even though heavier species are likely to adsorb preferentially and possibly result in long-term performance issues. We performed Molecular Dynamics (MD) simulations to understand the behavior of heavier components of NG adsorbed into carbon nanostructures. We focused on mixtures involving methane, ethane and propane. We show that the heavier components have significant preferential adsorption, partially inhibiting the adsorption of methane, and resulting in its saturation at lower pressures. Under room temperature conditions, propane adsorbs quasi irrevesibly, though remaining mobile within the pores. We discuss the diffusion regime of all gases and address methods to remove the adsorbed heavier gases by thermal cycling the tank. American Chemical Society Petroleum Research Fund.

Modeling of termokinetic oscillations at partial oxidation of methane

NASA Astrophysics Data System (ADS)

Arutyunov, A. V.; Belyaev, A. A.; Inovenkov, I. N.; Nefedov, V. V.

2017-12-01

Partial oxidation of natural gas at moderate temperatures below 1500 K has significant interest for a number of industrial applications. But such processes can proceed at different unstable regimes including oscillating modes. Nonlinear phenomena at partial oxidation of methane were observed at different conditions. The investigation of the complex nonlinear system of equations that describes this process is a real method to insure its stability at industrial conditions and, at the same time, is an effective tool for its further enhancement. Numerical analysis of methane oxidation kinetics in the continuous stirred-tank reactor, with the use of detailed kinetic model has shown the possibility of the appearance of oscillating modes in the appropriate range of reaction parameters that characterize the composition, pressure, reagents flow, thermophysical features of the system, and geometry of the reactor. The appearance of oscillating modes is connected both with the reaction kinetics, heat release and sink and reagents introduction and removing. At that, oscillations appear only at a limited range of parameters, but can be accompanied by significant change in the yield of products. We have determined the range of initial temperature and pressure at which oscillations can be observed, if all other parameters remained fixed. The boundaries of existence of oscillations on the phase plane were calculated. It was shown that depending on the position inside the oscillation region the oscillations have different frequency and amplitude. It was reviled the role of heat exchange with the environment: at the absence of heat exchange the oscillating modes are impossible. In the vicinity of the boundary of phase range, where oscillations exist, significant change of concentration of some products were observed, for example, that of CO2, which in this case one of the principal products is. At that, insignificant increase in pressure not only change the character of CO2 behaving with time, but as well lead to significant increase of its mole fraction simultaneously twice decreasing the mole fraction of CO.

The potential for biologically catalyzed anaerobic methane oxidation on ancient Mars.

PubMed

Marlow, Jeffrey J; Larowe, Douglas E; Ehlmann, Bethany L; Amend, Jan P; Orphan, Victoria J

2014-04-01

This study examines the potential for the biologically mediated anaerobic oxidation of methane (AOM) coupled to sulfate reduction on ancient Mars. Seven distinct fluids representative of putative martian groundwater were used to calculate Gibbs energy values in the presence of dissolved methane under a range of atmospheric CO2 partial pressures. In all scenarios, AOM is exergonic, ranging from -31 to -135 kJ/mol CH4. A reaction transport model was constructed to examine how environmentally relevant parameters such as advection velocity, reactant concentrations, and biomass production rate affect the spatial and temporal dependences of AOM reaction rates. Two geologically supported models for ancient martian AOM are presented: a sulfate-rich groundwater with methane produced from serpentinization by-products, and acid-sulfate fluids with methane from basalt alteration. The simulations presented in this study indicate that AOM could have been a feasible metabolism on ancient Mars, and fossil or isotopic evidence of this metabolic pathway may persist beneath the surface and in surface exposures of eroded ancient terrains.

Method and apparatus for the selective separation of gaseous coal gasification products by pressure swing adsorption

DOEpatents

Ghate, M.R.; Yang, R.T.

1985-10-03

Bulk separation of the gaseous components of multi-component gases provided by the gasification of coal including hydrogen, carbon monoxide, methane, and acid gases (carbon dioxide plus hydrogen sulfide) are selectively adsorbed by a pressure swing adsorption technique using activated carbon zeolite or a combination thereof as the adsorbent. By charging a column containing the adsorbent with a gas mixture and pressurizing the column to a pressure sufficient to cause the adsorption of the gases and then reducing the partial pressure of the contents of the column, the gases are selectively and sequentially desorbed. Hydrogen, the least absorbable gas of the gaseous mixture, is the first gas to be desorbed and is removed from the column in a co-current direction followed by the carbon monoxide, hydrogen and methane. With the pressure in the column reduced to about atmospheric pressure the column is evacuated in a countercurrent direction to remove the acid gases from the column. The present invention is particularly advantageous as a producer of high purity hydrogen from gaseous products of coal gasification and as an acid gas scrubber. 2 figs., 2 tabs.

On the Experimental and Theoretical Investigations of Lean Partially Premixed Combustion, Burning Speed, Flame Instability and Plasma Formation of Alternative Fuels at High Temperatures and Pressures

NASA Astrophysics Data System (ADS)

Askari, Omid

This dissertation investigates the combustion and injection fundamental characteristics of different alternative fuels both experimentally and theoretically. The subjects such as lean partially premixed combustion of methane/hydrogen/air/diluent, methane high pressure direct-injection, thermal plasma formation, thermodynamic properties of hydrocarbon/air mixtures at high temperatures, laminar flames and flame morphology of synthetic gas (syngas) and Gas-to-Liquid (GTL) fuels were extensively studied in this work. These subjects will be summarized in three following paragraphs. The fundamentals of spray and partially premixed combustion characteristics of directly injected methane in a constant volume combustion chamber have been experimentally studied. The injected fuel jet generates turbulence in the vessel and forms a turbulent heterogeneous fuel-air mixture in the vessel, similar to that in a Compressed Natural Gas (CNG) Direct-Injection (DI) engines. The effect of different characteristics parameters such as spark delay time, stratification ratio, turbulence intensity, fuel injection pressure, chamber pressure, chamber temperature, Exhaust Gas recirculation (EGR) addition, hydrogen addition and equivalence ratio on flame propagation and emission concentrations were analyzed. As a part of this work and for the purpose of control and calibration of high pressure injector, spray development and characteristics including spray tip penetration, spray cone angle and overall equivalence ratio were evaluated under a wide range of fuel injection pressures of 30 to 90 atm and different chamber pressures of 1 to 5 atm. Thermodynamic properties of hydrocarbon/air plasma mixtures at ultra-high temperatures must be precisely calculated due to important influence on the flame kernel formation and propagation in combusting flows and spark discharge applications. A new algorithm based on the statistical thermodynamics was developed to calculate the ultra-high temperature plasma composition and thermodynamic properties. The method was applied to compute the thermodynamic properties of hydrogen/air and methane/air plasma mixtures for a wide range of temperatures (1,000-100,000 K), pressures (10-6-100 atm) and different equivalence ratios within flammability limit. In calculating the individual thermodynamic properties of the atomic species, the Debye-Huckel cutoff criterion has been used for terminating the series expression of the electronic partition function. A new differential-based multi-shell model was developed in conjunction with Schlieren photography to measure laminar burning speed and to study the flame instabilities for different alternative fuels such as syngas and GTL. Flame instabilities such as cracking and wrinkling were observed during flame propagation and discussed in terms of the hydrodynamic and thermo-diffusive effects. Laminar burning speeds were measured using pressure rise data during flame propagation and power law correlations were developed over a wide range of temperatures, pressures and equivalence ratios. As a part of this work, the effect of EGR addition and substitution of nitrogen with helium in air on flame morphology and laminar burning speed were extensively investigated. The effect of cell formation on flame surface area of syngas fuel in terms of a newly defined parameter called cellularity factor was also evaluated. In addition to that the experimental onset of auto-ignition and theoretical ignition delay times of premixed GTL/air mixture were determined at high pressures and low temperatures over a wide range of equivalence ratios.

Oxidation of coal-water slurry feed to hydrogasifier

DOEpatents

Lee, Bernard S.

1976-01-01

An aqueous coal slurry is preheated, subjected to partial oxidation and vaporization by injection of high pressure oxygen and is introduced into a top section of a hydrogasifier in direct contact with hot methane-containing effluent gases where vaporization of the slurry is completed. The resulting solids are reacted in the hydrogasifier and the combined gases and vapors are withdrawn and subjected to purification and methanation to provide pipeline gas. The amount of oxygen injected into the slurry is controlled to provide the proper thermal balance whereby all of the water in the slurry can be evaporated in contact with the hot effluent gases from the hydrogasifier.

Modeling solubility of CO2/hydrocarbon gas in ionic liquid ([emim][FAP]) using Aspen Plus simulations.

PubMed

Bagchi, Bishwadeep; Sati, Sushmita; Shilapuram, Vidyasagar

2017-08-01

The Peng-Robinson equation of state with quadratic van der Waals (vdW) mixing rule model was chosen to perform the thermodynamic calculations in Flash3 column of Aspen Plus to predict the solubility of CO 2 or any one of the hydrocarbons (HCs) among methane, ethane, propane, and butane in an ionic liquid 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([emim][FAP]). Bubble point pressure, solubility, bubble point temperature, fugacity, and partial molar volume at infinite dilution were obtained from the simulations, and enthalpy of absorption, Gibbs free energy of solvation, and entropy change of absorption were estimated by thermodynamic relations. Results show that carbon chain length has a significant effect on the bubble point pressure. Methane has the highest bubble point pressure among all the considered HCs and CO 2 . The bubble point pressure and fugacity variation with temperature is different for CO 2 as compared to HCs for mole fractions above 0.2. Two different profiles are noticed for enthalpy of absorption when plotted as a function of mole fraction of gas soluble in IL. Partial molar volume of CO 2 decreases with increase in temperature in [emim][FAP], while it is increased for HCs. Bubble point temperature decreases with increase in the mole fraction of the solute. Entropy of solvation increases with temperature till a particular value followed by a decrease with further increase in temperature. Gibbs free energy change of solvation showed that the process of solubility was spontaneous.

Hydrogen generator, via catalytic partial oxidation of methane for fuel cells

NASA Astrophysics Data System (ADS)

Recupero, Vincenzo; Pino, Lidia; Di Leonardo, Raffaele; Lagana', Massimo; Maggio, Gaetano

It is well known that the most acknowledged process for generation of hydrogen for fuel cells is based upon the steam reforming of methane or natural gas. A valid alternative could be a process based on partial oxidation of methane, since the process is mildly exothermic and therefore not energy intensive. Consequently, great interest is expected from conversion of methane into syngas, if an autothermal, low energy intensive, compact and reliable process could be developed. This paper covers the activities, performed by the CNR Institute of Transformation and Storage of Energy (CNR-TAE), on theoretical and experimental studies for a compact hydrogen generator, via catalytic selective partial oxidation of methane, integrated with second generation fuel cells (EC-JOU2 contract). In particular, the project focuses the attention on methane partial oxidation via heterogeneous selective catalysts, in order to: demonstrate the basic catalytic selective partial oxidation of methane (CSPOM) technology in a subscale prototype, equivalent to a nominal output of 5 kWe; develop the CSPOM technology for its application in electric energy production by means of fuel cells; assess, by a balance of plant analysis, and a techno-economic evaluation, the potential benefits of the CSPOM for different categories of fuel cells.

First determination of volume changes and enthalpies of the high-pressure decomposition reaction of the structure H methane hydrate to the cubic structure I methane hydrate and fluid methane.

PubMed

Ogienko, Andrey G; Tkacz, Marek; Manakov, Andrey Yu; Lipkowski, Janusz

2007-11-08

Pressure-temperature (P-T) conditions of the decomposition reaction of the structure H high-pressure methane hydrate to the cubic structure I methane hydrate and fluid methane were studied with a piston-cylinder apparatus at room temperature. For the first time, volume changes accompanying this reaction were determined. With the use of the Clausius-Clapeyron equation the enthalpies of the decomposition reaction of the structure H high-pressure methane hydrate to the cubic structure I methane hydrate and fluid methane have been calculated.

Determination of Carbon Dioxide, Carbon Monoxide, and Methane Concentrations in Cigarette Smoke by Fourier Transform Infrared Spectroscopy

ERIC Educational Resources Information Center

Tan, T. L.; Lebron, G. B.

2012-01-01

The integrated absorbance areas of vibrational bands of CO[subscript 2], CO, and CH[subscript 4] gases in cigarette smoke were measured from Fourier transform infrared (FTIR) spectra to derive the partial pressures of these gases at different smoke times. The quantity of the three gas-phase components of cigarette smoke at different smoke times…

A System for Incubations at High Gas Partial Pressure

PubMed Central

Sauer, Patrick; Glombitza, Clemens; Kallmeyer, Jens

2012-01-01

High-pressure is a key feature of deep subsurface environments. High partial pressure of dissolved gasses plays an important role in microbial metabolism, because thermodynamic feasibility of many reactions depends on the concentration of reactants. For gases, this is controlled by their partial pressure, which can exceed 1 MPa at in situ conditions. Therefore, high hydrostatic pressure alone is not sufficient to recreate true deep subsurface in situ conditions, but the partial pressure of dissolved gasses has to be controlled as well. We developed an incubation system that allows for incubations at hydrostatic pressure up to 60 MPa, temperatures up to 120°C, and at high gas partial pressure. The composition and partial pressure of gasses can be manipulated during the experiment. To keep costs low, the system is mainly made from off-the-shelf components with only very few custom-made parts. A flexible and inert PVDF (polyvinylidene fluoride) incubator sleeve, which is almost impermeable for gases, holds the sample and separates it from the pressure fluid. The flexibility of the incubator sleeve allows for sub-sampling of the medium without loss of pressure. Experiments can be run in both static and flow-through mode. The incubation system described here is usable for versatile purposes, not only the incubation of microorganisms and determination of growth rates, but also for chemical degradation or extraction experiments under high gas saturation, e.g., fluid–gas–rock-interactions in relation to carbon dioxide sequestration. As an application of the system we extracted organic compounds from sub-bituminous coal using H2O as well as a H2O–CO2 mixture at elevated temperature (90°C) and pressure (5 MPa). Subsamples were taken at different time points during the incubation and analyzed by ion chromatography. Furthermore we demonstrated the applicability of the system for studies of microbial activity, using samples from the Isis mud volcano. We could detect an increase in sulfate reduction rate upon the addition of methane to the sample. PMID:22347218

LIF measurements and chemical kinetic analysis of methylidyne formation in high-pressure counter-flow partially premixed and non-premixed flames

NASA Astrophysics Data System (ADS)

Naik, S. V.; Laurendeau, N. M.

2004-11-01

We report quantitative, spatially resolved, linear laser-induced fluorescence (LIF) measurements of methylidyne concentration ([CH]) in laminar, methane air, counter-flow partially premixed and non-premixed flames using excitation near 431.5 nm in the A X (0,0) band. For partially premixed flames, fuel-side equivalence ratios (ϕB) of 1.45, 1.6 and 2.0 are studied at pressures of 1, 3, 6, 9 and 12 atm. For non-premixed flames, the fuel-side mixture consists of 25% CH4 and 75% N2; measurements are obtained at pressures of 1, 2, 3, 4, 5, 6, 9 and 12 atm. The quantitative CH measurements are compared with predictions from an opposed-flow flame code utilizing two GRI chemical kinetic mechanisms (versions 2.11 and 3.0). LIF measurements of [CH] are corrected for variations in the quenching rate coefficient by using major species concentrations and temperatures generated by the code along with suitable quenching cross sections for CH available from the literature. A pathway analysis provides relative contributions from important elementary reactions to the total amount of CH produced at various pressures. Key reactions controlling peak CH concentrations are also identified by using a sensitivity analysis. For the partially premixed flames, measured CH profiles are reproduced reasonably well by GRI 3.0, although some quantitative disagreement exists at all pressures. Two CH radical peaks are observed for ϕB=1.45 and ϕB=1.6 at pressures above 3 atm. Peak CH concentrations for the non-premixed flames are significantly underpredicted by GRI 3.0. The latter agrees with previously reported NO concentrations, which are also underpredicted in these same high-pressure counter-flow diffusion flames.

Microbial mats in the Black Sea that anaerobically oxidise methane

NASA Astrophysics Data System (ADS)

Nauhaus, K.; Knittel, K.; Krüger, M.; Boetius, A.; Michaelis, W.; Widdel, F.

2003-04-01

Reef-forming microbial mats were recovered from methane seeps in anoxic waters of the northwestern Black Sea (BS) shelf. The microbial mats consist mainly of archaea (ANME-1 cluster) and sulfate-reducing bacteria (Desulfosarcina/Desulfococcus group). Laboratory incubations with homogenized subsamples of the mats revealed their ability for the anaerobic oxidation of methane (AOM). The phylogentic relationship of the sulfate reducing partner is the same as in the AOM consortia studied in sediment samples from a methane hydrate area (Hydrate Ridge (HR), Oregon, USA (1,2)). The archaeal partner however belongs to a different cluster than in the HR samples (ANME-2). Methane oxidation is coupled to sulfate reduction in a 1:1 stoichiometry. Elevated methane partial pressures (0.1 to 1.1 MPa) increased the sulfate reduction rates in the Black Sea samples only two-fold in contrast to 5-fold in HR samples. The optimal temperature for the BS samples is between 10 and 25^oC. In both samples AOM was not taking place if typical inhibitors for sulfate-reduction or methanogenesis were added, thus indicating a syntrophic relationship between the partner organisms. The intermediate that is exchanged between the methane oxidizing archaea and the sulfate-reducing bacterium is still unknown. Additions of the possible intermediates (Acetate, Formate, Hydrogen) did not result in higher sulfate reduction rates in the absence of methane. (1) Boetius, A. et al. (2000) A marine microbial consortium apparently mediating anaerobic oxidation of methane. Nature. 407: 623--626 (2) Nauhaus, K., Boetius, A., Krüger, M., Widdel, F. (2002) In vitro demonstration of anaerobic oxidation of methane coupled to sulphate reduction in sediment from a marine gas hydrate area. Environ. Microbiol. 4 (5): 296--305

High-pressure anaerobic digestion up to 100 bar: influence of initial pressure on production kinetics and specific methane yields.

PubMed

Merkle, Wolfgang; Baer, Katharina; Haag, Nicola Leonard; Zielonka, Simon; Ortloff, Felix; Graf, Frank; Lemmer, Andreas

2017-02-01

To ensure an efficient use of biogas produced by anaerobic digestion, in some cases it would be advisable to upgrade the biogenic gases and inject them into the transnational gas grids. To investigate biogas production under high-pressure conditions up to 100 bar, new pressure batch methane reactors were developed for preliminary lab-scale experiments with a mixture of grass and maize silage hydrolysate. During this investigation, the effects of different initial pressures (1, 50 and 100 bar) on pressure increase, gas production and the specific methane yield using nitrogen as inert gas were determined. Based on the experimental findings increasing initial pressures alter neither significantly, further pressure increases nor pressure increase rates. All supplied organic acids were degraded and no measurable inhibition of the microorganisms was observed. The results show that methane reactors can be operated at operating pressures up to 100 bar without any negative effects on methane production.

Measured temperature and pressure dependence of Vp and Vs in compacted, polycrystalline sI methane and sII methane-ethane hydrate

USGS Publications Warehouse

Helgerud, M.B.; Waite, W.F.; Kirby, S.H.; Nur, A.

2003-01-01

We report on compressional- and shear-wave-speed measurements made on compacted polycrystalline sI methane and sII methane-ethane hydrate. The gas hydrate samples are synthesized directly in the measurement apparatus by warming granulated ice to 17??C in the presence of a clathrate-forming gas at high pressure (methane for sI, 90.2% methane, 9.8% ethane for sII). Porosity is eliminated after hydrate synthesis by compacting the sample in the synthesis pressure vessel between a hydraulic ram and a fixed end-plug, both containing shear-wave transducers. Wave-speed measurements are made between -20 and 15??C and 0 to 105 MPa applied piston pressure.

Microbial diversity in methane hydrate-bearing deep marine sediments core preserved in the original pressure.

NASA Astrophysics Data System (ADS)

Takahashi, Y.; Hata, T.; Nishida, H.

2017-12-01

In normal coring of deep marine sediments, the sampled cores are exposed to the pressure of the atmosphere, which results in dissociation of gas-hydrates and might change microbial diversity. In this study, we analyzed microbial composition in methane hydrate-bearing sediment core sampled and preserved by Hybrid-PCS (Pressure Coring System). We sliced core into three layers; (i) outside layer, which were most affected by drilling fluids, (ii) middle layer, and (iii) inner layer, which were expected to be most preserved as the original state. From each layer, we directly extracted DNA, and amplified V3-V4 region of 16S rRNA gene. We determined at least 5000 of nucleotide sequences of the partial 16S rDNA from each layer by Miseq (Illumina). In the all layers, facultative anaerobes, which can grow with or without oxygen because they can metabolize energy aerobically or anaerobically, were detected as majority. However, the genera which are often detected anaerobic environment is abundant in the inner layer compared to the outside layer, indicating that condition of drilling and preservation affect the microbial composition in the deep marine sediment core. This study was conducted as a part of the activity of the Research Consortium for Methane Hydrate Resources in Japan [MH21 consortium], and supported by JOGMEC (Japan Oil, Gas and Metals National Corporation). The sample was provided by AIST (National Institute of Advanced Industrial Science and Technology).

Influence of headspace pressure on methane production in Biochemical Methane Potential (BMP) tests.

PubMed

Valero, David; Montes, Jesús A; Rico, José Luis; Rico, Carlos

2016-02-01

The biochemical methane potential test is the most commonly applied method to determine methane production from organic wastes. One of the parameters measured is the volume of biogas produced which can be determined manometrically by keeping the volume constant and measuring increases in pressure. In the present study, the effect of pressure accumulation in the headspace of the reactors has been studied. Triplicate batch trials employing cocoa shell, waste coffee grounds and dairy manure as substrates have been performed under two headspace pressure conditions. The results obtained in the study showed that headspace overpressures higher than 600mbar affected methane production for waste coffee grounds. On the contrary, headspace overpressures within a range of 600-1000mbar did not affect methane production for cocoa shell and dairy manure. With the analyses performed in the present work it has not been possible to determine the reasons for the lower methane yield value obtained for the waste coffee grounds under high headspace pressures. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of Nickel Levels on Hydrogen Partial Pressure and Methane Production in Methanogens

PubMed Central

2016-01-01

Hydrogen (H2) consumption and methane (CH4) production in pure cultures of three different methanogens were investigated during cultivation with 0, 0.2 and 4.21 μM added nickel (Ni). The results showed that the level of dissolved Ni in the anaerobic growth medium did not notably affect CH4 production in the cytochrome-free methanogenic species Methanobacterium bryantii and Methanoculleus bourgensis MAB1, but affected CH4 formation rate in the cytochrome-containing Methanosarcina barkeri grown on H2 and CO2. Methanosarcina barkeri also had the highest amounts of Ni in its cells, indicating that more Ni is needed by cytochrome-containing than by cytochrome-free methanogenic species. The concentration of Ni affected threshold values of H2 partial pressure (pH2) for all three methanogen species studied, with M. bourgensis MAB1 reaching pH2 values as low as 0.1 Pa when Ni was available in amounts used in normal anaerobic growth medium. To our knowledge, this is the lowest pH2 threshold recorded to date in pure methanogen culture, which suggests that M.bourgensis MAB1 have a competitive advantage over other species through its ability to grow at low H2 concentrations. Our study has implications for research on the H2-driven deep subsurface biosphere and biogas reactor performance. PMID:27992585

Effect of Nickel Levels on Hydrogen Partial Pressure and Methane Production in Methanogens.

PubMed

Neubeck, Anna; Sjöberg, Susanne; Price, Alex; Callac, Nolwenn; Schnürer, Anna

2016-01-01

Hydrogen (H2) consumption and methane (CH4) production in pure cultures of three different methanogens were investigated during cultivation with 0, 0.2 and 4.21 μM added nickel (Ni). The results showed that the level of dissolved Ni in the anaerobic growth medium did not notably affect CH4 production in the cytochrome-free methanogenic species Methanobacterium bryantii and Methanoculleus bourgensis MAB1, but affected CH4 formation rate in the cytochrome-containing Methanosarcina barkeri grown on H2 and CO2. Methanosarcina barkeri also had the highest amounts of Ni in its cells, indicating that more Ni is needed by cytochrome-containing than by cytochrome-free methanogenic species. The concentration of Ni affected threshold values of H2 partial pressure (pH2) for all three methanogen species studied, with M. bourgensis MAB1 reaching pH2 values as low as 0.1 Pa when Ni was available in amounts used in normal anaerobic growth medium. To our knowledge, this is the lowest pH2 threshold recorded to date in pure methanogen culture, which suggests that M.bourgensis MAB1 have a competitive advantage over other species through its ability to grow at low H2 concentrations. Our study has implications for research on the H2-driven deep subsurface biosphere and biogas reactor performance.

Porewater methane transport within the gas vesicles of diurnally migrating Chaoborus spp.: An energetic advantage

NASA Astrophysics Data System (ADS)

McGinnis, Daniel F.; Flury, Sabine; Tang, Kam W.; Grossart, Hans-Peter

2017-03-01

Diurnally-migrating Chaoborus spp. reach populations of up to 130,000 individuals m-2 in lakes up to 70 meters deep on all continents except Antarctica. Linked to eutrophication, migrating Chaoborus spp. dwell in the anoxic sediment during daytime and feed in the oxic surface layer at night. Our experiments show that by burrowing into the sediment, Chaoborus spp. utilize the high dissolved gas partial pressure of sediment methane to inflate their tracheal sacs. This mechanism provides a significant energetic advantage that allows the larvae to migrate via passive buoyancy rather than more energy-costly swimming. The Chaoborus spp. larvae, in addition to potentially releasing sediment methane bubbles twice a day by entering and leaving the sediment, also transport porewater methane within their gas vesicles into the water column, resulting in a flux of 0.01-2 mol m-2 yr-1 depending on population density and water depth. Chaoborus spp. emerging annually as flies also result in 0.1-6 mol m-2 yr-1 of carbon export from the system. Finding the tipping point in lake eutrophication enabling this methane-powered migration mechanism is crucial for ultimately reconstructing the geographical expansion of Chaoborus spp., and the corresponding shifts in the lake’s biogeochemistry, carbon cycling and food web structure.

Critical pressure and multiphase flow in Blake Ridge gas hydrates

USGS Publications Warehouse

Flemings, P.B.; Liu, Xiuying; Winters, W.J.

2003-01-01

We use core porosity, consolidation experiments, pressure core sampler data, and capillary pressure measurements to predict water pressures that are 70% of the lithostatic stress, and gas pressures that equal the lithostatic stress beneath the methane hydrate layer at Ocean Drilling Program Site 997, Blake Ridge, offshore North Carolina. A 29-m-thick interconnected free-gas column is trapped beneath the low-permeability hydrate layer. We propose that lithostatic gas pressure is dilating fractures and gas is migrating through the methane hydrate layer. Overpressured gas and water within methane hydrate reservoirs limit the amount of free gas trapped and may rapidly export methane to the seafloor.

Modeling of anaerobic degradation of solid slaughterhouse waste: inhibition effects of long-chain fatty acids or ammonia.

PubMed

Lokshina, L Y; Vavilin, V A; Salminen, E; Rintala, J

2003-01-01

The anaerobic bioconversion of solid poultry slaughterhouse wastes was kinetically investigated. The modified version of simulation model was applied for description of experimental data in mesophilic laboratory digester and assays. Additionally, stages of formation and consumption of long chain fatty acids (LCFA) were included in the model. Batch data on volatile solids, ammonium, acetate, butyrate, propionate, LCFA concentrations, pH level, cumulative volume, and methane partial pressure were used for model calibration. As a reference, the model was used to describe digestion of solid sorted household waste. Simulation results showed that an inhibition of polymer hydrolysis by volatile fatty acids and acetogenesis by NH3 or LCFA could be responsible for the complex system dynamics during degradation of lipid- and protein-rich wastes.

Biomethanation of Syngas Using Anaerobic Sludge: Shift in the Catabolic Routes with the CO Partial Pressure Increase.

PubMed

Sancho Navarro, Silvia; Cimpoia, Ruxandra; Bruant, Guillaume; Guiot, Serge R

2016-01-01

Syngas generated by thermal gasification of biomass or coal can be steam reformed and purified into methane, which could be used locally for energy needs, or re-injected in the natural gas grid. As an alternative to chemical catalysis, the main components of the syngas (CO, CO2, and H2) can be used as substrates by a wide range of microorganisms, to be converted into gas biofuels, including methane. This study evaluates the carboxydotrophic (CO-consuming) methanogenic potential present in an anaerobic sludge from an upflow anaerobic sludge bed (UASB) reactor treating waste water, and elucidates the CO conversion routes to methane at 35 ± 3°C. Kinetic activity tests under CO at partial pressures (pCO) varying from 0.1 to 1.5 atm (0.09-1.31 mmol/L in the liquid phase) showed a significant carboxydotrophic activity potential for growing conditions on CO alone. A maximum methanogenic activity of 1 mmol CH4 per g of volatile suspended solid and per day was achieved at 0.2 atm of CO (0.17 mmol/L), and then the rate decreased with the amount of CO supplied. The intermediary metabolites such as acetate, H2, and propionate started to accumulate at higher CO concentrations. Inhibition experiments with 2-bromoethanesulfonic acid (BES), fluoroacetate, and vancomycin showed that in a mixed culture CO was converted mainly to acetate by acetogenic bacteria, which was further transformed to methane by acetoclastic methanogens, while direct methanogenic CO conversion was negligible. Methanogenesis was totally blocked at high pCO in the bottles (≥1 atm). However it was possible to achieve higher methanogenic potential under a 100% CO atmosphere after acclimation of the sludge to CO. This adaptation to high CO concentrations led to a shift in the archaeal population, then dominated by hydrogen-utilizing methanogens, which were able to take over acetoclastic methanogens, while syntrophic acetate oxidizing (SAO) bacteria oxidized acetate into CO2 and H2. The disaggregation of the granular sludge showed a negative impact on their methanogenic activity, confirming that the acetoclastic methanogens were the most sensitive to CO, and a contrario, the advantage of using granular sludge for further development toward large-scale methane production from CO-rich syngas.

Biomethanation of Syngas Using Anaerobic Sludge: Shift in the Catabolic Routes with the CO Partial Pressure Increase

PubMed Central

Sancho Navarro, Silvia; Cimpoia, Ruxandra; Bruant, Guillaume; Guiot, Serge R.

2016-01-01

Syngas generated by thermal gasification of biomass or coal can be steam reformed and purified into methane, which could be used locally for energy needs, or re-injected in the natural gas grid. As an alternative to chemical catalysis, the main components of the syngas (CO, CO2, and H2) can be used as substrates by a wide range of microorganisms, to be converted into gas biofuels, including methane. This study evaluates the carboxydotrophic (CO-consuming) methanogenic potential present in an anaerobic sludge from an upflow anaerobic sludge bed (UASB) reactor treating waste water, and elucidates the CO conversion routes to methane at 35 ± 3°C. Kinetic activity tests under CO at partial pressures (pCO) varying from 0.1 to 1.5 atm (0.09–1.31 mmol/L in the liquid phase) showed a significant carboxydotrophic activity potential for growing conditions on CO alone. A maximum methanogenic activity of 1 mmol CH4 per g of volatile suspended solid and per day was achieved at 0.2 atm of CO (0.17 mmol/L), and then the rate decreased with the amount of CO supplied. The intermediary metabolites such as acetate, H2, and propionate started to accumulate at higher CO concentrations. Inhibition experiments with 2-bromoethanesulfonic acid (BES), fluoroacetate, and vancomycin showed that in a mixed culture CO was converted mainly to acetate by acetogenic bacteria, which was further transformed to methane by acetoclastic methanogens, while direct methanogenic CO conversion was negligible. Methanogenesis was totally blocked at high pCO in the bottles (≥1 atm). However it was possible to achieve higher methanogenic potential under a 100% CO atmosphere after acclimation of the sludge to CO. This adaptation to high CO concentrations led to a shift in the archaeal population, then dominated by hydrogen-utilizing methanogens, which were able to take over acetoclastic methanogens, while syntrophic acetate oxidizing (SAO) bacteria oxidized acetate into CO2 and H2. The disaggregation of the granular sludge showed a negative impact on their methanogenic activity, confirming that the acetoclastic methanogens were the most sensitive to CO, and a contrario, the advantage of using granular sludge for further development toward large-scale methane production from CO-rich syngas. PMID:27536280

A review of oxygen removal from oxygen-bearing coal-mine methane.

PubMed

Zhao, Peiyu; Zhang, Guojie; Sun, Yinghui; Xu, Ying

2017-06-01

In this article, a comparison will be made concerning the advantages and disadvantages of five kinds of coal mine methane (CMM) deoxygenation method, including pressure swing adsorption, combustion, membrane separation, non-metallic reduction, and cryogenic distillation. Pressure swing adsorption has a wide range of application and strong production capacity. To achieve this goal, adsorbent must have high selectivity, adsorption capacity, and adequate adsorption/desorption kinetics, remain stable after several adsorption/desorption cycles, and possess good thermal and mechanical stabilities. Catalytic combustion deoxygenation is a high-temperature exothermic redox chemical reaction, which releases large amounts of thermal energy. So, the stable and accurate control of the temperature is not easy. Meanwhile partial methane is lost. The key of catalytic combustion deoxygenation lies in the development of high-efficiency catalyst. Membrane separation has advantages of high separation efficiency and low energy consumption. However, there are many obstacles, including higher costs. Membrane materials have the requirements of both high permeability and high selectivity. The development of new membrane materials is a key for membrane separation. Cryogenic distillation has many excellence advantages, such as high purity production and high recovery. However, the energy consumption increases with decreasing CH 4 concentrations in feed gas. Moreover, there are many types of operational security problems. And that several kinds of deoxygenation techniques mentioned above have an economic value just for oxygen-bearing CMM with methane content above 30%. Moreover, all the above methods are not applicable to deoxygenation of low concentration CMM. Non-metallic reduction method cannot only realize cyclic utilization of deoxidizer but also have no impurity gases generation. It also has a relatively low cost and low loss rate of methane, and the oxygen is removed thoroughly. In particular, the non-metallic reduction method has good development prospects for low concentration oxygen-bearing CMM. This article also points out the direction of future development of coal mine methane deoxygenation.

In situ Raman and X-ray diffraction studies on the high pressure and temperature stability of methane hydrate up to 55 GPa.

PubMed

Kadobayashi, Hirokazu; Hirai, Hisako; Ohfuji, Hiroaki; Ohtake, Michika; Yamamoto, Yoshitaka

2018-04-28

High-temperature and high-pressure experiments were performed under 2-55 GPa and 298-653 K using in situ Raman spectroscopy and X-ray diffraction combined with externally heated diamond anvil cells to investigate the stability of methane hydrate. Prior to in situ experiments, the typical C-H vibration modes of methane hydrate and their pressure dependence were measured at room temperature using Raman spectroscopy to make a clear discrimination between methane hydrate and solid methane which forms through the decomposition of methane hydrate at high temperature. The sequential in situ Raman spectroscopy and X-ray diffraction revealed that methane hydrate survives up to 633 K and 40.3 GPa and then decomposes into solid methane and ice VII above the conditions. The decomposition curve of methane hydrate estimated by the present experiments is >200 K lower than the melting curves of solid methane and ice VII, and moderately increases with increasing pressure. Our result suggests that although methane hydrate may be an important candidate for major constituents of cool exoplanets and other icy bodies, it is unlikely to be present in the ice mantle of Neptune and Uranus, where the temperature is expected to be far beyond the decomposition temperatures.

In situ Raman and X-ray diffraction studies on the high pressure and temperature stability of methane hydrate up to 55 GPa

NASA Astrophysics Data System (ADS)

Kadobayashi, Hirokazu; Hirai, Hisako; Ohfuji, Hiroaki; Ohtake, Michika; Yamamoto, Yoshitaka

2018-04-01

High-temperature and high-pressure experiments were performed under 2-55 GPa and 298-653 K using in situ Raman spectroscopy and X-ray diffraction combined with externally heated diamond anvil cells to investigate the stability of methane hydrate. Prior to in situ experiments, the typical C-H vibration modes of methane hydrate and their pressure dependence were measured at room temperature using Raman spectroscopy to make a clear discrimination between methane hydrate and solid methane which forms through the decomposition of methane hydrate at high temperature. The sequential in situ Raman spectroscopy and X-ray diffraction revealed that methane hydrate survives up to 633 K and 40.3 GPa and then decomposes into solid methane and ice VII above the conditions. The decomposition curve of methane hydrate estimated by the present experiments is >200 K lower than the melting curves of solid methane and ice VII, and moderately increases with increasing pressure. Our result suggests that although methane hydrate may be an important candidate for major constituents of cool exoplanets and other icy bodies, it is unlikely to be present in the ice mantle of Neptune and Uranus, where the temperature is expected to be far beyond the decomposition temperatures.

Pressurant requirements for discharge of liquid methane from a 1.52-meter-(5-ft-) diameter spherical tank under both static and slosh conditions

NASA Technical Reports Server (NTRS)

Dewitt, R. L.; Mcintire, T. O.

1974-01-01

Pressurized expulsion tests were conducted to determine the effect of various physical parameters on the pressurant gas (methane, helium, hydrogen, and nitrogen) requirements during the expulsion of liquid methane from a 1.52-meter-(5-ft-) diameter spherical tank and to compare results with those predicted by an analytical program. Also studied were the effects on methane, helium, and hydrogen pressurant requirements of various slosh excitation frequencies and amplitudes, both with and without slosh suppressing baffles in the tank. The experimental results when using gaseous methane, helium, and hydrogen show that the predictions of the analytical program agreed well with the actual pressurant requirements for static tank expulsions. The analytical program could not be used for gaseous nitrogen expulsions because of the large quantities of nitrogen which can dissolve in liquid methane. Under slosh conditions, a pronounced increase in gaseous methane requirements was observed relative to results obtained for the static tank expulsions. Slight decreases in the helium and hydrogen requirements were noted under similar test conditions.

Solubility of aqueous methane under metastable conditions: implications for gas hydrate nucleation.

PubMed

Guo, Guang-Jun; Rodger, P Mark

2013-05-30

To understand the prenucleation stage of methane hydrate formation, we measured methane solubility under metastable conditions using molecular dynamics simulations. Three factors that influence solubility are considered: temperature, pressure, and the strength of the modeled van der Waals attraction between methane and water. Moreover, the naturally formed water cages and methane clusters in the methane solutions are analyzed. We find that both lowering the temperature and increasing the pressure increase methane solubility, but lowering the temperature is more effective than increasing the pressure in promoting hydrate nucleation because the former induces more water cages to form while the latter makes them less prevalent. With an increase in methane solubility, the chance of forming large methane clusters increases, with the distribution of cluster sizes being exponential. The critical solubility, beyond which the metastable solutions spontaneously form hydrate, is estimated to be ~0.05 mole fraction in this work, corresponding to the concentration of 1.7 methane molecules/nm(3). This value agrees well with the cage adsorption hypothesis of hydrate nucleation.

Instruments for Characterizing Carbon and Sulfur-Resistant Core-Shell Redox Catalysts for Combined Hydrocarbon Reforming and Water-Splitting

DTIC Science & Technology

2015-11-22

SECURITY CLASSIFICATION OF: This project aims to investigate a novel core-shell redox catalyst for combined methane partial oxidation and water...Properly designed redox catalyst are shown to be highly effective for syngas production (from methane ) and water-splitting. The resulting syngas has a...27709-2211 redox catalyst, methane partial oxidation, water-splitting REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT NUMBER(S) 10. SPONSOR

Stable, Ultra-Low Residence Time Partial Oxidation

DOEpatents

Schmidt, Lanny D.; Hickman, Daniel A.

1997-07-15

A process for the catalytic partial oxidation of methane in gas phase at very short residence time (800,000 to 12,000,000 hr.sup.-1) by contacting a gas stream containing methane and oxygen with a metal supported catalyst, such as platinum deposited on a ceramic monolith.

Process for the production of ethylene and other hydrocarbons from coal

DOEpatents

Steinberg, M.; Fallon, P.

1984-02-15

The subject invention comprises the steps of first reacting particulate coal with methane at a temperature in the approximate range of 500/sup 0/C to 1100/sup 0/C and at a partial pressure of methane of less than about 200 psig for a period of less than 10 seconds. More preferably, the method of the subject invention is carried out at a temperature of approximately 850/sup 0/C to 1000/sup 0/C and a pressure of 50 psig for a period of approximately 1.5 seconds. Surprisingly, it has been found that in the practice of the subject invention not only are commercially significant quantities of ethylene produced, namely yields in excess of 10% (percent carbon converted to product), along with economically significant quantities of-benzene and light oils, namely toluene and xylene, but also that there is little, if any, net consumption of methane in the reaction and possibly even a small net production. Since it is apparent that the carbonaceous solids or char remaining after the reaction is carried out may be burned to provide the necessary energy to carry out the process of the subject invention, it is apparent that the subject invention advantageously provides a method for the conversion of coal to economically significant quantities of ethylene, benzene and light oils while requiring only coal and, possibly, small amounts of make-up methane. Other objects and advantages of the subject invention will be apparent to those skilled in the art from a consideration of the attached drawings, the detailed description of the invention, and the experimental examples set forth below.

Methane combustion reactivity during the metal→metallic oxide transformation of Pd-Pt catalysts: Effect of oxygen pressure

NASA Astrophysics Data System (ADS)

Qi, Wenjie; Ran, Jingyu; Zhang, Zhien; Niu, Juntian; Zhang, Peng; Fu, Lijuan; Hu, Bo; Li, Qilai

2018-03-01

Density functional theory combined with kinetic models were used to probe different kinetics consequences by which methane activation on different oxygen chemical potential surfaces as oxygen pressure increased. The metallic oxide → metal transformation temperature of Pd-Pt catalysts increased with the increase of the Pd content or/and O2 pressure. The methane conversion rate on Pt catalyst increased and then decreased to a constant value when increasing the O2 pressure, and Pd catalyst showed a poor activity performance in the case of low O2 pressure. Moreover, its activity increased as the oxygen chemical potential for O2 pressure increased in the range of 2.5-10 KPa. For metal clusters, the Csbnd H bond and Odbnd O bond activation steps occurred predominantly on *-* site pairs. The methane conversion rate was determined by O2 pressure because the adsorbed O atoms were rapidly consumed by other adsorbed species in this kinetic regime. As the O2 pressure increased, the metallic active sites for methane activation were decreased and there was no longer lack of adsorbed O atoms, resulting in the decrease of the methane conversion rate. Furthermore, when the metallic surfaces were completely covered by adsorbed oxygen atoms at higher oxygen chemical potentials, Pt catalyst showed a poor activity due to a high Csbnd H bond activation barrier on O*sbnd O*. In the case of high O2 pressure, Pd atoms preferred to segregate to the active surface of Pd-Pt catalysts, leading to the formation of PdO surfaces. The increase of Pd segregation promoted a subsequent increase in active sites and methane conversion rate. The PdO was much more active than metallic and O* saturated surfaces for methane activation, inferred from the theory and experimental study. Pd-rich bimetallic catalyst (75% molar Pd) showed a dual high methane combustion activity on O2-poor and O2-rich conditions.

Anaerobic biodegradation of cellulosic material: Batch experiments and modelling based on isotopic data and focusing on aceticlastic and non-aceticlastic methanogenesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qu, X.; Cemagref, UR-HBAN, Parc de Tourvoie, Antony cedex F-92163; Vavilin, V.A.

Utilizing stable carbon isotope data to account for aceticlastic and non-aceticlastic pathways of methane generation, a model was created to describe laboratory batch anaerobic decomposition of cellulosic materials (office paper and cardboard). The total organic and inorganic carbon concentrations, methane production volume, and methane and CO{sub 2} partial pressure values were used for the model calibration and validation. According to the fluorescent in situ hybridization observations, three groups of methanogens including strictly hydrogenotrophic methanogens, strictly aceticlastic methanogens (Methanosaeta sp.) and Methanosarcina sp., consuming both acetate and H{sub 2}/H{sub 2}CO{sub 3} as well as acetate-oxidizing syntrophs, were considered. It was shownmore » that temporary inhibition of aceticlastic methanogens by non-ionized volatile fatty acids or acidic pH was responsible for two-step methane production from office paper at 35 {sup o}C where during the first and second steps methane was generated mostly from H{sub 2}/H{sub 2}CO{sub 3} and acetate, respectively. Water saturated and unsaturated cases were tested. According to the model, at the intermediate moisture (150%), much lower methane production occurred because of full-time inhibition of aceticlastic methanogens. At the lowest moisture, methane production was very low because most likely hydrolysis was seriously inhibited. Simulations showed that during cardboard and office paper biodegradation at 55 {sup o}C, non-aceticlastic syntrophic oxidation by acetate-oxidizing syntrophs and hydrogenotrophic methanogens were the dominant methanogenic pathways.« less

A unified equation for calculating methane vapor pressures in the CH4-H2O system with measured Raman shifts

USGS Publications Warehouse

Lu, W.; Chou, I.-Ming; Burruss, R.C.; Song, Y.

2007-01-01

A unified equation has been derived by using all available data for calculating methane vapor pressures with measured Raman shifts of C-H symmetric stretching band (??1) in the vapor phase of sample fluids near room temperature. This equation eliminates discrepancies among the existing data sets and can be applied at any Raman laboratory. Raman shifts of C-H symmetric stretching band of methane in the vapor phase of CH4-H2O mixtures prepared in a high-pressure optical cell were also measured at temperatures between room temperature and 200 ??C, and pressures up to 37 MPa. The results show that the CH4 ??1 band position shifts to higher wavenumber as temperature increases. We also demonstrated that this Raman band shift is a simple function of methane vapor density, and, therefore, when combined with equation of state of methane, methane vapor pressures in the sample fluids at elevated temperatures can be calculated from measured Raman peak positions. This method can be applied to determine the pressure of CH4-bearing systems, such as methane-rich fluid inclusions from sedimentary basins or experimental fluids in hydrothermal diamond-anvil cell or other types of optical cell. ?? 2007 Elsevier Ltd. All rights reserved.

Gold-carbon composite thin films for electrochemical gas sensor prepared by reactive plasma sputtering

NASA Astrophysics Data System (ADS)

Okamoto, A.; Suzuki, Y.; Yoshitake, M.; Ogawa, S.; Nakano, N.

1997-01-01

We have investigated the properties of gold-carbon composite thin films prepared by a plasma sputtering deposition using argon and methane mixture gas. These composite films have an uneven surface in submicron scale or consist of nano-scale particles of gold polycrystalline. Such morphological properties can be controlled by the sputtering voltage and the partial pressure of methane gas. The working electrode of electrochemical gas sensor has needed a stable gas sensitivity and a good gas selectivity. Our composite film is one of the excellent candidates for a thin film working electrode of electrochemical gas sensor. It is described that the output current of sensor is related to the preparation conditions of the thin films and increase linearly as the concentration of PH 3 gas ranging from 0.1 to 1.0 ppm is increasing.

Diamond-anvil cell observations of a new methane hydrate phase in the 100-MPa pressure range

USGS Publications Warehouse

Chou, I.-Ming; Sharma, A.; Burruss, R.C.; Hemley, R.J.; Goncharov, A.F.; Stern, L.A.; Kirby, S.H.

2001-01-01

A new high-pressure phase of methane hydrate has been identified based on its high optical relief, distinct pressure-temperature phase relations, and Raman spectra. In-situ optical observations were made in a hydrothermal diamond-anvil cell at temperatures between -40?? and 60 ??C and at pressures up to 900 MPa. Two new invariant points were located at -8.7 ??C and 99 MPa for the assemblage consisting of the new phase, structure I methane hydrate, ice Ih, and water, and at 35.3 ??C and 137 MPa for the new phase-structure I methane hydrate-water-methane vapor. Existence of the new phase is critical for understanding the phase relations among the hydrates at low to moderate pressures, and may also have important implications for understanding the hydrogen bonding in H2O and the behavior of water in the planetary bodies, such as Europa, of the outer solar system.

Experimental Study and Mathematical Modeling of Self-Sustained Kinetic Oscillations in Catalytic Oxidation of Methane over Nickel.

PubMed

Lashina, Elena A; Kaichev, Vasily V; Saraev, Andrey A; Vinokurov, Zakhar S; Chumakova, Nataliya A; Chumakov, Gennadii A; Bukhtiyarov, Valerii I

2017-09-21

The self-sustained kinetic oscillations in the oxidation of CH 4 over Ni foil have been studied at atmospheric pressure using an X-ray diffraction technique and mass spectrometry. It has been shown that the regular oscillations appear under oxygen-deficient conditions; CO, CO 2 , H 2 , and H 2 O are detected as the products. According to in situ X-ray diffraction measurements, nickel periodically oxidizes to NiO initiating the reaction-rate oscillations. To describe the oscillations, we have proposed a five-stage mechanism of the partial oxidation of methane over Ni and a corresponding three-variable kinetic model. The mechanism considers catalytic methane decomposition, dissociative adsorption of oxygen, transformation of chemisorbed oxygen to surface nickel oxide, and reaction of adsorbed carbon and oxygen species to form CO. Analysis of the kinetic model indicates that the competition of two processes, i.e., the oxidation and the carbonization of the catalyst surface, is the driving force of the self-sustained oscillations in the oxidation of methane. We have compared this mechanism with the detailed 18-stage mechanism described previously by Lashina et al. (Kinetics and Catalysis 2012, 53, 374-383). It has been shown that both kinetic mechanisms coupled with a continuous stirred-tank reactor model describe well the oscillatory behavior in the oxidation of methane under non-isothermal conditions.

Investigation of combustion characteristics of methane-hydrogen fuels

NASA Astrophysics Data System (ADS)

Vetkin, A. V.; Suris, A. L.; Litvinova, O. A.

2015-01-01

Numerical investigations of combustion characteristics of methane-hydrogen fuel used at present in tube furnaces of some petroleum refineries are carried out and possible problems related to change-over of existing furnaces from natural gas to methane-hydrogen fuel are analyzed. The effect of the composition of the blended fuel, associated temperature and emissivity of combustion products, temperature of combustion chamber walls, mean beam length, and heat release on variation in the radiation heat flux is investigated. The methane concentration varied from 0 to 100%. The investigations were carried out both at arbitrary given gas temperatures and at effective temperatures determined based on solving a set of equations at various heat-release rates of the combustion chamber and depended on the adiabatic combustion temperature and the temperature at the chamber output. The approximation dependence for estimation of the radiation heat exchange rate in the radiant chamber of the furnace at change-over to fuel with a greater hydrogen content is obtained. Hottel data were applied in the present work in connection with the impossibility to use approximated formulas recommended by the normative method for heat calculation of boilers to determine the gas emissivity, which are limited by the relationship of partial pressures of water steam and carbon dioxide in combustion products . The effect of the methane-hydrogen fuel on the equilibrium concentration of nitrogen oxides is also investigated.

Discovery of a novel methanogen prevalent in thawing permafrost.

PubMed

Mondav, Rhiannon; Woodcroft, Ben J; Kim, Eun-Hae; McCalley, Carmody K; Hodgkins, Suzanne B; Crill, Patrick M; Chanton, Jeffrey; Hurst, Gregory B; VerBerkmoes, Nathan C; Saleska, Scott R; Hugenholtz, Philip; Rich, Virginia I; Tyson, Gene W

2014-01-01

Thawing permafrost promotes microbial degradation of cryo-sequestered and new carbon leading to the biogenic production of methane, creating a positive feedback to climate change. Here we determine microbial community composition along a permafrost thaw gradient in northern Sweden. Partially thawed sites were frequently dominated by a single archaeal phylotype, Candidatus 'Methanoflorens stordalenmirensis' gen. nov. sp. nov., belonging to the uncultivated lineage 'Rice Cluster II' (Candidatus 'Methanoflorentaceae' fam. nov.). Metagenomic sequencing led to the recovery of its near-complete genome, revealing the genes necessary for hydrogenotrophic methanogenesis. These genes are highly expressed and methane carbon isotope data are consistent with hydrogenotrophic production of methane in the partially thawed site. In addition to permafrost wetlands, 'Methanoflorentaceae' are widespread in high methane-flux habitats suggesting that this lineage is both prevalent and a major contributor to global methane production. In thawing permafrost, Candidatus 'M. stordalenmirensis' appears to be a key mediator of methane-based positive feedback to climate warming.

A laboratory study of anaerobic oxidation of methane in the presence of methane hydrate

NASA Astrophysics Data System (ADS)

Solem, R.; Bartlett, D.; Kastner, M.; Valentine, D.

2003-12-01

In order to mimic and study the process of anaerobic methane oxidation in methane hydrate regions we developed four high-pressure anaerobic bioreactors, designed to incubate environmental sediment samples, and enrich for populations of microbes associated with anaerobic methane oxidation (AMO). We obtained sediment inocula from a bacterial mat at the southern Hydrate Ridge, Cascadia, having cell counts approaching 1010 cells/cc. Ultimately, our goal is to produce an enriched culture of these microbes for characterization of the biochemical processes and chemical fluxes involved, as well as the unique adaptations required for, AMO. Molecular phylogenetic information along with results from fluorescent in situ hybridization indicate that consortia of Archaea and Bacteria are present which are related to those previously described for marine sediment AMO environments. Using a medium of enriched seawater and sediment in a 3:1 ratio, the system was incubated at 4° C under 43 atm of methane pressure; the temperature and pressure were kept constant. We have followed the reactions for seven months, particularly the vigorous consumption rates of dissolved sulfate and alkalinity production, as well as increases in HS-, and decreases in Ca concentrations. We also monitored the dissolved inorganic C (DIC) δ 13C values. The data were reproduced, and indicated that the process is extremely sensitive to changes in methane pressure. The rates of decrease in sulfate and increase in alkalinity concentrations were complimentary and showed considerable linearity with time. When the pressure in the reactor was decreased below the methane hydrate stability field, following the methane hydrate dissociation, sulfate reduction abruptly decreased. When the pressure was restored all the reactions returned to their previous rates. Much of the methane oxidation activity in the reactor is believed to occur in association with the methane hydrate. Upon the completion of one of the experiments, the chamber methane hydrate, liquid phase, and sediment were separated. FISH analyses of the dissociated hydrate fluid indicate a significant presence of Archaea in or on the hydrate. The cell densities in the bioreactor medium liquid phase were 7.2 x 107 cells/cc, and with the methane hydrate, 2.8 x 108 cells/cc.

A case study of methane gas migration through sealed mine GOB into active mine workings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garcia, F.; McCall, F.E.; Trevits, M.A.

1995-12-31

The U.S. Bureau of Mines investigated the influence of atmospheric pressure changes on methane gas migration through mine seals at a mine site located in the Pittsburgh Coalbed. The mine gained access to a coal reserve through part of an abandoned mine and constructed nine seals to isolate the extensive old workings from the active mine area. Underground problems were experienced when atmospheric pressure fell, causing methane gas to migrate around the seals and into the active workings. During mining operations, methane gas levels exceeded legal limits and coal production was halted until the ventilation system could be improved. Whenmore » mining resumed with increased air flow, methane gas concentrations occasionally exceeded the legal limits and production had to be halted until the methane level fell within the mandated limit. To assist the ventilation system, a pressure relief borehole located in the abandoned workings near the mine seals was proposed. Preliminary estimates by a gob gas simulator (computer model) suggested that a 0.76 m (2.5 ft) diameter pressure relief borehole with an exhaust fan would be necessary to remove enough methane from the abandoned area so that the ventilation system could dilute the gas in the active workings. However, by monitoring methane gas emissions and seal pressure, during periods of low atmospheric pressure, the amount of methane gas that migrated into the active mine workings was calculated. Researchers then determined that a relief borehole, 20.3 cm (8-in) with an exhaust fan could remove at least twice the maximum measured volume of migrating methane gas. Because gas concentrations in the abandoned workings could potentially reach explosive limits, it was proposed that the mine eliminate the exhaust fan. Installation of the recommended borehole and enlarging two other ventilation boreholes located In the abandoned area reduced methane gas leakage through the seals by at least 63%.« less

Spatial and Temporal Variations in the Partial Pressure and Emission of CO2 and CH4 in and Amazon Floodplain Lake

NASA Astrophysics Data System (ADS)

Forsberg, B. R.; Amaral, J. H.; Barbosa, P.; Kasper, D.; MacIntyre, S.; Cortes, A.; Sarmento, H.; Borges, A. V.; Melack, J. M.; Farjalla, V.

2015-12-01

The Amazon floodplain contains a variety of wetland environments which contribute CO2 and CH4 to the regional and global atmospheres. The partial pressure and emission of these greenhouse gases (GHGs) varies: 1) between habitats, 2) seasonally, as the characteristics these habitats changes and 3) diurnally, in response to diurnal stratification. In this study, we investigated the combined influence of these factors on the partial pressure and emission of GHGs in Lago Janauacá, a central Amazon floodplain lake (3o23' S; 60o18' O). All measurements were made between August of 2014 and April of 2015 at two different sites and in three distinct habitats: open water, flooded forest, flooded macrophytes. Concentrations of CO2 and CH4 in air were measured continuously with a cavity enhanced absorption spectrometer, Los Gatos Research´s Ultraportable Greenhouse Gas Analyzer (UGGA). Vertical profiles o pCO2 and pCH4 were measured using the UGGA connected to an electric pump and equilibrator. Diffusive surface emissions were estimated with the UGGA connected to a static floating chamber. To investigate the influence of vertical stratification and mixing on GHG partial pressure and emissions, a meteorological station and submersible sensor chain were deployed at each site. Meteorological sensors included wind speed and direction. The submersible chains included thermistors and oxygen sensors. Depth profiles of partial pressure and diffusive emissions for both CO2 and CH4 varied diurnally, seasonally and between habitats. Both pCO2 and pCH4 were consistently higher in bottom than surface waters with the largest differences occurring at high water when thermal stratification was most stable. Methane emissions and partial pressures were highest at low water while pCO2 and CO2 fluxes were highest during high water periods, with 35% of CO2 fluxes at low water being negative. The highest average surface value of pCO2 (5491 μatm), encountered during rising water, was ~3 times higher than that encountered at low water (1708 μatm). Partial pressures and emissions of both CO2 and CH4 were greatest in open water habitats and consistently higher at night. These patterns reflected the higher levels of wind driven mixing and turbulence in open water environments and higher convective mixing at night which promoted diffusive emission.

Publications - GMC 278 | Alaska Division of Geological & Geophysical

Science.gov Websites

DGGS GMC 278 Publication Details Title: High pressure methane adsorption analyses for coal samples of the Matanuska Valley coal-bed methane AK 94-CBM-1 hole as follows: Seam #1, Seam #6, Seam #9, and Seam , High pressure methane adsorption analyses for coal samples of the Matanuska Valley coal-bed methane AK

Stress and Dilatancy Relation of Methane Hydrate Bearing Sand with Various Fines Content

NASA Astrophysics Data System (ADS)

Hyodo, M.

2016-12-01

This study presents an experimental and numerical study on the shear behaviour of methane hydrate bearing sand with variable confining pressures and methane hydrate saturations. A representative grading curve of Nankai Trough is selected as the grain size distribution of host sand to artificially produce the methane hydrate bearing sand. A shear strength estimation equation for methane hydrate bearing sand from test results is established. A simple constitutive model has been proposed to predict the stress-strain response of methane hydrate bearing sand based on a few well-known relationships. Experimental results indicate that the inclination of stress-dilatancy curve becomes steeper with a rise in methane hydrate saturation. A revised stress-dilatancy equation has been integrated with this simple model to consider the variance in the inclination of stress-dilatancy curve. The mean stress Pcr at critical state when the peak stress ratio reduces to the residual stress ratio increases with the level of methane hydrate saturation. The dilatancy parameter a tends to increase with the methane hydrate saturation. The shear deformability parameter A exhibits a decreasing tendency with the rise in methane hydrate saturation at each confining pressure. This model is capable of reasonably predicting the strength and stiffness enhancement and the dilation behaviour as methane hydrate saturation increases. The volumetric variation from contraction to expansion of MH bearing sand at a lower confining pressure and only pure volumetric contraction a higher confining pressure can be represented by this simple model.

Transition mechanism of sH to filled-ice Ih structure of methane hydrate under fixed pressure condition

NASA Astrophysics Data System (ADS)

Kadobayashi, H.; Hirai, H.; Ohfuji, H.; Kojima, Y.; Ohishi, Y.; Hirao, N.; Ohtake, M.; Yamamoto, Y.

2017-10-01

The phase transition mechanism of methane hydrate from sH to filled-ice Ih structure was examined using a combination of time-resolved X-ray diffractometry (XRD) and Raman spectroscopy in conjunction with charge-coupled device (CCD) camera observation under fixed pressure conditions. Prior to time-resolved Raman experiments, the typical C-H vibration modes and their pressure dependence of three methane hydrate structures, fluid methane and solid methane were measured using Raman spectroscopy to distinguish the phase transitions of methane hydrates from decomposition to solid methane and ice VI or VII. Experimental results by XRD, Raman spectroscopy and CCD camera observation revealed that the structural transition of sH to filled-ice Ih occurs through a collapse of the sH framework followed by the release of fluid methane that is then gradually incorporated into the filled-ice Ih to reconstruct its structure. These observations suggest that the phase transition of sH to filled-ice Ih takes place by a typical reconstructive mechanism.

Experimental Study on Properties of Methane Diffusion of Coal Block under Triaxial Compressive Stress

PubMed Central

Zhao, Hong-Bao

2014-01-01

Taking the standard size coal block samples defined by ISRM as research objects, both properties of methane diffusion of coal block under triaxial compressive stress and characteristic influences caused by methane pressure were systematically studied with thermo-fluid-solid coupling with triaxial servocontrolled seepage equipment of methane-containing coal. The result shows the methane diffusion property of coal block under triaxial compressive stress was shown in four-stage as follow, first is sharply reduce stage, second is hyperbolic reduce stage, third is close to a fixed value stage, fourth stage is 0. There is a special point making the reduced rate of characteristic curve of methane diffusion speed become sharply small; the influences of shape of methane diffusion speed characteristic curve caused by methane pressure are not obvious, which only is shown in numerical size of methane diffusion speed. Test time was extended required by appear of the special point makes the reduce rate of methane diffusion speed become sharply small. The fitting four-phase relation of methane diffusion of coal block under triaxial compressive stress was obtained, and the idea is proposed that influences of the fitting four-phase relation caused by methane pressure were only shown in value of fitting parameters. PMID:25531000

Low pressure microenvironments: Methane production at 50 mbar and 100 mbar by methanogens

NASA Astrophysics Data System (ADS)

Mickol, Rebecca L.; Kral, Timothy A.

2018-04-01

Low pressure is often overlooked in terms of possible biocidal effects when considering a habitable environment on Mars. Few experiments have investigated the ability for microorganisms to actively grow under low pressure conditions, despite the atmosphere being a location on Earth where organisms could be exposed to these pressures. Three species of methanogens (Methanobacterium formicicum, Methanosarcina barkeri, Methanococcus maripaludis) were tested for their ability to actively grow (demonstrate an increase in methane production and optical density) within low-pressure microenvironments at 50 mbar or 100 mbar. M. formicicum was the only species to demonstrate both an increase in methane and an increase in optical density during the low-pressure exposure period for experiments conducted at 50 mbar and 100 mbar. In certain experiments, M. barkeri showed an increase in optical density during the low-pressure exposure period, likely due to the formation of multicellular aggregates, but minimal methane production (<1%). During incubation following exposure to low pressure, cultures of all species resumed methane production and increased in optical density. Thus, low pressure may not be a biocidal factor for certain methanogen species, with growth possible under low-pressure conditions. Results indicate that low pressure exposure may just be inhibitory during the exposure itself, and metabolism may resume following incubation under more ideal conditions. Further work is needed to address growth/survival under Mars surface pressures.

Regimes of an atmospheric pressure nanosecond repetitively pulsed discharge for methane partial oxidation

NASA Astrophysics Data System (ADS)

Maqueo, P. D. G.; Maier, M.; Evans, M. D. G.; Coulombe, S.; Bergthorson, J. M.

2018-04-01

The operation of a nanosecond repetitively pulsed discharge for partial oxidation of CH4 is characterized at atmospheric pressure and room temperature. Two regimes are observed: diffuse and filamentary. The first is a low power regime, characterized by low rotational temperatures around 400 K. The second is much more energetic with rotational temperatures close to 600 K. Both have vibrational temperatures of at least 10 times their rotational temperatures. The average electron number density was determined to be 8.9×1015 and 4.0×1017 cm-3, respectively, showing an increase in the ionization fraction in the more powerful filamentary regime. Results of CH4 conversion to H2, CO, CO2 and C2H6 are presented for the filamentary regime, while the diffuse regime shows no measurable conversion ability. As expected, oxidative mixtures show higher conversion ability than pure CH4. A maximum conversion efficiency of 26.3% and a maximum energy efficiency of 19.7% were reached for the oxidative mixtures.

Factors controlling headspace pressure in a manual manometric BMP method can be used to produce a methane output comparable to AMPTS.

PubMed

Himanshu, H; Voelklein, M A; Murphy, J D; Grant, J; O'Kiely, P

2017-08-01

The manual manometric biochemical methane potential (mBMP) test uses the increase in pressure to calculate the gas produced. This gas production may be affected by the headspace volume in the incubation bottle and by the overhead pressure measurement and release (OHPMR) frequency. The biogas and methane yields of cellulose, barley, silage and slurry were compared with three incubation bottle headspace volumes (50, 90 and 180ml; constant 70ml total medium) and four OHPMR frequencies (daily, each third day, weekly and solely at the end of experiment). The methane yields of barley, silage and slurry were compared with those from an automated volumetric method (AMPTS). Headspace volume and OHPMR frequency effects on biogas yield were mediated mainly through headspace pressure, with the latter having a negative effect on the biogas yield measured and relatively little effect on methane yield. Two mBMP treatments produced methane yields equivalent to AMPTS. Copyright © 2017 Elsevier Ltd. All rights reserved.

High pressure and temperature optical flow cell for near-infra-red spectroscopic analysis of gas mixtures.

PubMed

Norton, C G; Suedmeyer, J; Oderkerk, B; Fieback, T M

2014-05-01

A new optical flow cell with a new optical arrangement adapted for high pressures and temperatures using glass fibres to connect light source, cell, and spectrometer has been developed, as part of a larger project comprising new methods for in situ analysis of bio and hydrogen gas mixtures in high pressure and temperature applications. The analysis is based on measurements of optical, thermo-physical, and electromagnetic properties in gas mixtures with newly developed high pressure property sensors, which are mounted in a new apparatus which can generate gas mixtures with up to six components with an uncertainty of composition of as little as 0.1 mol. %. Measurements of several pure components of natural gases and biogases to a pressure of 20 MPa were performed on two isotherms, and with binary mixtures of the same pure gases at pressures to 17.5 MPa. Thereby a new method of analyzing the obtained spectra based on the partial density of methane was investigated.

Simultaneous enrichment of denitrifying anaerobic methane-oxidizing microorganisms and anammox bacteria in a hollow-fiber membrane biofilm reactor.

PubMed

Ding, Zhao-Wei; Lu, Yong-Ze; Fu, Liang; Ding, Jing; Zeng, Raymond J

2017-01-01

In this study, the coculture system of denitrifying anaerobic methane oxidation (DAMO) microbes and anaerobic ammonium oxidation (anammox) bacteria was successfully enriched in a hollow-fiber membrane biofilm reactor (HfMBR) using freshwater sediment as the inoculum. The maximal removal rates of nitrate and ammonium were 78 mg N/L/day (131 mg N/m 2 /day) and 26 mg N/L/day (43 mg N/m 2 /day), respectively. Due to the high rate of methane mass transfer in HfMBR, the activity of DAMO archaea continued to increase during the enrichment period, indicating that HfMBR could be a powerful tool to enrich DAMO microorganisms. Effects of partial methane pressure, temperature, and pH on the cocultures were obvious. However, the microbial activity in HfMBR could be recovered quickly after the shock change of environmental factors. Furthermore, the result also found that DAMO bacteria likely had a stronger competitive advantage than anammox bacteria under the operating conditions in this study. High-throughput sequencing 16S rRNA genes illustrated that the dominant microbes were NC10, Euryarchaeota, Proteobacteria, Planctomycetes, and Chlorobi with relative abundance of 38.8, 26.2, 13.78, 6.2, and 3.6 %, respectively.

On direct internal methane steam reforming kinetics in operating solid oxide fuel cells with nickel-ceria anodes

NASA Astrophysics Data System (ADS)

Thallam Thattai, A.; van Biert, L.; Aravind, P. V.

2017-12-01

Major operating challenges remain to safely operate methane fuelled solid oxide fuel cells due to undesirable temperature gradients across the porous anode and carbon deposition. This article presents an experimental study on methane steam reforming (MSR) global kinetics for single operating SOFCs with Ni-GDC (gadolinium doped ceria) anodes for low steam to carbon (S/C) ratios and moderate current densities. The study points out the hitherto insufficient research on MSR global and intrinsic kinetics for operating SOFCs with complete Ni-ceria anodes. Further, it emphasizes the need to develop readily applicable global kinetic models as a subsequent step from previously reported state-of-art and complex intrinsic models. Two rate expressions of the Power law (PL) and Langmuir-Hinshelwood (LH) type have been compared and based on the analysis, limitations of using previously proposed rate expressions for Ni catalytic beds to study MSR kinetics for complete cermet anodes have been identified. Firstly, it has been shown that methane reforming on metallic (Ni) current collectors may not be always negligible, contrary to literature reports. Both PL and LH kinetic models predict significantly different local MSR reaction rate and species partial pressure distributions along the normalized reactor length, indicating a strong need for further experimental verifications.

Simultaneous hydrogen utilization and in situ biogas upgrading in an anaerobic reactor.

PubMed

Luo, Gang; Johansson, Sara; Boe, Kanokwan; Xie, Li; Zhou, Qi; Angelidaki, Irini

2012-04-01

The possibility of converting hydrogen to methane and simultaneous upgrading of biogas was investigated in both batch tests and fully mixed biogas reactor, simultaneously fed with manure and hydrogen. Batch experiments showed that hydrogen could be converted to methane by hydrogenotrophic methanogenesis with conversion of more than 90% of the consumed hydrogen to methane. The hydrogen consumption rates were affected by both P(H₂) (hydrogen partial pressure) and mixing intensity. Inhibition of propionate and butyrate degradation by hydrogen (1 atm) was only observed under high mixing intensity (shaking speed 300 rpm). Continuous addition of hydrogen (flow rate of 28.6 mL/(L/h)) to an anaerobic reactor fed with manure, showed that more than 80% of the hydrogen was utilized. The propionate and butyrate level in the reactor was not significantly affected by the hydrogen addition. The methane production rate of the reactor with H₂ addition was 22% higher, compared to the control reactor only fed with manure. The CO₂ content in the produced biogas was only 15%, while it was 38% in the control reactor. However, the addition of hydrogen resulted in increase of pH (from 8.0 to 8.3) due to the consumption of bicarbonate, which subsequently caused slight inhibition of methanogenesis. Copyright © 2011 Wiley Periodicals, Inc.

Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ok, Salim; Hoyt, David W.; Andersen, Amity

Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nanoporous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, we observed changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) with 13C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed nonporous, 12 nm particle size silica and a mesoporous silica with 200more » nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. There was no significant thermal effects were found for the observed 13C chemical shifts at all pressures studied here (28.2, 32.6, 56.4, 65.1, 112.7, and 130.3 bar) for pure methane. However, the 13C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of 13C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD, and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.« less

Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study

DOE PAGES

Ok, Salim; Hoyt, David W.; Andersen, Amity; ...

2017-01-18

Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nanoporous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, we observed changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) with 13C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed nonporous, 12 nm particle size silica and a mesoporous silica with 200more » nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. There was no significant thermal effects were found for the observed 13C chemical shifts at all pressures studied here (28.2, 32.6, 56.4, 65.1, 112.7, and 130.3 bar) for pure methane. However, the 13C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of 13C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD, and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.« less

Surface Interactions and Confinement of Methane: A High Pressure Magic Angle Spinning NMR and Computational Chemistry Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ok, Salim; Hoyt, David W.; Andersen, Amity

Characterization and modeling of the molecular-level behavior of simple hydrocarbon gases, such as methane, in the presence of both nonporous and nano-porous mineral matrices allows for predictive understanding of important processes in engineered and natural systems. In this study, changes in local electromagnetic environments of the carbon atoms in methane under conditions of high pressure (up to 130 bar) and moderate temperature (up to 346 K) were observed with 13C magic-angle spinning (MAS) NMR spectroscopy while the methane gas was mixed with two model solid substrates: a fumed non-porous, 12 nm particle size silica and a mesoporous silica with 200more » nm particle size and 4 nm average pore diameter. Examination of the interactions between methane and the silica systems over temperatures and pressures that include the supercritical regime was allowed by a novel high pressure MAS sample containment system, which provided high resolution spectra collected under in situ conditions. For pure methane, no significant thermal effects were found for the observed 13C chemical shifts at all pressures studied here (28.2 bar, 32.6 bar, 56.4 bar, 65.1 bar, 112.7 bar, and 130.3 bar). However, the 13C chemical shifts of resonances arising from confined methane changed slightly with changes in temperature in mixtures with mesoporous silica. The chemical shift values of 13C nuclides in methane change measurably as a function of pressure both in the pure state and in mixtures with both silica matrices, with a more pronounced shift when meso-porous silica is present. Molecular-level simulations utilizing GCMC, MD and DFT confirm qualitatively that the experimentally measured changes are attributed to interactions of methane with the hydroxylated silica surfaces as well as densification of methane within nanopores and on pore surfaces.« less

Temperature- and pressure-dependent structural transformation of methane hydrates in salt environments

NASA Astrophysics Data System (ADS)

Shin, Donghoon; Cha, Minjun; Yang, Youjeong; Choi, Seunghyun; Woo, Yesol; Lee, Jong-Won; Ahn, Docheon; Im, Junhyuck; Lee, Yongjae; Han, Oc Hee; Yoon, Ji-Ho

2017-03-01

Understanding the stability of volatile species and their compounds under various surface and subsurface conditions is of great importance in gaining insights into the formation and evolution of planetary and satellite bodies. We report the experimental results of the temperature- and pressure-dependent structural transformation of methane hydrates in salt environments using in situ synchrotron X-ray powder diffraction, solid-state nuclear magnetic resonance, and Raman spectroscopy. We find that under pressurized and concentrated brine solutions methane hydrate forms a mixture of type I clathrate hydrate, ice, and hydrated salts. Under a low-pressure condition, however, the methane hydrates are decomposed through a rapid sublimation of water molecules from the surface of hydrate crystals, while NaCl · 2H2O undergoes a phase transition into a crystal growth of NaCl via the migration of salt ions. In ambient pressure conditions, the methane hydrate is fully decomposed in brine solutions at temperatures above 252 K, the eutectic point of NaCl · 2H2O.

Low-temperature superacid catalysis: Reactions of n - butane and propane catalyzed by iron- and manganese-promoted sulfated zirconia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsz-Keung, Cheung; d`Itri, J.L.; Lange, F.C.

1995-12-31

The primary goal of this project is to evaluate the potential value of solid superacid catalysts of the sulfated zirconia type for light hydrocarbon conversion. The key experiments catalytic testing of the performance of such catalysts in a flow reactor fed with streams containing, for example, n-butane or propane. Fe- and Mn-promoted sulfated zirconia was used to catalyze the conversion of n-butane at atmospheric pressure, 225-450{degrees}C, and n-butane partial pressures in the range of 0.0025-0.01 atm. At temperatures <225{degrees}C, these reactions were accompanied by cracking; at temperatures >350{degrees}C, cracking and isomerization occurred. Catalyst deactivation, resulting at least in part frommore » coke formation, was rapid. The primary cracking products were methane, ethane, ethylene, and propylene. The observation of these products along with an ethane/ethylene molar ratio of nearly 1 at 450{degrees}C is consistent with cracking occurring, at least in part, by the Haag-Dessau mechanism, whereby the strongly acidic catalyst protonates n-butane to give carbonium ions. The rate of methane formation from n-butane cracking catalyzed by Fe- and Mn-promoted sulfated zirconia at 450{degrees}C was about 3 x 10{sup -8} mol/(g of catalyst {center_dot}s). The observation of butanes, pentanes, and methane as products is consistent with Olah superacid chemistry, whereby propane is first protonated by a very strong acid to form a carbonium ion. The carbonium ion then decomposes into methane and an ethyl cation which undergoes oligocondensation reactions with propane to form higher molecular weight alkanes. The results are consistent with the identification of iron- and manganese-promoted sulfated zirconia as a superacid.« less

Reconstructing Methane Emission Events in the Arctic Ocean: Observations from the Past to Present

NASA Astrophysics Data System (ADS)

Panieri, G.; Mienert, J.; Fornari, D. J.; Torres, M. E.; Lepland, A.

2015-12-01

Methane hydrates are ice-like crystals that are present along continental margins, occurring in the pore space of deep sediments or as massive blocks near the seafloor. They form in high pressure and low temperature environments constrained by thermodynamic stability, and supply of methane. In the Arctic, gas hydrates are abundant, and the methane released by their destabilization can affect local to global carbon budgets and cycles, ocean acidification, and benthic community survival. With the aim to locate in space and time the periodicity of methane venting, CAGE is engaged in a vast research program in the Arctic, a component of which comprises the analyses of numerous sediment cores and correlative geophysical and geochemical data from different areas. Here we present results from combined analyses of biogenic carbonate archives along the western Svalbard Margin, which reveal past methane venting events in this region. The reconstruction of paleo-methane discharge is complicated by precipitation of secondary carbonate on foraminifera shells, driven by an increase in alkalinity during anaerobic oxidation of methane (AOM). The biogeochemical processes involved in methane cycling and processes that drive methane migration affect the depth where AOM occurs, with relevance to secondary carbonate formation. Our results show the value and complexity of separating primary vs. secondary signals in bioarchives with relevance to understanding fluid-burial history in methane seep provinces. Results from our core analyses are integrated with observations made during the CAGE15-2 cruise in May 2015, when we deployed a towed vehicle equipped with camera, multicore and water sampling capabilities. The instrument design was based on the Woods Hole Oceanographic Institution (WHOI) MISO TowCam sled equipped with a deep-sea digital camera and CTD real-time system. Sediment sampling was visually-guided using this system. In one of the pockmarks along the Vestnesa Ridge where high methane discharge was measured, we deployed the CAGE 888 marker as our first step in conducting time series studies to establish temporal variability going forward. This research is partially supported by the Research Council of Norway through its Centres of Excellence funding scheme, project number 223259.

Preparation of Ti3C2 and Ti2C MXenes by fluoride salts etching and methane adsorptive properties

NASA Astrophysics Data System (ADS)

Liu, Fanfan; Zhou, Aiguo; Chen, Jinfeng; Jia, Jin; Zhou, Weijia; Wang, Libo; Hu, Qianku

2017-09-01

Here we reported the preparation of Ti3C2 MXene and Ti2C MXene by etching Ti3AlC2 and Ti2AlC with various fluoride salts in hydrochloric acid (HCl), including lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), and ammonium fluoride (NH4F). As-prepared Ti2C was further delaminated by urea, dimethylsulfoxide or ammonium hydroxide. Based on theoretical calculation and XPS results, the type of positive ions (Li+, Na+, K+, or NH4+) in etchant solution affect the surface structure of prepared MXene, which, in turn, affects the methane adsorption properties of MXene. The highest methane adsorption capacity is 8.5 cm3/g for Ti3C2 and 11.6 cm3/g for Ti2C. MXenes made from LiF and NH4F can absorb methane under high pressure and can keep methane under normal pressure, these MXenes may have important application on capturing methane or other hazardous gas molecules. MXenes made from NaF and KF can absorb methane under high pressure and release methane under low pressure. They can have important application in the adsorb storage of nature gas.

Tables of critical-flow functions and thermodynamic properties for methane and computational procedures for both methane and natural gas

NASA Technical Reports Server (NTRS)

Johnson, R. C.

1972-01-01

Procedures for calculating the mass flow rate of methane and natural gas through nozzles are given, along with the FORTRAN 4 subroutines used to make these calculations. Three sets of independent variables are permitted in these routines. In addition to the plenum pressure and temperature, the third independent variable is either nozzle exit pressure, Mach number, or temperature. A critical-flow factor that becomes a convenient means for determining the mass flow rate of methane through critical-flow nozzles is tabulated. Other tables are included for nozzle throat velocity and critical pressure, density, and temperature ratios, along with some thermodynamic properties of methane, including compressibility factor, enthalpy, entropy, specific heat, specific-heat ratio, and speed of sound. These tabulations cover a temperature range from 120 to 600 K and pressures to 3 million N/sq m.

Molecular dynamics study of structure H clathrate hydrates of methane and large guest molecules.

PubMed

Susilo, Robin; Alavi, Saman; Ripmeester, John A; Englezos, Peter

2008-05-21

Methane storage in structure H (sH) clathrate hydrates is attractive due to the relatively higher stability of sH as compared to structure I methane hydrate. The additional stability is gained without losing a significant amount of gas storage density as happens in the case of structure II (sII) methane clathrate. Our previous work has showed that the selection of a specific large molecule guest substance (LMGS) as the sH hydrate former is critical in obtaining the optimum conditions for crystallization kinetics, hydrate stability, and methane content. In this work, molecular dynamics simulations are employed to provide further insight regarding the dependence of methane occupancy on the type of the LMGS and pressure. Moreover, the preference of methane molecules to occupy the small (5(12)) or medium (4(3)5(6)6(3)) cages and the minimum cage occupancy required to maintain sH clathrate mechanical stability are examined. We found that thermodynamically, methane occupancy depends on pressure but not on the nature of the LMGS. The experimentally observed differences in methane occupancy for different LMGS may be attributed to the differences in crystallization kinetics and/or the nonequilibrium conditions during the formation. It is also predicted that full methane occupancies in both small and medium clathrate cages are preferred at higher pressures but these cages are not fully occupied at lower pressures. It was found that both small and medium cages are equally favored for occupancy by methane guests and at the same methane content, the system suffers a free energy penalty if only one type of cage is occupied. The simulations confirm the instability of the hydrate when the small and medium cages are empty. Hydrate decomposition was observed when less than 40% of the small and medium cages are occupied.

Rapid and Simple Capillary-Rise/Vanishing Interfacial Tension Method To Determine Crude Oil Minimum Miscibility Pressure: Pure and Mixed CO 2, Methane, and Ethane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hawthorne, Steven B.; Miller, David J.; Jin, Lu

Here, we report a simplification of the capillary-rise/vanishing interfacial tension (IFT) method to measure minimum miscibility pressure (MMP) based on only requiring knowledge of when the interfacial tension approaches zero. Simply measuring the height of the crude oil in a capillary at several pressures from ambient to near the MMP pressure and extrapolating the oil height versus pressure plot to zero oil height yields the MMP without the need of the additional instrumentation and labor required to perform actual IFT measurements. A total of 2-4 MMP values can be determined per day with only one experimental apparatus, and the methodmore » greatly reduces the initial cost and complexity of the required instrumentation. The use of three capillaries having different inner diameters allows for triplicate determinations of MMP from each experiment. Because the actual MMP pressure need not be reached during the experiment, MMP values that exceed the pressure ratings of the equipment can be reasonably estimated (e.g., MMPs using pure nitrogen). The method was used to determine the MMP pressure for crude oil samples from a conventional Muddy Formation reservoir in the Powder River Basin [American Petroleum Institute (API) gravity of 35.8°] and an unconventional Bakken Formation reservoir in the Williston Basin (API gravity of 38.7°). The method is reproducible [typically <4% relative standard deviation (RSD)], and the method gave good agreement for a “live” Bakken oil with the results from a slim tube test of a commercial laboratory. Approximately 80 MMP values were measured using pure CO 2, methane, and ethane as well as 0-100% mole ratios of methane/CO 2 and methane/ethane. For both oil samples, ethane MMPs were ca. one-half those with CO 2, while methane MMPs were ca. double or triple those with CO 2. MMPs with mixed methane/CO 2 showed a linear increase with mole percent methane for both crude oils, while both oils showed an exponential increase in MMP with mole percent methane in ethane, with a little increase in MMP until ca. 20 mol % methane in ethane.« less

Rapid and Simple Capillary-Rise/Vanishing Interfacial Tension Method To Determine Crude Oil Minimum Miscibility Pressure: Pure and Mixed CO 2, Methane, and Ethane

DOE PAGES

Hawthorne, Steven B.; Miller, David J.; Jin, Lu; ...

2016-07-10

Here, we report a simplification of the capillary-rise/vanishing interfacial tension (IFT) method to measure minimum miscibility pressure (MMP) based on only requiring knowledge of when the interfacial tension approaches zero. Simply measuring the height of the crude oil in a capillary at several pressures from ambient to near the MMP pressure and extrapolating the oil height versus pressure plot to zero oil height yields the MMP without the need of the additional instrumentation and labor required to perform actual IFT measurements. A total of 2-4 MMP values can be determined per day with only one experimental apparatus, and the methodmore » greatly reduces the initial cost and complexity of the required instrumentation. The use of three capillaries having different inner diameters allows for triplicate determinations of MMP from each experiment. Because the actual MMP pressure need not be reached during the experiment, MMP values that exceed the pressure ratings of the equipment can be reasonably estimated (e.g., MMPs using pure nitrogen). The method was used to determine the MMP pressure for crude oil samples from a conventional Muddy Formation reservoir in the Powder River Basin [American Petroleum Institute (API) gravity of 35.8°] and an unconventional Bakken Formation reservoir in the Williston Basin (API gravity of 38.7°). The method is reproducible [typically <4% relative standard deviation (RSD)], and the method gave good agreement for a “live” Bakken oil with the results from a slim tube test of a commercial laboratory. Approximately 80 MMP values were measured using pure CO 2, methane, and ethane as well as 0-100% mole ratios of methane/CO 2 and methane/ethane. For both oil samples, ethane MMPs were ca. one-half those with CO 2, while methane MMPs were ca. double or triple those with CO 2. MMPs with mixed methane/CO 2 showed a linear increase with mole percent methane for both crude oils, while both oils showed an exponential increase in MMP with mole percent methane in ethane, with a little increase in MMP until ca. 20 mol % methane in ethane.« less

Thermodynamic properties of hydrate phases immersed in ice phase

NASA Astrophysics Data System (ADS)

Belosludov, V. R.; Subbotin, O. S.; Krupskii, D. S.; Ikeshoji, T.; Belosludov, R. V.; Kawazoe, Y.; Kudoh, J.

2006-01-01

Thermodynamic properties and the pressure of hydrate phases immersed in the ice phase with the aim to understand the nature of self-preservation effect of methane hydrate in the framework of macroscopic and microscopic molecular models was studied. It was show that increasing of pressure is happen inside methane hydrate phases immersed in the ice phase under increasing temperature and if the ice structure does not destroy, the methane hydrate will have larger pressure than ice phase. This is because of the thermal expansion of methane hydrate in a few times larger than ice one. The thermal expansion of the hydrate is constrained by the thermal expansion of ice because it can remain in a region of stability within the methane hydrate phase diagram. The utter lack of preservation behavior in CS-II methane- ethane hydrate can be explain that the thermal expansion of ethane-methane hydrate coincide with than ice one it do not pent up by thermal expansion of ice. The pressure and density during the crossing of interface between ice and hydrate was found and dynamical and thermodynamic stability of this system are studied in accordance with relation between ice phase and hydrate phase.

Methane Post-Processor Development to Increase Oxygen Recovery beyond State-of-the-Art Carbon Dioxide Reduction Technology

NASA Technical Reports Server (NTRS)

Abney, Morgan; Miller, Lee; Greenwood, Zach; Iannantuono, Michelle; Jones, Kenny

2013-01-01

State-of-the-art life support carbon dioxide (CO2) reduction technology, based on the Sabatier reaction, is theoretically capable of 50% recovery of oxygen from metabolic CO2. This recovery is constrained by the limited availability of reactant hydrogen. Post-processing of the methane byproduct from the Sabatier reactor results in hydrogen recycle and a subsequent increase in oxygen recovery. For this purpose, a Methane Post-Processor Assembly containing three sub-systems has been developed and tested. The assembly includes a Methane Purification Assembly (MePA) to remove residual CO2 and water vapor from the Sabatier product stream, a Plasma Pyrolysis Assembly (PPA) to partially pyrolyze methane into hydrogen and acetylene, and an Acetylene Separation Assembly (ASepA) to purify the hydrogen product for recycle. The results of partially integrated testing of the sub-systems are reported.

Methane Post-Processor Development to Increase Oxygen Recovery beyond State-of-the-Art Carbon Dioxide Reduction Technology

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Greenwood, Zachary; Miller, Lee A.; Alvarez, Giraldo; Iannantuono, Michelle; Jones, Kenny

2013-01-01

State-of-the-art life support carbon dioxide (CO2) reduction technology, based on the Sabatier reaction, is theoretically capable of 50% recovery of oxygen from metabolic CO2. This recovery is constrained by the limited availability of reactant hydrogen. Post-processing of the methane byproduct from the Sabatier reactor results in hydrogen recycle and a subsequent increase in oxygen recovery. For this purpose, a Methane Post-Processor Assembly containing three sub-systems has been developed and tested. The assembly includes a Methane Purification Assembly (MePA) to remove residual CO2 and water vapor from the Sabatier product stream, a Plasma Pyrolysis Assembly (PPA) to partially pyrolyze methane into hydrogen and acetylene, and an Acetylene Separation Assembly (ASepA) to purify the hydrogen product for recycle. The results of partially integrated testing of the sub-systems are reported

Methane heat transfer investigation

NASA Technical Reports Server (NTRS)

1984-01-01

Future high chamber pressure LOX/hydrocarbon booster engines require copper base alloy main combustion chamber coolant channels similar to the SSME to provide adequate cooling and reusable engine life. Therefore, it is of vital importance to evaluate the heat transfer characteristics and coking thresholds for LNG (94% methane) cooling, with a copper base alloy material adjacent to he fuel coolant. High pressure methane cooling and coking characteristics recently evaluated at Rocketdyne using stainless steel heated tubes at methane bulk temperatures and coolant wall temperatures typical of advanced engine operation except at lower heat fluxes as limited by the tube material. As expected, there was no coking observed. However, coking evaluations need be conducted with a copper base surface exposed to the methane coolant at higher heat fluxes approaching those of future high chamber pressure engines.

Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria

USGS Publications Warehouse

Coleman, D.D.; Risatti, J.B.; Schoell, M.

1981-01-01

Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by these bacteria could therefore be misinterpreted. We cultured methane-oxidizing bacteria at two different temperatures and monitored the carbon and hydrogen isotopic compositions of the residual methane. The residual methane was enriched in both 13C and D. For both isotopic species, the enrichment at equivalent levels of conversion was greater at 26??C than at 11.5??C. The change in ??D relative to the change in ??13C was independent of temperature within the range studied. One culture exhibited a change in the fractionation pattern for carbon (but not for hydrogen) midway through the experiment, suggesting that bacterial oxidation of methane may occur via more than one pathway. The change in the ??D value for the residual methane was from 8 to 14 times greater than the change in the ??13C value, indicating that combined carbon and hydrogen isotopic analysis may be an effective way of identifying methane which has been subjected to partial oxidation by bacteria. ?? 1981.

Monocopper active site for partial methane oxidation in Cu-exchanged 8MR zeolites

DOE PAGES

Kulkarni, Ambarish R.; Zhao, Zhi -Jian; Siahrostami, Samira; ...

2016-08-17

Direct conversion of methane to methanol using oxygen is experiencing renewed interest owing to the availability of new natural gas resources. Copper-exchanged zeolites such as mordenite and ZSM-5 have shown encouraging results, and di- and tri-copper species have been suggested as active sites. Recently, small eight-membered ring (8MR) zeolites including SSZ-13, -16, and -39 have been shown to be active for methane oxidation, but the active sites and reaction mechanisms in these 8MR zeolites are not known. In this work, we use density functional theory (DFT) calculations to systematically evaluate monocopper species as active sites for the partial methane oxidationmore » reaction in Cu-exchanged SSZ-13. On the basis of kinetic and thermodynamic arguments, we suggest that [Cu IIOH] + species in the 8MR are responsible for the experimentally observed activity. Furthermore, our results successfully explain the available spectroscopic data and experimental observations including (i) the necessity of water for methanol extraction and (ii) the effect of Si/Al ratio on the catalyst activity. Monocopper species have not yet been suggested as an active site for the partial methane oxidation reaction, and our results suggest that [Cu IIOH] + active site may provide complementary routes for methane activation in zeolites in addition to the known [Cu–O–Cu] 2+ and Cu 3O 3 motifs.« less

Elasticity of methane hydrate phases at high pressure.

PubMed

Beam, Jennifer; Yang, Jing; Liu, Jin; Liu, Chujie; Lin, Jung-Fu

2016-04-21

Determination of the full elastic constants (cij) of methane hydrates (MHs) at extreme pressure-temperature environments is essential to our understanding of the elastic, thermodynamic, and mechanical properties of methane in MH reservoirs on Earth and icy satellites in the solar system. Here, we have investigated the elastic properties of singe-crystal cubic MH-sI, hexagonal MH-II, and orthorhombic MH-III phases at high pressures in a diamond anvil cell. Brillouin light scattering measurements, together with complimentary equation of state (pressure-density) results from X-ray diffraction and methane site occupancies in MH from Raman spectroscopy, were used to derive elastic constants of MH-sI, MH-II, and MH-III phases at high pressures. Analysis of the elastic constants for MH-sI and MH-II showed intriguing similarities and differences between the phases' compressional wave velocity anisotropy and shear wave velocity anisotropy. Our results show that these high-pressure MH phases can exhibit distinct elastic, thermodynamic, and mechanical properties at relevant environments of their respective natural reservoirs. These results provide new insight into the determination of how much methane exists in MH reservoirs on Earth and on icy satellites elsewhere in the solar system and put constraints on the pressure and temperature conditions of their environment.

Microchannel Reactors for ISRU Applications

NASA Astrophysics Data System (ADS)

Carranza, Susana; Makel, Darby B.; Blizman, Brandon; Ward, Benjamin J.

2005-02-01

Affordable planning and execution of prolonged manned space missions depend upon the utilization of local resources and the waste products which are formed in manned spacecraft and surface bases. Successful in-situ resources utilization (ISRU) will require component technologies which provide optimal size, weight, volume, and power efficiency. Microchannel reactors enable the efficient chemical processing of in situ resources. The reactors can be designed for the processes that generate the most benefit for each mission. For instance, propellants (methane) can be produced from carbon dioxide from the Mars atmosphere using the Sabatier reaction and ethylene can be produced from the partial oxidation of methane. A system that synthesizes ethylene could be the precursor for systems to synthesize ethanol and polyethylene. Ethanol can be used as a nutrient for Astrobiology experiments, as well as the production of nutrients for human crew (e.g. sugars). Polyethylene can be used in the construction of habitats, tools, and replacement parts. This paper will present recent developments in miniature chemical reactors using advanced Micro Electro Mechanical Systems (MEMS) and microchannel technology to support ISRU of Mars and lunar missions. Among other applications, the technology has been demonstrated for the Sabatier process and for the partial oxidation of methane. Microchannel reactors were developed based on ceramic substrates as well as metal substrates. In both types of reactors, multiple layers coated with catalytic material are bonded, forming a monolithic structure. Such reactors are readily scalable with the incorporation of extra layers. In addition, this reactor structure minimizes pressure drop and catalyst settling, which are common problems in conventional packed bed reactors.

Methane storage in nanoporous material at supercritical temperature over a wide range of pressures

PubMed Central

Wu, Keliu; Chen, Zhangxin; Li, Xiangfang; Dong, Xiaohu

2016-01-01

The methane storage behavior in nanoporous material is significantly different from that of a bulk phase, and has a fundamental role in methane extraction from shale and its storage for vehicular applications. Here we show that the behavior and mechanisms of the methane storage are mainly dominated by the ratio of the interaction between methane molecules and nanopores walls to the methane intermolecular interaction, and a geometric constraint. By linking the macroscopic properties of the methane storage to the microscopic properties of a system of methane molecules-nanopores walls, we develop an equation of state for methane at supercritical temperature over a wide range of pressures. Molecular dynamic simulation data demonstrates that this equation is able to relate very well the methane storage behavior with each of the key physical parameters, including a pore size and shape and wall chemistry and roughness. Moreover, this equation only requires one fitted parameter, and is simple, reliable and powerful in application. PMID:27628747

Rapid and Simple Capillary-Rise/Vanishing Interfacial Tension Method To Determine Crude Oil Minimum Miscibility Pressure: Pure and Mixed CO 2 , Methane, and Ethane

DOE PAGES

Hawthorne, Steven B.; Miller, David J.; Jin, Lu; ...

2016-07-20

We report here a simplification of the capillary-rise/vanishing interfacial tension (IFT) method to measure minimum miscibility pressure (MMP) based on only requiring knowledge of when the interfacial tension approaches zero. Simply measuring the height of the crude oil in a capillary at several pressures from ambient to near the MMP pressure and extrapolating the oil height versus pressure plot to zero oil height yields the MMP without the need of the additional instrumentation and labor required to perform actual IFT measurements. A total of 2−4 MMP values can be determined per day with only one experimental apparatus, and the methodmore » greatly reduces the initial cost and complexity of the required instrumentation. The use of three capillaries having different inner diameters allows for triplicate determinations of MMP from each experiment. Because the actual MMP pressure need not be reached during the experiment, MMP values that exceed the pressure ratings of the equipment can be reasonably estimated (e.g., MMPs using pure nitrogen). The method was used to determine the MMP pressure for crude oil samples from a conventional Muddy Formation reservoir in the Powder River Basin [American Petroleum Institute (API) gravity of 35.8°] and an unconventional Bakken Formation reservoir in the Williston Basin (API gravity of 38.7°). The method is reproducible [typically <4% relative standard deviation (RSD)], and the method gave good agreement for a “live” Bakken oil with the results from a slim tube test of a commercial laboratory. Approximately 80 MMP values were measured using pure CO2, methane, and ethane as well as 0−100% mole ratios of methane/CO2 and methane/ethane. For both oil samples, ethane MMPs were ca. one-half those with CO2, while methane MMPs were ca. double or triple those with CO2. MMPs with mixed methane/CO2 showed a linear increase with mole percent methane for both crude oils, while both oils showed an exponential increase in MMP with mole percent methane in ethane, with a little increase in MMP until ca. 20 mol % methane in ethane.« less

Investigation of flame structure and burning intensity of partially premixed methane enrichment of syngas using OH-PLIF and kinetic simulation

NASA Astrophysics Data System (ADS)

Pu, Ge; Huang, Beibei; Zhang, Xun; Du, Jiantai; Zhu, Tuanhui; Chen, Bei

2018-05-01

Various experiments were conducted to study the combustion characteristics of partially premixed methane enrichment of syngas by using the OH-PLIF technique. Experiments were conducted on a co-flow burner, and the methane concentration (XCH4 = CH4/(H2+CO+CH4)) was varied from 0 to 20%, the overall equivalence ratio was varied from 0.4 to 1.2 and the inner equivalence ratio was varied from 1.5 to 3.5. Kinetic simulation was conducted by using OPPDIF module of CHEMKIN-Pro software. Results show that an increase in XCH4 and ϕoverall weakens the OH signal intensity. Adding methane into the fuel greatly increases the height of the inner flame front, and the increase of methane concentration has a negative effect on flame propagation speed. Meanwhile, simulation results remain consistent with the experiments. The main OH radical production reaction changes from R46: H+HO2 = 2OH to R38: H+O2 = O+OH when methane concentration contained in the fuel mixture increases. Sensitivity analysis also indicates that reaction which plays a dominant effect on temperature changes with the increase of methane concentration.

Fast start-up reactor for partial oxidation of methane with electrically-heated metallic monolith catalyst

NASA Astrophysics Data System (ADS)

Jung, Heon; Yoon, Wang Lai; Lee, Hotae; Park, Jong Soo; Shin, Jang Sik; La, Howon; Lee, Jong Dae

A palladium-washcoated metallic monolith catalyst is applied to the partial oxidation of methane to syngas. This catalyst is highly active at a gas hourly space velocity (GHSV) of 100,000 h -1. The compact partial oxidation (POX) reactor equipped with both 96 cc of the metallic monolith catalyst and an electrically-heated catalyst (EHC) has a start-up time of less than 1.5 min and a syngas generation capacity of 9.5 Nm 3 h -1. The POX reaction is sustained without the need for an external heater. With the stand-alone POX reactor, the methane conversion can be increased either by preheating the reactant mixture heat-exchanged with the product gas, or by supplying a larger amount of oxygen than is necessary for the reaction stoichiometry.

Analysis of Decomposition for Structure I Methane Hydrate by Molecular Dynamics Simulation

NASA Astrophysics Data System (ADS)

Wei, Na; Sun, Wan-Tong; Meng, Ying-Feng; Liu, An-Qi; Zhou, Shou-Wei; Guo, Ping; Fu, Qiang; Lv, Xin

2018-05-01

Under multi-nodes of temperatures and pressures, microscopic decomposition mechanisms of structure I methane hydrate in contact with bulk water molecules have been studied through LAMMPS software by molecular dynamics simulation. Simulation system consists of 482 methane molecules in hydrate and 3027 randomly distributed bulk water molecules. Through analyses of simulation results, decomposition number of hydrate cages, density of methane molecules, radial distribution function for oxygen atoms, mean square displacement and coefficient of diffusion of methane molecules have been studied. A significant result shows that structure I methane hydrate decomposes from hydrate-bulk water interface to hydrate interior. As temperature rises and pressure drops, the stabilization of hydrate will weaken, decomposition extent will go deep, and mean square displacement and coefficient of diffusion of methane molecules will increase. The studies can provide important meanings for the microscopic decomposition mechanisms analyses of methane hydrate.

Thermal conductivity measurements in porous mixtures of methane hydrate and quartz sand

USGS Publications Warehouse

Waite, W.F.; deMartin, B.J.; Kirby, S.H.; Pinkston, J.; Ruppel, C.D.

2002-01-01

Using von Herzen and Maxwell's needle probe method, we measured thermal conductivity in four porous mixtures of quartz sand and methane gas hydrate, with hydrate composing 0, 33, 67 and 100% of the solid volume. Thermal conductivities were measured at a constant methane pore pressure of 24.8 MPa between -20 and +15??C, and at a constant temperature of -10??C between 3.5 and 27.6 MPa methane pore pressure. Thermal conductivity decreased with increasing temperature and increased with increasing methane pore pressure. Both dependencies weakened with increasing hydrate content. Despite the high thermal conductivity of quartz relative to methane hydrate, the largest thermal conductivity was measured in the mixture containing 33% hydrate rather than in hydrate-free sand. This suggests gas hydrate enhanced grain-to-grain heat transfer, perhaps due to intergranular contact growth during hydrate synthesis. These results for gas-filled porous mixtures can help constrain thermal conductivity estimates in porous, gas hydrate-bearing systems.

Structural stability of methane hydrate at high pressures

USGS Publications Warehouse

Shu, J.; Chen, X.; Chou, I-Ming; Yang, W.; Hu, Jiawen; Hemley, R.J.; Mao, Ho-kwang

2011-01-01

The structural stability of methane hydrate under pressure at room temperature was examined by both in-situ single-crystal and powder X-ray diffraction techniques on samples with structure types I, II, and H in diamond-anvil cells. The diffraction data for types II (sII) and H (sH) were refined to the known structures with space groups Fd3m and P63/mmc, respectively. Upon compression, sI methane hydrate transforms to the sII phase at 120 MPa, and then to the sH phase at 600 MPa. The sII methane hydrate was found to coexist locally with sI phase up to 500 MPa and with sH phase up to 600 MPa. The pure sH structure was found to be stable between 600 and 900 MPa. Methane hydrate decomposes at pressures above 3 GPa to form methane with the orientationally disordered Fm3m structure and ice VII (Pn3m). The results highlight the role of guest (CH4)-host (H2O) interactions in the stabilization of the hydrate structures under pressure.

Elastic wave speeds and moduli in polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate

USGS Publications Warehouse

Helgerud, M.B.; Waite, W.F.; Kirby, S.H.; Nur, A.

2009-01-01

We used ultrasonic pulse transmission to measure compressional, P, and shear, S, wave speeds in laboratory-formed polycrystalline ice Ih, si methane hydrate, and sll methane-ethane hydrate. From the wave speed's linear dependence on temperature and pressure and from the sample's calculated density, we derived expressions for bulk, shear, and compressional wave moduli and Poisson's ratio from -20 to 15??C and 22.4 to 32.8 MPa for ice Ih, -20 to 15??C and 30.5 to 97.7 MPa for si methane hydrate, and -20 to 10??C and 30.5 to 91.6 MPa for sll methane-ethane hydrate. All three materials had comparable P and S wave speeds and decreasing shear wave speeds with increasing applied pressure. Each material also showed evidence of rapid intergranular bonding, with a corresponding increase in wave speed, in response to pauses in sample deformation. There were also key differences. Resistance to uniaxial compaction, indicated by the pressure required to compact initially porous samples, was significantly lower for ice Ih than for either hydrate. The ice Ih shear modulus decreased with increasing pressure, in contrast to the increase measured in both hydrates ?? 2009.

High pressure flame system for pollution studies with results for methane-air diffusion flames

NASA Technical Reports Server (NTRS)

Miller, I. M.; Maahs, H. G.

1977-01-01

A high pressure flame system was designed and constructed for studying nitrogen oxide formation in fuel air combustion. Its advantages and limitations were demonstrated by tests with a confined laminar methane air diffusion flame over the pressure range from 1 to 50 atm. The methane issued from a 3.06 mm diameter port concentrically into a stream of air contained within a 20.5 mm diameter chimney. As the combustion pressure is increased, the flame changes in shape from wide and convex to slender and concave, and there is a marked increase in the amount of luminous carbon. The height of the flame changes only moderately with pressure.

Studies of Methane Counterflow Flames at Low Pressures

NASA Astrophysics Data System (ADS)

Burrell, Robert Roe

Methane is the smallest hydrocarbon molecule, the fuel most widely studied in fundamental flame structure studies, and a major component of natural gas. Despite many decades of research into the fundamental chemical kinetics involved in methane oxidation, ongoing advancements in research suggest that more progress can be made. Though practical combustors of industrial and commercial significance operate at high pressures and turbulent flow conditions, fundamental understanding of combustion chemistry in flames is more readily obtained for low pressure and laminar flow conditions. Measurements were performed from 1 to 0.1 atmospheres for premixed methane/air and non-premixed methane-nitrogen/oxygen flames in a counterflow. Comparative modeling with quasi-one-dimensional strained flame codes revealed bias-induced errors in measured velocities up to 8% at 0.1 atmospheres due to tracer particle phase velocity slip in the low density gas reacting flow. To address this, a numerically-assisted correction scheme consisting of direct simulation of the particle phase dynamics in counterflow was implemented. Addition of reactions describing the prompt dissociation of formyl radicals to an otherwise unmodified USC Mech II kinetic model was found to enhance computed flame reactivity and substantially improve the predictive capability of computed results for measurements at the lowest pressures studied. Yet, the same modifications lead to overprediction of flame data at 1 atmosphere where results from the unmodified USC Mech II kinetic mechanism agreed well with ambient pressure flame data. The apparent failure of a single kinetic model to capture pressure dependence in methane flames motivates continued skepticism regarding the current understanding of pressure dependence in kinetic models, even for the simplest fuels.

A high pressure modulated molecular beam mass spectrometric sampling system

NASA Technical Reports Server (NTRS)

Stearns, C. A.; Kohl, F. J.; Fryburg, G. C.; Miller, R. A.

1977-01-01

The current state of understanding of free-jet high pressure sampling is critically reviewed and modifications of certain theoretical and empirical considerations are presented. A high pressure, free-jet expansion, modulated molecular beam, mass spectrometric sampling apparatus was constructed and this apparatus is described in detail. Experimental studies have demonstrated that the apparatus can be used to sample high temperature systems at pressures up to one atmosphere. Condensible high temperature gaseous species have been routinely sampled and the mass spectrometric detector has provided direct identification of sampled species. System sensitivity is better than one tenth of a part per million. Experimental results obtained with argon and nitrogen beams are presented and compared to theoretical predictions. These results and the respective comparison are taken to indicate acceptable performance of the sampling apparatus. Results are also given for two groups of experiments related to hot corrosion studies. The formation of gaseous sodium sulfate in doped methane-oxygen flames was characterized and the oxidative vaporization of metals was studied in an atmospheric pressure flowing gas system to which gaseous salt partial pressures were added.

Temperature-pressure conditions in coalbed methane reservoirs of the Black Warrior basin: Implications for carbon sequestration and enhanced coalbed methane recovery

USGS Publications Warehouse

Pashin, J.C.; McIntyre, M.R.

2003-01-01

Sorption of gas onto coal is sensitive to pressure and temperature, and carbon dioxide can be a potentially volatile supercritical fluid in coalbed methane reservoirs. More than 5000 wells have been drilled in the coalbed methane fields of the Black Warrior basin in west-central Alabama, and the hydrologic and geothermic information from geophysical well logs provides a robust database that can be used to assess the potential for carbon sequestration in coal-bearing strata.Reservoir temperature within the coalbed methane target zone generally ranges from 80 to 125 ??F (27-52 ??C), and geothermal gradient ranges from 6.0 to 19.9 ??F/1000 ft (10.9-36.2 ??C/km). Geothermal gradient data have a strong central tendency about a mean of 9.0 ??F/1000 ft (16.4 ??C/km). Hydrostatic pressure gradients in the coalbed methane fields range from normal (0.43 psi/ft) to extremely underpressured (<0.05 psi/ft). Pressure-depth plots establish a bimodal regime in which 70% of the wells have pressure gradients greater than 0.30 psi/ft, and 20% have pressure gradients lower than 0.10 psi/ft. Pockets of underpressure are developed around deep longwall coal mines and in areas distal to the main hydrologic recharge zone, which is developed in structurally upturned strata along the southeastern margin of the basin.Geothermal gradients within the coalbed methane fields are high enough that reservoirs never cross the gas-liquid condensation line for carbon dioxide. However, reservoirs have potential for supercritical fluid conditions beyond a depth of 2480 ft (756 m) under normally pressured conditions. All target coal beds are subcritically pressured in the northeastern half of the coalbed methane exploration fairway, whereas those same beds were in the supercritical phase window prior to gas production in the southwestern half of the fairway. Although mature reservoirs are dewatered and thus are in the carbon dioxide gas window, supercritical conditions may develop as reservoirs equilibrate toward a normal hydrostatic pressure gradient after abandonment. Coal can hold large quantities of carbon dioxide under supercritical conditions, and supercritical isotherms indicate non-Langmiur conditions under which some carbon dioxide may remain mobile in coal or may react with formation fluids or minerals. Hence, carbon sequestration and enhanced coalbed methane recovery show great promise in subcritical reservoirs, and additional research is required to assess the behavior of carbon dioxide in coal under supercritical conditions where additional sequestration capacity may exist. ?? 2003 Elsevier Science B.V. All rights reserved.

Models of a partially hydrated Titan interior with a clathrate crust

NASA Astrophysics Data System (ADS)

Lunine, J. I.; Castillo-Rogez, J. C.; Choukroun, M.; Sotin, C.

2012-04-01

We present a model of the interior evolution of Titan over time, assuming the silicate core was hydrated early in Titan’s history and is dehydrating over time. The original model presented in Castillo-Rogez and Lunine (2010) was motivated by a Cassini-derived moment of inertia (Iess et al., 2010) for Titan too large to be accommodated by classical fully differentiated models in which an anhydrous silicate core was overlain by a water ice (with possible perched ocean) mantle. Our model consists of a silicate core still in the process of dehydrating today, a situation made possible by the leaching of radiogenic potassium from the silicates into the perched liquid water ocean. The most recent version of our model accounts for the likely presence of large amounts of methane in the upper crust invoked to explain methane’s persistence at present and through geologic time (Tobie et al. 2006). The methane-rich crust turns out to have essentially no bearing on the temperature of the silicate core and hence the timing of dehydration, but it profoundly affects the thickness of the high-pressure ice layer beneath the ocean. Indeed, the insulating effect of the methane clathrate crust could have delayed the formation of the high-pressure layer, resulting in the interaction of liquid water with the silicate core for extended periods of time. Although a high-pressure ice layer is likely in place today, it is thin enough that plumes of hot water from the dehydrating core probably breach that layer. The implications of such a deep hydrothermal system for the later stages of the evolution of Titan’s interior and surface will be discussed. Part of this work has been performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. Government sponsorship acknowledged. References: Castillo-Rogez, J., Lunine, J.: “Evolution of Titan’s rocky core constrained by Cassini observations”. GRL, Vol. 37, L20205, 2010. Iess, L., et al.: “Gravity field, shape, and moment of inertia of Titan”. Science, Vol. 327, 1367-1369. Tobie, G., et al.: “Episodic outgassing as the origin of atmospheric methane on Titan”. Nature 440: 61-64, 2006.

Tandem Gravimetric and Volumetric Apparatus for Methane Sorption Measurements

NASA Astrophysics Data System (ADS)

Burress, Jacob; Bethea, Donald

Concerns about global climate change have driven the search for alternative fuels. Natural gas (NG, methane) is a cleaner fuel than gasoline and abundantly available due to hydraulic fracturing. One hurdle to the adoption of NG vehicles is the bulky cylindrical storage vessels needed to store the NG at high pressures (3600 psi, 250 bar). The adsorption of methane in microporous materials can store large amounts of methane at low enough pressures for the allowance of conformable, ``flat'' pressure vessels. The measurement of the amount of gas stored in sorbent materials is typically done by measuring pressure differences (volumetric, manometric) or masses (gravimetric). Volumetric instruments of the Sievert type have uncertainties that compound with each additional measurement. Therefore, the highest-pressure measurement has the largest uncertainty. Gravimetric instruments don't have that drawback, but can have issues with buoyancy corrections. An instrument will be presented with which methane adsorption measurements can be performed using both volumetric and gravimetric methods in tandem. The gravimetric method presented has no buoyancy corrections and low uncertainty. Therefore, the gravimetric measurements can be performed throughout an entire isotherm or just at the extrema to verify the results from the volumetric measurements. Results from methane sorption measurements on an activated carbon (MSC-30) and a metal-organic framework (Cu-BTC, HKUST-1, MOF-199) will be shown. New recommendations for calculations of gas uptake and uncertainty measurements will be discussed.

Methane Leakage From Hydrocarbon Wellbores into Overlying Groundwater: Numerical Investigation of the Multiphase Flow Processes Governing Migration

NASA Astrophysics Data System (ADS)

Rice, Amy K.; McCray, John E.; Singha, Kamini

2018-04-01

Methane leakage due to compromised hydrocarbon well integrity can lead to impaired groundwater quality. Here we use a three-dimensional, multiphase (vapor and aqueous), multicomponent (methane, water, salt), numerical model (TOUGH2 EOS7C) to investigate hydrogeological conditions that could result in groundwater contamination from natural gas wellbore leakage that migrates upward toward a freshwater aquifer. The conceptual model used for the simulations assumes methane leakage at 20-30 m below groundwater. We perform 180 simulations for a sensitivity analysis, examining (1) multiphase flow parameters related to storage, capillarity, and relative permeability, including porosity (ϕ), initial fluid-phase saturation (SL), and van Genuchten n and α, (2) geostatistical variations in intrinsic permeability (ki), and (3) methane source-zone pressure. Simulated mean ki values are 10-18 and 10-13 m2 with variances of 1 and 5 m4. Simulated source-zone pressures range from just over ambient hydrostatic pressure at the depth of leakage (100 kPa) to the maximum pressure that steel casings are commonly rated to withstand (20,340 kPa). ki, initial SL, ϕ, and van Genuchten's n and α were the most important parameters in determining the volume of methane reaching groundwater during a given time period. Multiphase parameterization of formations underlying freshwater aquifers and overlying hydrocarbon production zones is fundamental to assessing aquifer vulnerability to methane leakage.

Passive landfill gas emission - Influence of atmospheric pressure and implications for the operation of methane-oxidising biofilters.

PubMed

Gebert, Julia; Groengroeft, Alexander

2006-01-01

A passively vented landfill site in Northern Germany was monitored for gas emission dynamics through high resolution measurements of landfill gas pressure, flow rate and composition as well as atmospheric pressure and temperature. Landfill gas emission could be directly related to atmospheric pressure changes on all scales as induced by the autooscillation of air, diurnal variations and the passage of pressure highs and lows. Gas flux reversed every 20 h on average, with 50% of emission phases lasting only 10h or less. During gas emission phases, methane loads fed to a connected methane oxidising biofiltration unit varied between near zero and 247 g CH4 h(-1)m(-3) filter material. Emission dynamics not only influenced the amount of methane fed to the biofilter but also the establishment of gas composition profiles within the biofilter, thus being of high relevance for biofilter operation. The duration of the gas emission phase emerged as most significant variable for the distribution of landfill gas components within the biofilter.

46 CFR 154.703 - Methane (LNG).

Code of Federal Regulations, 2012 CFR

2012-10-01

... SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Design, Construction and Equipment Cargo Pressure and Temperature Control § 154.703 Methane (LNG). Unless a cargo tank carrying methane (LNG) can...

46 CFR 154.703 - Methane (LNG).

Code of Federal Regulations, 2014 CFR

2014-10-01

... SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Design, Construction and Equipment Cargo Pressure and Temperature Control § 154.703 Methane (LNG). Unless a cargo tank carrying methane (LNG) can...

46 CFR 154.703 - Methane (LNG).

Code of Federal Regulations, 2013 CFR

2013-10-01

... SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Design, Construction and Equipment Cargo Pressure and Temperature Control § 154.703 Methane (LNG). Unless a cargo tank carrying methane (LNG) can...

46 CFR 154.703 - Methane (LNG).

Code of Federal Regulations, 2011 CFR

2011-10-01

... SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Design, Construction and Equipment Cargo Pressure and Temperature Control § 154.703 Methane (LNG). Unless a cargo tank carrying methane (LNG) can...

46 CFR 154.703 - Methane (LNG).

Code of Federal Regulations, 2010 CFR

2010-10-01

... SELF-PROPELLED VESSELS CARRYING BULK LIQUEFIED GASES Design, Construction and Equipment Cargo Pressure and Temperature Control § 154.703 Methane (LNG). Unless a cargo tank carrying methane (LNG) can...

Improvement of gas hydrate preservation by increasing compression pressure to simple hydrates of methane, ethane, and propane

NASA Astrophysics Data System (ADS)

Kida, Masato; Jin, Yusuke; Watanabe, Mizuho; Murayama, Tetsuro; Nagao, Jiro

2017-09-01

In this report, we describe the dissociation behavior of gas hydrate grains pressed at 1 and 6 MPa. Certain simple gas hydrates in powder form show anomalous preservation phenomenon under their thermodynamic unstable condition. Investigation of simple hydrates of methane, ethane, and propane reveals that high pressure applied to the gas hydrate particles enhances their preservation effects. Application of high pressure increases the dissociation temperature of methane hydrate and has a restrictive effect against the dissociation of ethane and propane hydrate grains. These improvements of gas hydrate preservation by increasing pressure to the initial gas hydrate particles imply that appropriate pressure applied to gas hydrate particles enhances gas hydrate preservation effects.

Measurement of pressure-broadening and lineshift coefficients at 77 and 296 K of methane lines in the 727 nm band using intracavity laser spectroscopy

NASA Technical Reports Server (NTRS)

Singh, Kuldip; O'Brien, James J.

1994-01-01

Pressure-broadening coefficients and pressure-induced lineshifts of several rotational-vibrational lines have been measured in the 727 nm absorption band of methane at temperatures of 77 and 296 K, using nitrogen, hydrogen, and helium as the foreign-gas collision partners. A technique involving intracavity laser spectroscopy is used to record the methane spectra. Average values of the broadening coefficients (/cm/atm) at 77 K are: 0.199, 0.139, 0.055, and 0.29 for collision partners N2, H2, He, and CH4, respectively. Typical average values of the pressure-induced lineshifts (/cm/atm) at 77 K and for the range of foreign gas pressures between 10 and 200 torr are -0.052 for N2, -0.063 for H2, and +0.031 for He. All the values obtained at 296 K are considerably different from the corresponding values at 77 K. This represents the first report of pressure-broadening and shifting coefficients for the methane transitions in a region where the delta nu(sub C-H) = 5 band occurs.

Thermal conductivity and thermal diffusivity of methane hydrate formed from compacted granular ice

NASA Astrophysics Data System (ADS)

Zhao, Jie; Sun, Shicai; Liu, Changling; Meng, Qingguo

2018-05-01

Thermal conductivity and thermal diffusivity of pure methane hydrate samples, formed from compacted granular ice (0-75 μm), and were measured simultaneously by the transient plane source (TPS) technique. The temperature dependence was measured between 263.15 and 283.05 K, and the gas-phase pressure dependence was measured between 2 and 10 MPa. It is revealed that the thermal conductivity of pure methane hydrate exhibits a positive trend with temperature and increases from 0.4877 to 0.5467 W·m-1·K-1. The thermal diffusivity of methane hydrate has inverse dependence on temperature and the values in the temperature range from 0.2940 to 0.3754 mm2·s-1, which is more than twice that of water. The experimental results show that the effects of gas-phase pressure on the thermal conductivity and thermal diffusivity are very small. Thermal conductivity of methane hydrate is found to have weakly positive gas-phase pressure dependence, whereas the thermal diffusivity has slightly negative trend with gas-phase pressure.

Quantifying the loss of methane through secondary gas mass transport (or 'slip') from a micro-porous membrane contactor applied to biogas upgrading.

PubMed

McLeod, Andrew; Jefferson, Bruce; McAdam, Ewan J

2013-07-01

Secondary gas transport during the separation of a binary gas with a micro-porous hollow fibre membrane contactor (HMFC) has been studied for biogas upgrading. In this application, the loss or 'slip' of the secondary gas (methane) during separation is a known concern, specifically since methane possesses the intrinsic calorific value. Deionised (DI) water was initially used as the physical solvent. Under these conditions, carbon dioxide (CO2) and methane (CH4) absorption were dependent upon liquid velocity (V(L)). Whilst the highest CO2 flux was recorded at high V(L), selectivity towards CO2 declined due to low residence times and a diminished gas-side partial pressure, and resulted in slip of approximately 5.2% of the inlet methane. Sodium hydroxide was subsequently used as a comparative chemical absorption solvent. Under these conditions, CO2 mass transfer increased by increasing gas velocity (VG) which is attributed to the excess of reactive hydroxide ions present in the solvent, and the fast conversion of dissolved CO2 to carbonate species reinitiating the concentration gradient at the gas-liquid interface. At high gas velocities, CH4 slip was reduced to 0.1% under chemical conditions. Methane slip is therefore dependent upon whether the process is gas phase or liquid phase controlled, since methane mass transport can be adequately described by Henry's law within both physical and chemical solvents. The addition of an electrolyte was found to further retard CH4 absorption via the salting out effect. However, their applicability to physical solvents is limited since electrolytic concentration similarly impinges upon the solvents' capacity for CO2. This study illustrates the significance of secondary gas mass transport, and furthermore demonstrates that gas-phase controlled systems are recommended where greater selectivity is required. Copyright © 2013 Elsevier Ltd. All rights reserved.

In situ study of mass transfer in aqueous solutions under high pressures via Raman spectroscopy: A new method for the determination of diffusion coefficients of methane in water near hydrate formation conditions

USGS Publications Warehouse

Lu, W.J.; Chou, I.-Ming; Burruss, R.C.; Yang, M.Z.

2006-01-01

A new method was developed for in situ study of the diffusive transfer of methane in aqueous solution under high pressures near hydrate formation conditions within an optical capillary cell. Time-dependent Raman spectra of the solution at several different spots along the one-dimensional diffusion path were collected and thus the varying composition profile of the solution was monitored. Diffusion coefficients were estimated by the least squares method based on the variations in methane concentration data in space and time in the cell. The measured diffusion coefficients of methane in water at the liquid (L)-vapor (V) stable region and L-V metastable region are close to previously reported values determined at lower pressure and similar temperature. This in situ monitoring method was demonstrated to be suitable for the study of mass transfer in aqueous solution under high pressure and at various temperature conditions and will be applied to the study of nucleation and dissolution kinetics of methane hydrate in a hydrate-water system where the interaction of methane and water would be more complicated than that presented here for the L-V metastable condition. ?? 2006 Society for Applied Spectroscopy.

Molecular Simulation of the Phase Diagram of Methane Hydrate: Free Energy Calculations, Direct Coexistence Method, and Hyperparallel Tempering.

PubMed

Jin, Dongliang; Coasne, Benoit

2017-10-24

Different molecular simulation strategies are used to assess the stability of methane hydrate under various temperature and pressure conditions. First, using two water molecular models, free energy calculations consisting of the Einstein molecule approach in combination with semigrand Monte Carlo simulations are used to determine the pressure-temperature phase diagram of methane hydrate. With these calculations, we also estimate the chemical potentials of water and methane and methane occupancy at coexistence. Second, we also consider two other advanced molecular simulation techniques that allow probing the phase diagram of methane hydrate: the direct coexistence method in the Grand Canonical ensemble and the hyperparallel tempering Monte Carlo method. These two direct techniques are found to provide stability conditions that are consistent with the pressure-temperature phase diagram obtained using rigorous free energy calculations. The phase diagram obtained in this work, which is found to be consistent with previous simulation studies, is close to its experimental counterpart provided the TIP4P/Ice model is used to describe the water molecule.

Methane hydrate formation in partially water-saturated Ottawa sand

USGS Publications Warehouse

Waite, W.F.; Winters, W.J.; Mason, D.H.

2004-01-01

Bulk properties of gas hydrate-bearing sediment strongly depend on whether hydrate forms primarily in the pore fluid, becomes a load-bearing member of the sediment matrix, or cements sediment grains. Our compressional wave speed measurements through partially water-saturated, methane hydrate-bearing Ottawa sands suggest hydrate surrounds and cements sediment grains. The three Ottawa sand packs tested in the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) contain 38(1)% porosity, initially with distilled water saturating 58, 31, and 16% of that pore space, respectively. From the volume of methane gas produced during hydrate dissociation, we calculated the hydrate concentration in the pore space to be 70, 37, and 20% respectively. Based on these hydrate concentrations and our measured compressional wave speeds, we used a rock physics model to differentiate between potential pore-space hydrate distributions. Model results suggest methane hydrate cements unconsolidated sediment when forming in systems containing an abundant gas phase.

Permeability of sediment cores from methane hydrate deposit in the Eastern Nankai Trough, Japan

NASA Astrophysics Data System (ADS)

Konno, Y.; Yoneda, J.; Egawa, K.; Ito, T.; Jin, Y.; Kida, M.; Suzuki, K.; Nakatsuka, Y.; Nagao, J.

2013-12-01

Effective and absolute permeability are key parameters for gas production from methane-hydrate-bearing sandy sediments. Effective and/or absolute permeability have been measured using methane-hydrate-bearing sandy cores and clayey and silty cores recovered from Daini Atsumi Knoll in the Eastern Nankai Trough during the 2012 JOGMEC/JAPEX Pressure coring operation. Liquid-nitrogen-immersed cores were prepared by rapid depressurization of pressure cores recovered by a pressure coring system referred to as the Hybrid PCS. Cores were shaped cylindrically on a lathe with spraying of liquid nitrogen to prevent hydrate dissociation. Permeability was measured by a flooding test or a pressure relaxation method under near in-situ pressure and temperature conditions. Measured effective permeability of hydrate-bearing sediments is less than tens of md, which are order of magnitude less than absolute permeability. Absolute permeability of clayey cores is approximately tens of μd, which would perform a sealing function as cap rocks. Permeability reduction due to a swelling effect was observed for a silty core during flooding test of pure water mimicking hydrate-dissociation-water. Swelling effect may cause production formation damage especially at a later stage of gas production from methane hydrate deposits. This study was financially supported by the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) that carries out Japan's Methane Hydrate R&D Program conducted by the Ministry of Economy, Trade and Industry (METI).

Determination of methane concentrations in water in equilibrium with sI methane hydrate in the absence of a vapor phase by in situ Raman spectroscopy

USGS Publications Warehouse

Lu, W.; Chou, I.-Ming; Burruss, R.C.

2008-01-01

Most submarine gas hydrates are located within the two-phase equilibrium region of hydrate and interstitial water with pressures (P) ranging from 8 to 60 MPa and temperatures (T) from 275 to 293 K. However, current measurements of solubilities of methane in equilibrium with hydrate in the absence of a vapor phase are limited below 20 MPa and 283.15 K, and the differences among these data are up to 30%. When these data were extrapolated to other P-T conditions, it leads to large and poorly known uncertainties. In this study, in situ Raman spectroscopy was used to measure methane concentrations in pure water in equilibrium with sI (structure one) methane hydrate, in the absence of a vapor phase, at temperatures from 276.6 to 294.6 (??0.3) K and pressures at 10, 20, 30 and 40 (??0.4%) MPa. The relationship among concentration of methane in water in equilibrium with hydrate, in mole fraction [X(CH4)], the temperature in K, and pressure in MPa was derived as: X(CH4) = exp [11.0464 + 0.023267 P - (4886.0 + 8.0158 P)/T]. Both the standard enthalpy and entropy of hydrate dissolution at the studied T-P conditions increase slightly with increasing pressure, ranging from 41.29 to 43.29 kJ/mol and from 0.1272 to 0.1330 kJ/K ?? mol, respectively. When compared with traditional sampling and analytical methods, the advantages of our method include: (1) the use of in situ Raman signals for methane concentration measurements eliminates possible uncertainty caused by sampling and ex situ analysis, (2) it is simple and efficient, and (3) high-pressure data can be obtained safely. ?? 2007 Elsevier Ltd. All rights reserved.

Solubility of crude oil in methane as a function of pressure and temperature

USGS Publications Warehouse

Price, L.C.; Wenger, L.M.; Ging, T.; Blount, C.W.

1983-01-01

The solubility of a 44?? API (0.806 sp. gr.) whole crude oil has been measured in methane with water present at temperatures of 50 to 250??C and pressures of 740 to 14,852 psi, as have the solubilities of two high molecular weight petroleum distillation fractions at temperatures of 50 to 250??C and pressures of 4482 to 25,266 psi. Both increases in pressure and temperature increase the solubility of crude oil and petroleum distillation fractions in methane, the effect of pressure being greater than that of temperature. Unexpectedly high solubility levels (0.5-1.5 grams of oil per liter of methane-at laboratory temperature and pressure) were measured at moderate conditions (50-200??C and 5076-14504 psi). Similar results were found for the petroleum distillation fractions, one of which was the highest molecular weight material of petroleum (material boiling above 266??C at 6 microns pressure). Unexpectedly mild conditions (100??C and 15,200 psi; 200??C and 7513 psi) resulted in cosolubility of crude oil and methane. Under these conditions, samples of the gas-rich phase gave solubility values of 4 to 5 g/l, or greater. Qualitative analyses of the crude-oil solute samples showed that at low pressure and temperature equilibration conditions, the solute condensate would be enriched in C5-C15 range hydrocarbons and in saturated hydrocarbons in the C15+ fraction. With increases in temperature and especially pressure, these tendencies were reversed, and the solute condensate became identical to the starting crude oil. The data of this study, compared to that of previous studies, shows that methane, with water present, has a much greater carrying capacity for crude oil than in dry systems. The presence of water also drastically lowers the temperature and pressure conditions required for cosolubility. The data of this and/or previous studies demonstrate that the addition of carbon dioxide, ethane, propane, or butane to methane also has a strong positive effect on crude oil solubility, as does the presence of fine grained rocks. The n-paraffin distributions (as well as the overall composition) of the solute condensates are controlled by the temperature and pressure of solution and exsolution, as well as by the composition of the original starting material. It appears quite possible that primary migration by gaseous solution could 'strip' a source rock of crude-oil like components leaving behind a bitumen totally unlike the migrated crude oil. The data of this study demonstrate previous criticisms of primary petroleum migration by gas solution are invalid; that primary migration by gaseous solution cannot occur because methane cannot dissolve sufficient volumes of crude oil or cannot dissolve the highest molecular weight components of petroleum (tars and asphaltenes). ?? 1983.

In-situ visual observation for the formation and dissociation of methane hydrates in porous media by magnetic resonance imaging.

PubMed

Zhao, Jiafei; Lv, Qin; Li, Yanghui; Yang, Mingjun; Liu, Weiguo; Yao, Lei; Wang, Shenglong; Zhang, Yi; Song, Yongchen

2015-05-01

In this work, magnetic resonance imaging (MRI) was employed to observe the in-situ formation and dissociation of methane hydrates in porous media. Methane hydrate was formed in a high-pressure cell with controlled temperature, and then the hydrate was dissociated by thermal injection. The process was photographed by the MRI, and the pressure was recorded. The images confirmed that the direct visual observation was achieved; these were then employed to provide detailed information of the nucleation, growth, and decomposition of the hydrate. Moreover, the saturation of methane hydrate during the dissociation was obtained from the MRI intensity data. Our results showed that the hydrate saturation initially decreased rapidly, and then slowed down; this finding is in line with predictions based only on pressure. The study clearly showed that MRI is a useful technique to investigate the process of methane hydrate formation and dissociation in porous media. Copyright © 2015 Elsevier Inc. All rights reserved.

Direct measurement of methane hydrate composition along the hydrate equilibrium boundary

USGS Publications Warehouse

Circone, S.; Kirby, S.H.; Stern, L.A.

2005-01-01

The composition of methane hydrate, namely nW for CH 4??nWH2O, was directly measured along the hydrate equilibrium boundary under conditions of excess methane gas. Pressure and temperature conditions ranged from 1.9 to 9.7 MPa and 263 to 285 K. Within experimental error, there is no change in hydrate composition with increasing pressure along the equilibrium boundary, but nW may show a slight systematic decrease away from this boundary. A hydrate stoichiometry of n W = 5.81-6.10 H2O describes the entire range of measured values, with an average composition of CH4??5.99(??0.07) H2O along the equilibrium boundary. These results, consistent with previously measured values, are discussed with respect to the widely ranging values obtained by thermodynamic analysis. The relatively constant composition of methane hydrate over the geologically relevant pressure and temperature range investigated suggests that in situ methane hydrate compositions may be estimated with some confidence. ?? 2005 American Chemical Society.

In-Situ Sampling and Characterization of Naturally Occurring Marine Methane Hydrate Using the D/V JOIDES Resolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rack, Frank; Storms, Michael; Schroeder, Derryl

The primary accomplishments of the JOI Cooperative Agreement with DOE/NETL in this quarter were (1) the preliminary postcruise evaluation of the tools and measurement systems that were used during ODP Leg 204 to study hydrate deposits on Hydrate Ridge, offshore Oregon from July through September 2002; and (2) the preliminary study of the hydrate-bearing core samples preserved in pressure vessels and in liquid nitrogen cryofreezers, which are now stored at the ODP Gulf Coast Repository in College Station, TX. During ODP Leg 204, several newly modified downhole tools were deployed to better characterize the subsurface lithologies and environments hosting microbialmore » populations and gas hydrates. A preliminary review of the use of these tools is provided herein. The DVTP, DVTP-P, APC-methane, and APC-Temperature tools (ODP memory tools) were used extensively and successfully during ODP Leg 204 aboard the D/V JOIDES Resolution. These systems provided a strong operational capability for characterizing the in situ properties of methane hydrates in subsurface environments on Hydrate Ridge during ODP Leg 204. Pressure was also measured during a trial run of the Fugro piezoprobe, which operates on similar principles as the DVTP-P. The final report describing the deployments of the Fugro Piezoprobe is provided in Appendix A of this report. A preliminary analysis and comparison between the piezoprobe and DVTP-P tools is provided in Appendix B of this report. Finally, a series of additional holes were cored at the crest of Hydrate Ridge (Site 1249) specifically geared toward the rapid recovery and preservation of hydrate samples as part of a hydrate geriatric study partially funded by the Department of Energy (DOE). In addition, the preliminary results from gamma density non-invasive imaging of the cores preserved in pressure vessels are provided in Appendix C of this report. An initial visual inspection of the samples stored in liquid nitrogen is provided in Appendix D of this report.« less

Current and temperature distributions in-situ acquired by electrode-segmentation along a microtubular solid oxide fuel cell operating with syngas

NASA Astrophysics Data System (ADS)

Aydın, Özgür; Nakajima, Hironori; Kitahara, Tatsumi

2015-10-01

Addressing the fuel distribution and endothermic cooling by the internal reforming, we have measured longitudinal current/temperature variations by ;Electrode-segmentation; in a microtubular solid oxide fuel cell operated with syngas (50% pre-reformed methane) and equivalent H2/N2 (100% conversion of syngas to H2) at three different flow rates. Regardless of the syngas flow rates, currents and temperatures show irregular fluctuations with varying amplitudes from upstream to downstream segment. Analysis of the fluctuations suggests that the methane steam reforming reaction is highly affected by the H2 partial pressure. Current-voltage curves plotted for the syngas and equivalent H2/N2 flow rates reveal that the fuel depletion is enhanced toward the downstream during the syngas operation, resulting in a larger performance degradation. All the segments exhibit temperature drops with the syngas flow compared with the equivalent H2/N2 flow due to the endothermic cooling by the methane steam reforming reaction. Despite the drops, the segment temperatures remain above the furnace temperature; besides, the maximum temperature difference along the cell diminishes. The MSR reaction rate does not consistently increase with the decreasing gas inlet velocity (increasing residence time on the catalyst); which we ascribe to the dominating impact of the local temperatures.

Electrical resistivity of fluid methane multiply shock compressed to 147 GPa

NASA Astrophysics Data System (ADS)

Wang, Yi-Gao; Liu, Fu-Sheng; Liu, Qi-Jun; Wang, Wen-Peng

2018-01-01

Shock wave experiments were carried out to measure the electrical resistivity of fluid methane. The pressure range of 89-147 GPa and the temperature range from 1800 to 2600 K were achieved with a two-stage light-gas gun. We obtained a minimum electrical resistivity value of 4.5 × 10-2 Ω cm at pressure and temperature of 147 GPa and 2600 K, which is two orders of magnitude higher than that of hydrogen under similar conditions. The data are interpreted in terms of a continuous transition from insulator to semiconductor state. One possibility reason is chemical decomposition of methane in the shock compression process. Along density and temperature increase with Hugoniot pressure, dissociation of fluid methane increases continuously to form a H2-rich fluid.

Models of a partially hydrated Titan interior with clathrate crust

NASA Astrophysics Data System (ADS)

Lunine, J. I.; Castillo-Rogez, J.

2012-04-01

We present an updated model of the interior evolution of Titan over time, assuming the silicate core was hydrated early in Titan's history and is dehydrating over time. The original model presented in Castillo-Rogez and Lunine (2010) was motivated by a Cassini-derived moment of inertia (Iess et al., 2010) for Titan too large to be accommodated by classical fully differentiated models in which an anhydrous silicate core was overlain by a water ice (with possible perched ocean) mantle. Our model consisted of a silicate core still in the process of dehydrating today, a situation made possible by the leaching of radiogenic potassium from the silicates into the liquid water ocean. The crust of Titan was assumed to be pure water ice I. The model was consistent with the moment of inertia of Titan, but neglected the presence of large amounts of methane in the upper crust invoked to explain methane's persistence at present and through geologic time (Tobie et al. 2006). We have updated our model with such a feature. We have also improved our modeling with a better physical model for the dehydration of antigorite and other hydrated minerals. In particular our modeling now simulates heat advection resulting from water circulation (e.g., Seipold and Schilling 2003), rather than the purely conductive heat transfer regime assumed in the first version of our model. The modeling proceeds as in Castillo-Rogez and Lunine (2010), with the thermal conductivity of the methane clathrate crust rather than that of ice I. The former is several times lower than that of the latter, and the two have rather different temperature dependences (English and Tse, 2009). The crust turns out to have essentially no bearing on the temperature of the silicate core and hence the timing of dehydration, but it profoundly affects the thickness of the high-pressure ice layer beneath the ocean. Indeed, with the insulating methane clathrate crust, there must be a liquid water ocean beneath the methane clathrate crust and in contact with the silicates beneath for most of Titan's history. Although a high-pressure ice layer is likely in place today, it is thin enough that plumes of hot water from the dehydrating core probably breach the high pressure ice layer maintaining contact between the ocean and the silicate core. Part of this work has been performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. Government sponsorship acknowledged.

Experimental pressure enhancement of the rate of homogenous methanogenesis: implications for abiotic methane yields in terrestrial and planetary environments

NASA Astrophysics Data System (ADS)

Lazar, C.; Cody, G. D.

2011-12-01

Abiotic methane may play a role in the development of a biosphere on an otherwise lifeless planet. Methane concentrations in fluids emanating from serpentinite-hosted submarine springs such as Rainbow and Logatchev are below that required for equilibrium with coexisting CO2 and H2, indicating that the compositions of such fluids may be kinetically-controlled. The presence of transition metal-bearing accessory minerals in serpentinites has led to the hypothesis that heterogeneous catalysis may influence the rate of methanogenesis. We present new experiments that show pressure can also significantly accelerate homogenous methanogenesis, i.e., methane production in the absence of mineral catalysts. A series of cold-seal experiments were performed from 1-3.5 kbar at 300C for two weeks, using dilute isotopically labeled formic acid as a carbon and hydrogen source (70mmol solution). The experiments showed a significant increase in 13CH4 yield with pressure: e.g., the yield at 3.5 kbar was ~20X the yield at 1 kbar. This pressure enhancement is consistent with our previous results on homogeneous and heterogeneous methanogenesis and suggests that mineral catalysts are not necessary for CH4 equilibration in high pressure environments such as Precambrian crystalline basements or regional blueschist-grade metamorphic systems. Furthermore, in hydrothermal systems wherein fluid residence times are too short to permit equilibration, the reaction progress of methanogenesis is expected to increase with pressure. Recently discovered methane plumes above the mid-Cayman trough have been attributed to methanogenesis in deep serpentinites-hosted springs. The current experimental results lead to the prediction that the mid-Cayman springs (>1 kbar) contain higher methane concentrations than their lower pressure analogues at Rainbow and Logatchev (<0.5kbar). Fluids escaping forearc serpentinization in cold, steeply-dipping subduction zones may yield more methane than in warm shallow-dipping subduction zones, consistent with the detection of abiotic CH4 in serpentine mud along the Marianas forearc. The methane production rate from water-rock interaction on a deep planetary seafloor may be higher than from analogous terrestrial settings: e.g, on Europa (2.5 kbar seafloor) and Titan (8 kbar seafloor). Since many of the mineral catalysts commonly found in serpentinites (awaruite, heazlewoodite, e.g.) are not present during basaltic metamorphism, the potential for pressure-enhanced homogenous methanogenesis presents the possibility that deep hydrothermal alteration of the basaltic Martian crust could be the source for atmospheric methane on Mars. If methanogenic microbes are sustained by an energy imbalance made possible by kinetic barriers to the reduction of CO2 to CH4, then the habitability of hydrothermal systems with respect to methanogens may decrease with depth as the reaction progress of methanogenesis increases.

Investigating the effects of critical phenomena in premixed methane-oxygen flames at cryogenic conditions

NASA Astrophysics Data System (ADS)

Gopal, Abishek; Yellapantula, Shashank; Larsson, Johan

2017-11-01

Methane is increasingly becoming viable as a rocket fuel in the latest generation of launch vehicles. In liquid rocket engines, fuel and oxidizer are injected under cryogenic conditions into the combustion chamber. At high pressures, typical of rocket combustion chambers, the propellants exist in supercritical states where the ideal gas thermodynamics are no longer valid. We investigate the effects of real-gas thermodynamics on transcritical laminar premixed methane-oxygen flames. The effect of the real-gas cubic equations of state and high-pressure transport properties on flame dynamics is presented. We also study real-gas effects on the extinction limits of the methane-oxygen flame.

Analysis of three-phase equilibrium conditions for methane hydrate by isometric-isothermal molecular dynamics simulations.

PubMed

Yuhara, Daisuke; Brumby, Paul E; Wu, David T; Sum, Amadeu K; Yasuoka, Kenji

2018-05-14

To develop prediction methods of three-phase equilibrium (coexistence) conditions of methane hydrate by molecular simulations, we examined the use of NVT (isometric-isothermal) molecular dynamics (MD) simulations. NVT MD simulations of coexisting solid hydrate, liquid water, and vapor methane phases were performed at four different temperatures, namely, 285, 290, 295, and 300 K. NVT simulations do not require complex pressure control schemes in multi-phase systems, and the growth or dissociation of the hydrate phase can lead to significant pressure changes in the approach toward equilibrium conditions. We found that the calculated equilibrium pressures tended to be higher than those reported by previous NPT (isobaric-isothermal) simulation studies using the same water model. The deviations of equilibrium conditions from previous simulation studies are mainly attributable to the employed calculation methods of pressure and Lennard-Jones interactions. We monitored the pressure in the methane phase, far from the interfaces with other phases, and confirmed that it was higher than the total pressure of the system calculated by previous studies. This fact clearly highlights the difficulties associated with the pressure calculation and control for multi-phase systems. The treatment of Lennard-Jones interactions without tail corrections in MD simulations also contributes to the overestimation of equilibrium pressure. Although improvements are still required to obtain accurate equilibrium conditions, NVT MD simulations exhibit potential for the prediction of equilibrium conditions of multi-phase systems.

Analysis of three-phase equilibrium conditions for methane hydrate by isometric-isothermal molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Yuhara, Daisuke; Brumby, Paul E.; Wu, David T.; Sum, Amadeu K.; Yasuoka, Kenji

2018-05-01

To develop prediction methods of three-phase equilibrium (coexistence) conditions of methane hydrate by molecular simulations, we examined the use of NVT (isometric-isothermal) molecular dynamics (MD) simulations. NVT MD simulations of coexisting solid hydrate, liquid water, and vapor methane phases were performed at four different temperatures, namely, 285, 290, 295, and 300 K. NVT simulations do not require complex pressure control schemes in multi-phase systems, and the growth or dissociation of the hydrate phase can lead to significant pressure changes in the approach toward equilibrium conditions. We found that the calculated equilibrium pressures tended to be higher than those reported by previous NPT (isobaric-isothermal) simulation studies using the same water model. The deviations of equilibrium conditions from previous simulation studies are mainly attributable to the employed calculation methods of pressure and Lennard-Jones interactions. We monitored the pressure in the methane phase, far from the interfaces with other phases, and confirmed that it was higher than the total pressure of the system calculated by previous studies. This fact clearly highlights the difficulties associated with the pressure calculation and control for multi-phase systems. The treatment of Lennard-Jones interactions without tail corrections in MD simulations also contributes to the overestimation of equilibrium pressure. Although improvements are still required to obtain accurate equilibrium conditions, NVT MD simulations exhibit potential for the prediction of equilibrium conditions of multi-phase systems.

Oxidation of contaminative methane traces with radio-frequency discharge

NASA Technical Reports Server (NTRS)

Flamm, D. L.; Wydeven, T. L.

1976-01-01

An 11.8 MHz glow discharge was used to oxidize trace levels of methane in oxygen. The concentration of methane can be reduced by three orders of magnitude. The effects of power (0-400 W), flow rate (10-1000 cc-STP/min) and concentration (70-8000 ppm) were investigated at pressures ranging from 50 torr to almost 1 atm. No organic reaction products were detected in the treated gas stream. The process may prove useful for the removal of atmospheric trace contaminants at ambient pressure.

Comparative Ecology of H2 Cycling in Organotrophic and Phototrophic Ecosystems

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Alperin, Marc J.; Albert, Daniel B.; Bebout, Brad M.; Martens, Christopher S.; DesMarais, David J.; DeVincenzi, Don (Technical Monitor)

2001-01-01

The simple biochemistry of H2 is critical to a large number of microbial processes, affecting the interaction of organisms with each other and with the environment. The sensitivity of these many processes to H2 can be described quantitatively, at a basic thermodynamic level. This shared dependence on H2 may provide a means for interpreting the ecology and system-level biogeochemistry of widely variant microbial ecosystems on a common (and quantitative) level. Understanding the factors that control H2 itself is a critical prerequisite. Here, we examine two ecosystems that vary widely with respect to H2 cycling. In anoxic, 'organotrophic' sediments from Cape Lookout Bight (North Carolina, USA), H2 partial pressures are strictly maintained at low, steady-state levels by H2-consuming organisms, in a fashion that can be quantitatively predicted by simple thermodynamic calculations. In phototrophic microbial mats from Baja, Mexico, H2 partial pressures are instead controlled by the activity of light-sensitive H2-producing organisms. In consequence, H2 partial pressures within the system fluctuate by orders of magnitude on hour-long time scales. The differences in H2 cycling subsequently impact H2-sensitive microbial processes, such as methanogenesis. For example, the presence of sulfate in the organotrophic system always yielded low levels of H2 that were inhibitory to methanogenesis; however, the elevated levels of H2 in the phototrophic system favored methane production at significant levels, even in the presence of high sulfate concentrations. The myriad of other H2-sensitive microbial processes are expected to exhibit similar behavior.

Coal-bed methane water effects on dill and essential oils

USDA-ARS?s Scientific Manuscript database

Pumping water from coal seams decreases the pressure in the seam and in turn releases trapped methane; this is the most common and economic way of methane extraction. The water that is pumped out is known as coal-bed methane water (CBMW), which is high in sodium and other salts. In past 25 years, th...

The effect of coal-bed methane water on spearmint and peppermint

USDA-ARS?s Scientific Manuscript database

Coal bed methane (CBM) is extracted from underground coal seams, flooded with water. In order to reduce the pressure and release the methane, the trapped water needs to be pumped out. The resulting ‘waste water’ is known as coal-bed methane water (CBMW). Major concerns with the use of CBMW are the h...

Process for producing methane from gas streams containing carbon monoxide and hydrogen

DOEpatents

Frost, Albert C.

1980-01-01

Carbon monoxide-containing gas streams are passed over a catalyst capable of catalyzing the disproportionation of carbon monoxide so as to deposit a surface layer of active surface carbon on the catalyst essentially without formation of inactive coke thereon. The surface layer is contacted with steam and is thus converted to methane and CO.sub.2, from which a relatively pure methane product may be obtained. While carbon monoxide-containing gas streams having hydrogen or water present therein can be used only the carbon monoxide available after reaction with said hydrogen or water is decomposed to form said active surface carbon. Although hydrogen or water will be converted, partially or completely, to methane that can be utilized in a combustion zone to generate heat for steam production or other energy recovery purposes, said hydrogen is selectively removed from a CO--H.sub.2 -containing feed stream by partial oxidation thereof prior to disproportionation of the CO content of said stream.

Dissolution of Hydrocarbon Gas Hydrates in Seawater at 1030-m; Effects of Porosity, Structure, and Compositional Variation as Determined by High-Definition Video and SEM Imaging.

NASA Astrophysics Data System (ADS)

Stern, L. A.; Peltzer, E. T.; Durham, W. B.; Kirby, S. H.; Brewer, P. G.; Circone, S.; Rehder, G.

2002-12-01

We compare dissolution rates of pure, porous, compacted, and oil-contaminated sI methane hydrate and sII methane-ethane hydrate to rates measured previously on pure, compacted, sI methane hydrate and sI carbon dioxide hydrate (Rehder et al., Fall AGU 2001). Laboratory-synthesized test specimens were used in both studies, allowing characterization of test materials prior to their transport and exposure to seawater at 1030-meter depth on the Monterey Canyon seafloor, off coastal Moss Landing, CA. Although pressure and temperature (P-T) conditions at this site are within the nominal P-T equilibrium fields of all gas hydrates tested here, the seawater is undersaturated with respect to the hydrate-forming gas species. Hence, samples dissolve with time, at a rate dependent on water current flow. Four samples were deployed in this second experiment: (1) pure, 30% porous methane hydrate; (2) pure, compacted methane hydrate; (3) pure methane hydrate compacted and then contaminated with a low-T mineral oil; and (4) pure, compacted sII methane-ethane hydrate with methane:ethane molar ratio 0.72. Samples were transferred by pressure vessel at 0 ° C and 15 MPa to the seafloor observatory via the MBARI remotely operated vehicle Ventana. Samples were then exposed to the deep ocean environment and monitored by HDTV camera for several hours at the beginning and end of a 25-hour period. Local current speed and direction were also measured throughout the experiment. Those samples that did not undergo complete dissolution after 25 h were successfully recovered to the laboratory for subsequent analysis by scanning electron microscopy (SEM). Previously, video analysis showed dissolution rates corresponding to 4.0 +/- 0.5 mmole CO2/m2 s for compacted CO2 hydrate samples, and 0.37 +/- 0.03 mmole CH4/m2s for compacted methane hydrate samples (Rehder et al, AGU 2001). The ratio of dissolution rates fits a simple diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site. These calculations assume that dissolution occurred only along the outer (i.e. imaged) surface of the samples. This assumption is now validated by SEM analysis of recovered samples from the second dive, showing little to no internal alteration of compacted material following their partial dissolution. Quantitative comparison of results from the two dives poses challenges due to variations in sample size and orientation. However, both compacted methane hydrate samples from the second dive in fact exhibited comparable behavior to that measured in the previous experiment; the oily sample did not dissolve at a slower rate, as might be expected if a hydrophobic contaminant inhibits seawater contact. Surprisingly, the porous methane hydrate exhibited significantly slower face retreat than its compacted counterparts. The sII methane-ethane hydrate dissolved measurably slower than all other samples, consistent with the solubility properties of its guest components. While these results represent only a first step in emulating the more complex interactions of seawater with naturally occurring hydrate-bearing sediments, such end member studies should aid preliminary modelling investigations of the chemical stability and lifetime of gas hydrates exposed at the seafloor.

Simultaneous determination of thermal conductivity, thermal diffusivity and specific heat in sI methane hydrate

USGS Publications Warehouse

Waite, W.F.; Stern, L.A.; Kirby, S.H.; Winters, W.J.; Mason, D.H.

2007-01-01

Thermal conductivity, thermal diffusivity and specific heat of sI methane hydrate were measured as functions of temperature and pressure using a needle probe technique. The temperature dependence was measured between −20°C and 17°C at 31.5 MPa. The pressure dependence was measured between 31.5 and 102 MPa at 14.4°C. Only weak temperature and pressure dependencies were observed. Methane hydrate thermal conductivity differs from that of water by less than 10 per cent, too little to provide a sensitive measure of hydrate content in water-saturated systems. Thermal diffusivity of methane hydrate is more than twice that of water, however, and its specific heat is about half that of water. Thus, when drilling into or through hydrate-rich sediment, heat from the borehole can raise the formation temperature more than 20 per cent faster than if the formation's pore space contains only water. Thermal properties of methane hydrate should be considered in safety and economic assessments of hydrate-bearing sediment.

Cyclic formation and dissociation of methane hydrate within partially water saturated sand

NASA Astrophysics Data System (ADS)

Kneafsey, T. J.; Nakagawa, S.

2010-12-01

For partially water-saturated sediments, laboratory experiments have shown that methane hydrate forms heterogeneously within a sample at the core scale. The heterogeneous distribution of hydrate in combination with grain-scale hydrate location (eg. grain cementing, load bearing, and pore filling), determines the overall mechanical properties of hydrate-bearing sediments including shear strength and seismic properties. For this reason, understanding the heterogeneity of hydrate-bearing sample is essential when the bulk properties of the sample are examined in the laboratory. We present a series of laboratory methane hydrate formation and dissociation experiments with concurrent x-ray CT imaging and low-frequency (near 1 kHz) seismic measurements. The seismic measurements were conducted using a new acoustic resonant bar technique called the Split Hopkinson Resonant Bar method, which allows using a small sediment core (3.75 cm diameter, 7.5 cm length). The experiment was conducted using a jacketed, pre-compacted, fine-grain silica sand sample with a 40% distilled water saturation. Under isotropic confining stress of 6.9 MPa and a temperature 4 oC, the hydrate was formed in the sample by injecting pure methane gas at 5.6 MPa. Once the hydrate formed, it was dissociated by reducing the pore pressure to 2.8 MPa. This cycle was repeated by three times (dissociation test for the third cycle was not done) to examine the resulting changes in the hydrate distribution and seismic signatures. The repeated formation of hydrate resulted in significant changes in its distribution, which resulted in differences in the overall elastic properties of the sample, determined from the seismic measurements. Interestingly, the time intervals between the dissociation and subsequent formation of hydrate affected the rate of hydrate formation, shorter intervals resulting in faster formation. This memory effect, possibly caused by the presence of residual “seed crystals” in the pore water providing nucleation points for hydrate formation, did not result in rapid formation at all locations in the sample. In spite of heterogeneity, observed seismic properties were very similar for the two measurements during dissociation.

Structural changes and preferential cage occupancy of ethane hydrate and methane-ethane mixed gas hydrate under very high pressure.

PubMed

Hirai, Hisako; Takahara, Naoya; Kawamura, Taro; Yamamoto, Yoshitaka; Yagi, Takehiko

2008-12-14

High-pressure experiments of ethane hydrate and methane-ethane mixed hydrates with five compositions were performed using a diamond anvil cell in a pressure range of 0.1-2.8 GPa at room temperature. X-ray diffractometry and Raman spectroscopy showed structural changes as follows. The initial structure, structure I (sI), of ethane hydrate was retained up to 2.1 GPa without any structural change. For the mixed hydrates, sI was widely distributed throughout the region examined except for the methane-rich and lower pressure regions. For the ethane-rich and intermediate composition regions (73 mol % ethane sample and 53% sample), sI was maintained up to 2.1 GPa. With increasing methane component (34% and 30% samples), sI existed at pressures from 0.1 to about 1.0 GPa. Hexagonal structure (sH) appeared in addition to sI at 1.3 GPa for the 34% sample and at 1.1 GPa for the 30% sample. By further increasing the methane component (22% sample), structure II (sII) existed solely up to 0.3 GPa. From 0.3 to 0.6 GPa, sII and sI coexisted, and from 0.6 to 1.0 GPa only sI existed. At 1.2 GPa sH appeared, and sH and sI coexisted up to 2.1 GPa. Above 2.1 GPa, ethane hydrate and all of the mixed hydrates decomposed into ice VI and ethane fluid or methane-ethane fluid, respectively. The Raman study revealed that occupation of the small cages by ethane molecules occurred above 0.1 GPa in ethane hydrate and continued up to decomposition at 2.1 GPa, although it is thought that ethane molecules are contained only in the large cage.

Competitive interactions between methane- and ammonia-oxidizing bacteria modulate carbon and nitrogen cycling in paddy soil

NASA Astrophysics Data System (ADS)

Zheng, Y.; Huang, R.; Wang, B. Z.; Bodelier, P. L. E.; Jia, Z. J.

2014-06-01

Pure culture studies have demonstrated that methanotrophs and ammonia oxidizers can both carry out the oxidation of methane and ammonia. However, the expected interactions resulting from these similarities are poorly understood, especially in complex, natural environments. Using DNA-based stable isotope probing and pyrosequencing of 16S rRNA and functional genes, we report on biogeochemical and molecular evidence for growth stimulation of methanotrophic communities by ammonium fertilization, and that methane modulates nitrogen cycling by competitive inhibition of nitrifying communities in a rice paddy soil. Pairwise comparison between microcosms amended with CH4, CH4+Urea, and Urea indicated that urea fertilization stimulated methane oxidation activity 6-fold during a 19-day incubation period, while ammonia oxidation activity was significantly suppressed in the presence of CH4. Pyrosequencing of the total 16S rRNA genes revealed that urea amendment resulted in rapid growth of Methylosarcina-like MOB, and nitrifying communities appeared to be partially inhibited by methane. High-throughput sequencing of the 13C-labeled DNA further revealed that methane amendment resulted in clear growth of Methylosarcina-related MOB while methane plus urea led to an equal increase in Methylosarcina and Methylobacter-related type Ia MOB, indicating the differential growth requirements of representatives of these genera. An increase in 13C assimilation by microorganisms related to methanol oxidizers clearly indicated carbon transfer from methane oxidation to other soil microbes, which was enhanced by urea addition. The active growth of type Ia methanotrops was significantly stimulated by urea amendment, and the pronounced growth of methanol-oxidizing bacteria occurred in CH4-treated microcosms only upon urea amendment. Methane addition partially inhibited the growth of Nitrosospira and Nitrosomonas in urea-amended microcosms, as well as growth of nitrite-oxidizing bacteria. These results suggest that type I methanotrophs can outcompete type II methane oxidizers in nitrogen-rich environments, rendering the interactions among methane and ammonia oxidizers more complicated than previously appreciated.

Molecular dynamics simulations of methane hydrate decomposition.

PubMed

Myshakin, Evgeniy M; Jiang, Hao; Warzinski, Robert P; Jordan, Kenneth D

2009-03-12

Molecular dynamics simulations have been carried out to study decomposition of methane hydrate at different cage occupancies. The decomposition rate is found to depend sensitively on the hydration number. The rate of the destruction of the cages displays Arrhenius behavior, consistent with an activated mechanism. During the simulations, reversible formation of partial water cages around methane molecules in the liquid was observed at the interface at temperatures above the computed hydrate decomposition temperature.

Geochemistry of a naturally occurring massive marine gas hydrate

USGS Publications Warehouse

Kvenvolden, K.A.; Claypool, G.E.; Threlkeld, C.N.; Dendy, Sloan E.

1984-01-01

During Deep Sea Drilling Project (DSDP) Leg 84 a core 1 m long and 6 cm in diameter of massive gas hydrate was unexpectedly recovered at Site 570 in upper slope sediment of the Middle America Trench offshore of Guatemala. This core contained only 5-7% sediment, the remainder being the solid hydrate composed of gas and water. Samples of the gas hydrate were decomposed under controlled conditions in a closed container maintained at 4??C. Gas pressure increased and asymptotically approached the equilibrium decomposition pressure for an ideal methane hydrate, CH4.5-3/4H2O, of 3930 kPa and approached to this pressure after each time gas was released, until the gas hydrate was completely decomposed. The gas evolved during hydrate decomposition was 99.4% methane, ???0.2% ethane, and ???0.4% CO2. Hydrocarbons from propane to heptane were also present, but in concentrations of less than 100 p.p.m. The carbon-isotopic composition of methane was -41 to -44 permil(( 0 00), relative to PDB standard. The observed volumetric methane/water ratio was 64 or 67, which indicates that before it was stored and analyzed, the gas hydrate probably had lost methane. The sample material used in the experiments was likely a mixture of methane hydrate and water ice. Formation of this massive gas hydrate probably involved the following processes: (i) upward migration of gas and its accumulation in a zone where conditions favored the growth of gas hydrates, (ii) continued, unusually rapid biological generation of methane, and (iii) release of gas from water solution as pressure decreased due to sea level lowering and tectonic uplift. ?? 1984.

The effect of elevated methane pressure on methane hydrate dissociation

USGS Publications Warehouse

Circone, S.; Stern, L.A.; Kirby, S.H.

2004-01-01

Methane hydrate, equilibrated at P, T conditions within the hydrate stability field, was rapidly depressurized to 1.0 or 2.0 MPa and maintained at isobaric conditions outside its stability field, while the extent and rate of hydrate dissociation was measured at fixed, externally maintained temperatures between 250 and 288 K. The dissociation rate decreases with increasing pressure at a given temperature. Dissociation rates at 1.0 MPa parallel the complex, reproducible T-dependence previously observed between 250 and 272 K at 0.1 MPa. The lowest rates were observed near 268 K, such that >50% of the sample can persist for more than two weeks at 0.1 MPa to more than a month at 1 and 2 MPa. Varying the pressure stepwise in a single experiment increased or decreased the dissociation rate in proportion to the rates observed in the isobaric experiments, similar to the rate reversibility previously observed with stepwise changes in temperature at 0.1 MPa. At fixed P, T conditions, the rate of methane hydrate dissociation decreases monotonically with time, never achieving a steady rate. The relationship between time (t) and the extent of hydrate dissociation is empirically described by: Evolved gas (%) = A??tB where the pre-exponential term A ranges from 0 to 16% s-B and the exponent B is generally <1. Based on fits of the dissociation results to Equation 1 for the full range of temperatures (204 to 289 K) and pressures (0.1 to 2.0 MPa) investigated, the derived parameters can be used to predict the methane evolution curves for pure, porous methane hydrate to within ??5%. The effects of sample porosity and the presence of quartz sand and seawater on methane hydrate dissociation are also described using Equation 1.

Methane-bearing fluids in subduction zones: an experimental study of abiotic methanogenesis during serpentinization at 12 kbar and 300°C

NASA Astrophysics Data System (ADS)

Lazar, C.; Manning, C. E.

2009-12-01

Serpentinization within subduction zones may generate reduced fluids that contain higher concentrations of abiotic methane than near-surface ultramafic environments. We present preliminary experimental data suggesting that the kinetics of abiotic methanogenesis are enhanced at high pressures. Thermodynamic calculations of C-O-H fluid speciations at the low oxygen fugacities attained during early serpentinization suggest complete conversion of oxidized carbon to methane, yet previous field and experimental investigations have reported fluid compositions with CH4/CO2 far below equilibrium (McCollom and Seewald, 2007). Much experimental work, therefore, has focused on CH4 production rates and the kinetic effects of temperature and mineral catalysis (Horita and Berdt, 1999; Foustoukos and Seyfried, 2004). Methane has been shown experimentally to form at very high pressures (Scott et al, 2004), but the quantitative effect of pressure on methanogenesis kinetics is unknown. We present preliminary results of a comparison of methane production rates at 0.35 and 12 kbar, 300°C, using experiments performed in piston cylinder and cold seal hydrothermal apparatus. Carbon was introduced as a roughly 70 mmol solution of isotopically-labeled formic acid, H13COOH, known to decompose to 13CO2 and H2 at run conditions. Roughly 15 mL of this solution, along with 1.9 mg of natural awaruite (Ni3Fe), was loaded into a gold capsule and then sealed via DC spot welding. Awaruite, a known methane catalyst (Horita and Berndt, 1999), was added to increase the overall rates of all experiments in order to boost the concentration for analysis and as an fO2 buffer appropriate for serpentinization. The experiments were held at T and P for approximately 160 hours. After each run, the capsule was placed in a gas vial and punctured with a needle. The contents of the vial were extracted via gas syringe and injected into gas chromatograph mass spectrometer (GC-MS). CH4 concentration in the 12 kbar run was approximately twice that of the low pressure experiment. In addition to this kinetic enhancement, high pressure strongly favors calcite dissolution (Caciagli and Manning, 2003), thus providing fluids rich in CO2, a reactant in the canonical hydrothermal abiotic methanogenesis reaction, CO2 + 4H2 = CH4 + 2H2O. Hydrogen should also be common within subduction zones, given the significant potential for serpentinization of ultramafic rocks in the forearc mantle and the oceanic lithospheric mantle. Metasomatism of the forearc mantle by CO2-H2O fluids, for example, should generate methane-rich fluids. The details of high pressure methane are complicated by graphite saturation, fluid flow, carbonate stability, fluid-rock ratio, and other geochemical parameters, to be addressed in the future. Nevertheless, given the likely widespread distribution of high pressure serpentinization environments throughout the Solar System, high pressure methane may play a role in atmospheric methane on Mars, the Faint Young Sun problem on the early Earth, the potential for life on Europa, and the synthesis of prebiotic chemicals on any geologically active planet.

40 CFR 63.457 - Test methods and procedures.

Code of Federal Regulations, 2014 CFR

2014-07-01

... of methane or n-hexane and air at a concentration of approximately, but less than, 10,000 parts per million by volume methane or n-hexane. (e) Negative pressure procedures. To demonstrate negative pressure... between 6.95 and 7.05. (4) To prepare the 0.1 normality (N) sodium thiosulfate solution, dissolve 25 g of...

An experimental investigation of the internal methane pressure in hydrogen attack

NASA Technical Reports Server (NTRS)

Natan, M.; Johnson, H. H.

1983-01-01

An experimental investigation of the internal methane pressure that is the driving force for bubble growth in hydrogen attack (HA) was done on pure iron (204 ppm C) and on two low carbon steels of slightly different compositions. The methane content N (c.c gas/g. material) in attacked specimens was measured by a vacuum extraction technique. The total void volume V (c.c) was determined from density measurements before and after HA exposure. The two values, N and V, were then used in an equation of state to calculate an average methane pressure P for the attack stages beyond a density loss (d.l.) greater than 0.05 pct. It was determined that N and P depend on hydrogen exposure conditions and the presence of traces of strong carbide forming alloying elements (in steel). They are independent of specimen size and grain size over a limited range. P varies as the bubble volume increases, showing a generally decreasing trend which brings it to values lower than calculated equilibrium pressures, although well within the same order of magnitude. Possible reasons for this behavior are discussed.

Buffer Gas Experiments in Mercury (Hg+) Ion Clock

NASA Technical Reports Server (NTRS)

Chung, Sang K.; Prestage, John D.; Tjoelker, Robert L.; Maleki, Lute

2004-01-01

We describe the results of the frequency shifts measured from various buffer gases that might be used as a buffer gas to increase the loading efficiency and cooling of ions trapped in a small mercury ion clock. The small mass, volume and power requirement of space clock precludes the use of turbo pumps. Hence, a hermetically sealed vacuum system, incorporating a suitable getter material with a fixed amount of inert buffer gas may be a practical alternative to the groundbased system. The collision shifts of 40,507,347.996xx Hz clock transition for helium, neon and argon buffer gases were measured in the ambient earth magnetic field. In addition to the above non-getterable inert gases we also measured the frequency shifts due to getterable, molecular hydrogen and nitrogen gases which may be used as buffer gases when incorporated with a miniature ion pump. We also examined the frequency shift due to the low methane gas partial pressure in a fixed higher pressure neon buffer gas environment. Methane gas interacted with mercury ions in a peculiar way as to preserve the ion number but to relax the population difference in the two hyperfine clock states and thereby reducing the clock resonance signal. The same population relaxation was also observed for other molecular buffer gases (N H,) but at much reduced rate.

Methane absorption in the visible spectra of the outer planets and Titan

NASA Technical Reports Server (NTRS)

Owen, T.; Cess, R. D.

1975-01-01

New spectra of Jupiter, Saturn, and Titan show weak methane bands in the region below 6000 A which have been known for many years in the spectra of Uranus and Neptune. Adopting the known abundance of methane on Jupiter, we have used a band model to determine CH4 abundances and broadening pressures for the other objects. The results indicate high values of the CH4 to H2 concentration ratio for Uranus and Neptune; for Titan, a surface pressure in excess of 1 atm is implied.

Results of coalbed-methane drilling, Mylan Park, Monongalia County, West Virginia: Chapter G.3 in Coal and petroleum resources in the Appalachian basin: distribution, geologic framework, and geochemical character

USGS Publications Warehouse

Ruppert, Leslie F.; Fedorko, Nick; Warwick, Peter D.; Grady, William C.; Britton, James Q.; Schuller, William A.; Crangle, Robert D.; Ruppert, Leslie F.; Ryder, Robert T.

2014-01-01

High-pressure carbon-dioxide adsorption isotherms were measured on composite coal samples of the Upper Kittanning coal bed and the Middle Kittanning and Clarion coal zones. Assuming that the reservoir pressure in the Mylan Park coals is equivalent to the normal hydrostatic pressure, the estimated maximum carbon-dioxide adsorption pressures range from a low of about 300 pounds per square inch (lb/in2 ) in coals from the Clarion coal zone to 500 lb/in2 for coals from the Upper Kittanning coal bed. The estimated maximum methane adsorption isotherms show that the coals from the Upper Kittanning coal bed and the Middle Kittanning coal zone are undersaturated in methane, but coals from the Clarion coal zone are close to saturation.

Methanosarcina as the dominant aceticlastic methanogens during mesophilic anaerobic digestion of putrescible waste.

PubMed

Vavilin, Vasily A; Qu, Xian; Mazéas, Laurent; Lemunier, Melanie; Duquennoi, Christian; He, Pinjing; Bouchez, Theodore

2008-11-01

Taking into account isotope (13)C value a mathematical model was developed to describe the dynamics of methanogenic population during mesophilic anaerobic digestion of putrescible solid waste and waste imitating Chinese municipal solid waste. Three groups of methanogens were considered in the model including unified hydrogenotrophic methanogens and two aceticlastic methanogens Methanosaeta sp. and Methanosarcina sp. It was assumed that Methanosaeta sp. and Methanosarcina sp. are inhibited by high volatile fatty acids concentration. The total organic and inorganic carbon concentrations, methane production, methane and carbon dioxide partial pressures as well as the isotope (13)C incorporation in PSW and CMSW were used for the model calibration and validation. The model showed that in spite of the high initial biomass concentration of Methanosaeta sp. Methanosarcina sp. became the dominant aceticlastic methanogens in the system. This prediction was confirmed by FISH. It is concluded that Methanosarcina sp. forming multicellular aggregates may resist to inhibition by volatile fatty acids (VFAs) because a slow diffusion rate of the acids limits the VFA concentrations inside the Methanosarcina sp. aggregates.

Analysis of fixed bed data for the extraction of a rate mechanism for the reaction of hematite with methane

DOE PAGES

Breault, Ronald W.; Monazam, Esmail R.

2015-04-01

In this study, chemical looping combustion is a promising technology for the capture of CO 2 involving redox materials as oxygen carriers. The effects of reduction conditions, namely, temperature and fuel partial pressure on the conversion products are investigated. The experiments were conducted in a laboratory fixed-bed reactor that was operated cyclically with alternating reduction and oxidation periods. Reactions are assumed to occur in the shell surrounding the particle grains with diffusion of oxygen to the surface from the grain core. Activation energies for the shell and core reactions range from 9 to 209 kJ/mol depending on the reaction step.

Mid-infrared multi-mode absorption spectroscopy, MUMAS, using difference frequency generation

NASA Astrophysics Data System (ADS)

Northern, Henry; O'Hagan, Seamus; Hamilton, Michelle L.; Ewart, Paul

2015-03-01

Multi-mode absorption spectroscopy of ammonia and methane at 3.3 μm has been demonstrated using a source of multi-mode mid-infrared radiation based on difference frequency generation. Multi-mode radiation at 1.56 μm from a diode-pumped Er:Yb:glass laser was mixed with a single-mode Nd:YAG laser at 1.06 μm in a periodically poled lithium niobate crystal to produce multi-mode radiation in the region of 3.3 μm. Detection, by direct multi-mode absorption, of NH3 and CH4 is reported for each species individually and also simultaneously in mixtures allowing measurements of partial pressures of each species.

Partial oxidation of methane by pulsed corona discharges

NASA Astrophysics Data System (ADS)

Hoeben, W. F. L. M.; Boekhoven, W.; Beckers, F. J. C. M.; van Heesch, E. J. M.; Pemen, A. J. M.

2014-09-01

Pulsed corona-induced partial oxidation of methane in humid oxygen or carbon dioxide atmospheres has been investigated for future fuel synthesis applications. The obtained product spectrum is wide, i.e. saturated, unsaturated and oxygen-functional hydrocarbons. The generally observed methane conversion levels are 6-20% at a conversion efficiency of about 100-250 nmol J-1. The main products are ethane, ethylene and acetylene. Higher saturated hydrocarbons up to C6 have been detected. The observed oxygen-functional hydrocarbons are methanol, ethanol and lower concentrations of aldehydes, ketones, dimethylether and methylformate. Methanol seems to be exclusively produced with CH4/O2 mixtures at a maximum production efficiency of 0.35 nmol J-1. CH4/CO2 mixtures appear to yield higher hydrocarbons. Carboxylic acids appear to be mainly present in the aqueous reactor phase, possibly together with higher molecular weight species.

Characteristics of molecular hydrogen and CH* radicals in a methane plasma in a magnetically enhanced capacitive RF discharge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Avtaeva, S. V.; Lapochkina, T. M.

2007-09-15

The parameters of a methane-containing plasma in an asymmetric RF capacitive discharge in an external magnetic field were studied using optical emission spectroscopy. The power deposited in the discharge was 90 W and the gas pressure and magnetic field were varied in the ranges 1-5 Pa and 50-200 G, respectively. The vibrational and rotational temperatures of hydrogen molecules and CH* radicals were measured as functions of the magnetic field and methane pressure. The ratio between the densities of atomic and molecular hydrogen was estimated. The processes responsible for the excitation of molecular hydrogen and CH* radicals in a methane-containing plasmamore » in an RF capacitive discharge are analyzed.« less

Pressure-relief and methane production performance of pressure relief gas extraction technology in the longwall mining

NASA Astrophysics Data System (ADS)

Zhang, Cun; Tu, Shihao; Chen, Min; Zhang, Lei

2017-02-01

Pressure relief gas extraction technology (PRGET) has been successfully implemented at many locations as a coal mine methane exploitation and outburst prevention technology. Comprehensive PRGET including gob gas venthole (GGV), crossing seam drilling hole (CSDH), large diameter horizontal long drilling hole (LDHLDH) and buried pipe for extraction (BPE) have been used to extract abundant pressure-relief methane (PRM) during protective coal seam mining; these techniques mitigated dangers associated with coal and gas outbursts in 13-1 coal seam mining in the Huainan coalfield. These extraction technologies can ensure safe protective seam mining and effectively extract coal and gas. This article analyses PRGET production performance and verifies it with the field measurement. The results showed that PRGET drilling to extract PRM from the protected coal seam significantly reduced methane emissions from a longwall ventilation system and produced highly efficient extraction. Material balance analyses indicated a significant decrease in gas content and pressure in the protected coal seam, from 8.78 m3 t-1 and 4.2 MPa to 2.34 m3 t-1 and 0.285 MPa, respectively. The field measurement results of the residual gas content in protected coal seam (13-1 coal seam) indicated the reliability of the material balance analyses and the pressure relief range of PRGET in the protected coal seam is obtained.

High-Frequency Measurements of Tree Methane Fluxes Indicate a Primary Souce Inside Tree Tissue

NASA Astrophysics Data System (ADS)

Brewer, P.; Megonigal, P.

2017-12-01

Methane emissions from the boles and shoots of living upland trees is a recent discovery with significant implications for methane budgets. Forest soil methane uptake is the greatest terrestrial methane sink, but studies have shown this may be partially for fully offset by tree methane sources. However, our ability to quantify the tree source has been hampered because the ultimate biological source(s) of methane is unclear. We measured methane fluxes from two species of living tree boles in an Eastern North American deciduous forest over 100 consecutive days. Our two hour sampling intervals allowed us to characterize diurnal patterns and seasonal dynamics. We observed wide intraspecific differences in average flux rates and diurnal dynamics, even between adjacent individuals. This and other properties of the fluxes indicates the primary methane source is likely within the tree tissues, not in soil or groundwater. Emissions of methane from trees offset approximately 10% of soil uptake on average, but at times tree fluxes were much higher. Preliminary analyses indicate the highest rates are related to tree life history, tree growth, temperature, ground-water depth, and soil moisture.

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

NASA Astrophysics Data System (ADS)

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

2016-06-01

Despite massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix-a limiting step in shale gas extraction. Using molecular simulations, we here show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30-47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3-35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.

Miller-Urey Experiments to Assess the Production of Amino Acids under Impact Conditions on Early Titan

NASA Astrophysics Data System (ADS)

Turse, Carol; Khan, A.; Leitner, J. J.; Firneis, M. G.; Schulze-Makuch, D.

2012-05-01

We performed Miller-Urey type experiments to determine the organic synthesis of amino acids under conditions that have likely occurred on Saturn's moon Titan and are also relevant to Jupiter's moon Europa. We conducted the first set of experiments under early Earth conditions, similar to the original Miller-Urey experiments (Miller, 1953). In brief, the 250ml round bottom flask was filled with approximately 200mL of filtered sterile water and the apparatus was placed under vacuum for 10 minutes to purge the water of gases. The system was then flushed with hydrogen gas and placed under vacuum three times. Gases were then added in the following order: hydrogen gas to 0.1 bar, methane gas to 0.45 bar and ammonia to 0.45 bar ( 1bar total). The water was then brought to a boil and the spark was applied using the tesla coil up to a maximum of 50,000 volts. The apparatus was run for approximately 5-7 days. Between the runs the apparatus was cleaned using a hot 10% sodium hydroxide solution followed by a dilute sulfuric acid wash and four rinses with Millipure water. In the second set of experiments we simulated conditions that could have existed on an early, warm Titan or after an asteroid strike on Titan (Schulze-Makuch and Grinspoon, 2005), particularly if the strike would have occurred in the subpolar areas that exhibit vast ethane-methane lakes. If the asteroid or comet would be of sufficient size, it would also puncture the icy crust and access a vast reservoir of the subsurface liquid ammonia-water mixture. Thompson and Sagan (1992) showed that a liquid water-ammonia body could exist for millions of years on Titan after an asteroid impact. Thus, we modified the experimental conditions as described above and report on the results. Assuming a moderate impact in the subpolar areas of Titan, we used an atmosphere of currently 1.5 bar, but increased the partial pressure of methane to 1 bar (and 0.1 bar ammonia assuming a minor amount of ammonia-water ice being evaporated during the impact) (1) Assuming a major impact that would puncture the icy crust and evaporate a significant portion of ammonia on impact, we increased the ammonia partial pressure to 0.5 bar (keeping methane constant at 1 bar) and used a 30 % ammonia water mixture as liquid reservoir in the experiment. (2) Titan's atmosphere also contains various higher organic trace constituents, commonly referred to as tholins, which include ethylene, ethane, acetylene, hydrogen cyanide and various aromatic compounds. A selection of these compounds was added in trace amounts to the experimental run.

The impact of compaction and leachate recirculation on waste degradation in simulated landfills.

PubMed

Ko, Jae Hac; Yang, Fan; Xu, Qiyong

2016-07-01

This study investigated the impact of compaction and leachate recirculation on anaerobic degradation of municipal solid waste (MSW) at different methane formation phases. Two stainless steel lysimeters, C1 and C2, were constructed by equipping a hydraulic cylinder to apply pressure load (42kPs) on the MSW. When MSW started to produce methane, C1 was compacted, but C2 was compacted when the methane production rate declined from the peak generation rate. Methane production of C1was inhibited by the compaction and resulted in producing a total of 106L methane (44L/kgVS). However, the compaction in C2 promoted MSW degradation resulting in producing a total of 298L methane (125L/kgVS). The concentrations of volatile fatty acids and chemical oxygen demand showed temporary increases, when pressure load was applied. It was considered that the increased substrate accessibility within MSW by compaction could cause either the inhibition or the enhancement of methane production, depending the tolerability of methanogens on the acidic inhibition. Leachate recirculation also gave positive effects on methane generation from wet waste in the decelerated methanogenic phase by increasing mass transfer and the concentrations of volatile fatty acids. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hydrogenation of Carbon Dioxide to Methane by Ruthenium Nanoparticles in Ionic Liquid.

PubMed

Melo, Catarina I; Szczepańska, Anna; Bogel-Łukasik, Ewa; Nunes da Ponte, Manuel; Branco, Luís C

2016-05-23

The efficient transformation of carbon dioxide into fuels can be an excellent alternative to sequestration. In this work, we describe CO2 hydrogenation to methane in imidazolium-based ionic liquid media, using ruthenium nanoparticles prepared in situ as catalyst. The best yield of methane (69 %) was achieved using 0.24 mol % ruthenium catalyst (in [omim][NTf2 ], 1-octyl-3-methylimidazolium bistrifluoromethanesulfonylimide, at 40 bar of hydrogen pressure plus 40 bar of CO2 pressure, and at 150 °C. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling of Methane Migration in Shallow Aquifers from Shale Gas Well Drilling.

PubMed

Zhang, Liwei; Soeder, Daniel J

2016-05-01

The vertical portion of a shale gas well, known as the "tophole" is often drilled using an air-hammer bit that may introduce pressures as high as 2400 kPa (350 psi) into groundwater while penetrating shallow aquifers. A 3-D TOUGH2 model was used to simulate the flow of groundwater under the high hydraulic heads that may be imposed by such trapped compressed air, based on an observed case in West Virginia (USA) in 2012. The model realizations show that high-pressure air trapped in aquifers may cause groundwater to surge away from the drill site at observable velocities. If dissolved methane is present within the aquifer, the methane can be entrained and transported to a maximum distance of 10.6 m per day. Results from this study suggest that one cause of the reported increase in methane concentrations in groundwater near shale gas production wells may be the transport of pre-existing methane via groundwater surges induced by air drilling, not necessarily direct natural gas leakage from the unconventional gas reservoir. The primary transport mechanisms are advective transport of dissolved methane with water flow, and diffusive transport of dissolved methane. © 2015, National Ground Water Association.

The Atmospheres of Directly Imaged Planets: Where Has All the Methane Gone?

NASA Technical Reports Server (NTRS)

Marley, Mark S.; Zahnle, Kevin

2014-01-01

Methane and ammonia both first appear at lower effective temperatures in brown dwarf atmospheres than equilibrium chemistry models would suggest. This has traditionally been understood as a consequence of vertical mixing timescales being shorter than chemical equilibration timescales in brown dwarf photospheres. Indeed the eddy diffusivity, a variable accounting for the vigor of vertical mixing, has become a standard part of the description of brown dwarf atmosphere models, along with Teff and log g. While some models have suggested that methane is less favored at lower gravity, the almost complete absence of methane in the atmospheres of directly imaged planets, such as those orbiting HR 8799, even at effective temperatures where methane is readily apparent in brown dwarf spectra, has been puzzling. To better understand the paucity of methane in low gravity atmospheres we have revisited the problem of methane chemistry and mixing. We employed a 1-D atmospheric chemistry code augmented with an updated and complete network of the chemical reactions that link CO to CH4. We find the methane abundance at altitudes at or above the effective photosphere is a strong function of surface gravity because higher g shifts the p-T structure to higher pressures (i.e., a given optical depth is proportional to p/g, a relation mitigated somewhat by pressure broadening). Thus quenching in more massive brown dwarfs occurs at a lower temperature and higher pressure, both favoring CH4. We predict that in the lowest mass young giant planets, methane will appear very late, at effective temperatures as low as 600 K rather than the 1200 K seen among field brown dwarfs. This methane deficiency has important implications for the interpretation of spectra as well as methane-based planetary companion searches, such as the NICI survey. The GPI and SPHERE surveys will test these ideas and probe atmospheric chemistry and composition in an entire new range of parameter space. A caveat is that these calculations presume that the C to O ratio is comfortably less than one; the behavior is quite different if C and O are equally abundant, and of course CH4 is always present if C exceeds O.

Dissociation of Laboratory-Synthesized Methane Hydrate in Coarse-Grained Sediments by Slow Depressurization

NASA Astrophysics Data System (ADS)

Phillips, S. C.; You, K.; Borgfeldt, T.; Meyer, D.; Dong, T.; Flemings, P. B.

2016-12-01

We performed four dissociation experiments in which experimentally-formed methane hydrate was dissociated via slow, stepwise depressurization, revealing in situ salinity conditions. Overall, these results suggest the occurrence of local pore water freshening around dissociating hydrate in which bulk equilibrium behavior is limited by salt diffusion. Depressurization was performed at a constant confining temperature over 1 to 3 weeks by releasing small volumes of methane gas from the top of a vertically-oriented sample into an inverted graduated cylinder. We identify three distinct regimes of depressurization based on pressure drop behavior: (1) release of free gas down to initial hydrate dissociation at 3.3 MPa in NaBr or 4.64 MPa in NaCl, (2) dissociation of methane hydrate characterized by a slow, logarithmic increase in pressure after each gas release and (3) residual free gas release. Initial hydrate dissociation in NaCl brine at 4.64 MPa corresponds to the phase boundary for hydrate in 9.6 wt% NaCl. In the NaCl experiment, pressure increases of 0.16 MPa while the sample was shut in over 3 days likely correspond to a recovery in salinity of 0.7 wt. %. Salt ions likely diffuse from brine ahead of the hydrate front, based on a length scale for diffusion of NaCl of 6.3 cm for 3 days. In this experiment dissociation at bulk equilibrium is expected to decline from 4.54 to 4.04 MPa; however actual dissociation during 73 gas releases over 15 days, results in a pressure drop from 4.64 to 3.25 MPa. Hydrate samples were formed by injection of methane gas at 1 ºC and 12.24 MPa within a cylinder packed with medium-grained quartz sand and initially saturated in a 7 wt% NaBr or NaCl solution. In two experiments in which the system was thoroughly leak tested, total methane consumed during formation and recovered during depressurization match within 7% indicating this approach to be relatively accurate for determining total methane in experimental or pressure core samples.

Transformations in methane hydrates

USGS Publications Warehouse

Chou, I.-Ming; Sharma, A.; Burruss, R.C.; Shu, J.; Mao, Ho-kwang; Hemley, R.J.; Goncharov, A.F.; Stern, L.A.; Kirby, S.H.

2000-01-01

Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) A?? and volume V = 5051.3(13) A??3; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) A??, c = 9.992(3) A??, and V = 1241.9(5) A??3. The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins.

Light-Dependent Aerobic Methane Oxidation Reduces Methane Emissions from Seasonally Stratified Lakes

PubMed Central

Oswald, Kirsten; Milucka, Jana; Brand, Andreas; Littmann, Sten; Wehrli, Bernhard; Kuypers, Marcel M. M.; Schubert, Carsten J.

2015-01-01

Lakes are a natural source of methane to the atmosphere and contribute significantly to total emissions compared to the oceans. Controls on methane emissions from lake surfaces, particularly biotic processes within anoxic hypolimnia, are only partially understood. Here we investigated biological methane oxidation in the water column of the seasonally stratified Lake Rotsee. A zone of methane oxidation extending from the oxic/anoxic interface into anoxic waters was identified by chemical profiling of oxygen, methane and δ13C of methane. Incubation experiments with 13C-methane yielded highest oxidation rates within the oxycline, and comparable rates were measured in anoxic waters. Despite predominantly anoxic conditions within the zone of methane oxidation, known groups of anaerobic methanotrophic archaea were conspicuously absent. Instead, aerobic gammaproteobacterial methanotrophs were identified as the active methane oxidizers. In addition, continuous oxidation and maximum rates always occurred under light conditions. These findings, along with the detection of chlorophyll a, suggest that aerobic methane oxidation is tightly coupled to light-dependent photosynthetic oxygen production both at the oxycline and in the anoxic bottom layer. It is likely that this interaction between oxygenic phototrophs and aerobic methanotrophs represents a widespread mechanism by which methane is oxidized in lake water, thus diminishing its release into the atmosphere. PMID:26193458

Pump-to-Wheels Methane Emissions from the Heavy-Duty Transportation Sector.

PubMed

Clark, Nigel N; McKain, David L; Johnson, Derek R; Wayne, W Scott; Li, Hailin; Akkerman, Vyacheslav; Sandoval, Cesar; Covington, April N; Mongold, Ronald A; Hailer, John T; Ugarte, Orlando J

2017-01-17

Pump-to-wheels (PTW) methane emissions from the heavy-duty (HD) transportation sector, which have climate change implications, are poorly documented. In this study, methane emissions from HD natural gas fueled vehicles and the compressed natural gas (CNG) and liquefied natural gas (LNG) fueling stations that serve them were characterized. A novel measurement system was developed to quantify methane leaks and losses. Engine related emissions were characterized from twenty-two natural gas fueled transit buses, refuse trucks, and over-the-road (OTR) tractors. Losses from six LNG and eight CNG stations were characterized during compression, fuel delivery, storage, and from leaks. Cryogenic boil-off pressure rise and pressure control venting from LNG storage tanks were characterized using theoretical and empirical modeling. Field and laboratory observations of LNG storage tanks were used for model development and evaluation. PTW emissions were combined with a specific scenario to view emissions as a percent of throughput. Vehicle tailpipe and crankcase emissions were the highest sources of methane. Data from this research are being applied by the authors to develop models to forecast methane emissions from the future HD transportation sector.

A high-pressure premixed flat-flame burner for chemical process studies. [of pollutant formation in hydrocarbon flames

NASA Technical Reports Server (NTRS)

Miller, I. M.

1978-01-01

A premixed flat-flame burner was designed and tested with methane-air mixtures at pressures from 1.1 to 20 atm and equivalence ratios from 0.7 to 1.1. Reactant velocity in the burner mixing chamber was used to characterize the range of stable flames at each pressure-equivalence-ratio condition. Color photographs of the flames were used to determine flame zone thickness and flame height. The results show that this burner can be used for chemical process studies in premixed high pressure methane-air flames up to 20 atm.

Synthesis of polycrystalline methane hydrate, and its phase stability and mechanical properties at elevated pressure

USGS Publications Warehouse

Stern, L.A.; Kirby, S.H.; Durham, W.B.

1997-01-01

Test specimens of methane hydrate were grown under static conditions by combining cold, pressurized CH4 gas with H2O ice grains, then warming the system to promote the reaction CH4 (g) + 6H2O (s???l) ??? CH4??6H2O. Hydrate formation evidently occurs at the nascent ice/liquid water interface, and complete reaction was achieved by warming the system above 271.5 K and up to 289 K, at 25-30 MPa, for approximately 8 hours. The resulting material is pure methane hydrate with controlled grain size and random texture. Fabrication conditions placed the H2O ice well above its melting temperature before reaction completed, yet samples and run records showed no evidence for bulk melting of the ice grains. Control experiments using Ne, a non-hydrate-forming gas, verified that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting is easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably at temperatures well above its melting point. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T= 140-200 K, Pc= 50-100 MPa, and ????= 10-4-10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to a higher degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; x-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Polyacrylonitrile-Derived Sponge-Like Micro/Macroporous Carbon for Selective CO2 Separation.

PubMed

Guo, Li-Ping; Hu, Qing-Tao; Zhang, Peng; Li, Wen-Cui; Lu, An-Hui

2018-06-12

CO 2 capture under a dynamical flow situation requires adsorbents possessing balanced proportion of macropores as diffusion path and micropores as adsorption reservoir. However, the construction of interconnected micro-/macropores structure coupled with abundant nitrogen species into one carbon skeleton remains a challenge. Here, we report a new approach to prepare sponge-like carbon with a well-developed micro-/macroporous structure and enriched nitrogen species through aqueous phase polymerization of acrylonitrile in the presence of graphene oxide. The tension stress caused by the uniform thermal shrinkage of polyacrylonitrile during the pyrolysis together with the favorable flexibility of graphene oxide sheets are responsible for the formation of the sponge-like morphology. The synergistic effect of micro-/macroporous framework and rich CO 2 -philic site enables such carbon to decrease resistance to mass transfer and show high CO 2 dynamic selectivity over N 2 (454) and CH 4 (11), as well as good CO 2 capacity at 298 K under low CO 2 partial pressure (0.17 bar, a typical CO 2 partial pressure in flue gas). The above attributes make this porous carbon a promising candidate for CO 2 capture from flue gas, methane sources and other relevant applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molybdenum Nitrogenase Catalyzes the Reduction and Coupling of CO to Form Hydrocarbons*♦

PubMed Central

Yang, Zhi-Yong; Dean, Dennis R.; Seefeldt, Lance C.

2011-01-01

The molybdenum-dependent nitrogenase catalyzes the multi-electron reduction of protons and N2 to yield H2 and 2NH3. It also catalyzes the reduction of a number of non-physiological doubly and triply bonded small molecules (e.g. C2H2, N2O). Carbon monoxide (CO) is not reduced by the wild-type molybdenum nitrogenase but instead inhibits the reduction of all substrates catalyzed by nitrogenase except protons. Here, we report that when the nitrogenase MoFe protein α-Val70 residue is substituted by alanine or glycine, the resulting variant proteins will catalyze the reduction and coupling of CO to form methane (CH4), ethane (C2H6), ethylene (C2H4), propene (C3H6), and propane (C3H8). The rates and ratios of hydrocarbon production from CO can be adjusted by changing the flux of electrons through nitrogenase, by substitution of other amino acids located near the FeMo-cofactor, or by changing the partial pressure of CO. Increasing the partial pressure of CO shifted the product ratio in favor of the longer chain alkanes and alkenes. The implications of these findings in understanding the nitrogenase mechanism and the relationship to Fischer-Tropsch production of hydrocarbons from CO are discussed. PMID:21454640

Quantifying the Presence and Activity of Aerobic, Vinyl Chloride-Degrading Microorganisms in Dilute Groundwater Plumes by Using Real-Time PCR

DTIC Science & Technology

2013-07-01

throughout the observation period. A 0.25-ml Pressure-Lok gas -tight syringe with a side-ported needle was used to take 0.1 ml headspace samples during...33. Biodegradation of methane, VC and a methane+VC mixture by methane enrichment cultures derived from Carver well RB63I. These results indicate that...VC and a methane+VC mixture by methane enrichment cultures derived from Carver well RB63I. These results are a repeat of the experiment depicted in

High methane natural gas/air explosion characteristics in confined vessel.

PubMed

Tang, Chenglong; Zhang, Shuang; Si, Zhanbo; Huang, Zuohua; Zhang, Kongming; Jin, Zebing

2014-08-15

The explosion characteristics of high methane fraction natural gas were investigated in a constant volume combustion vessel at different initial conditions. Results show that with the increase of initial pressure, the peak explosion pressure, the maximum rate of pressure rise increase due to a higher amount (mass) of flammable mixture, which delivers an increased amount of heat. The increased total flame duration and flame development time result as a consequence of the higher amount of flammable mixture. With the increase of the initial temperature, the peak explosion pressures decrease, but the pressure increase during combustion is accelerated, which indicates a faster flame speed and heat release rate. The maximum value of the explosion pressure, the maximum rate of pressure rise, the minimum total combustion duration and the minimum flame development time is observed when the equivalence ratio of the mixture is 1.1. Additionally, for higher methane fraction natural gas, the explosion pressure and the maximum rate of pressure rise are slightly decreased, while the combustion duration is postponed. The combustion phasing is empirically correlated with the experimental parameters with good fitting performance. Furthermore, the addition of dilute gas significantly reduces the explosion pressure, the maximum rate of pressure rise and postpones the flame development and this flame retarding effect of carbon dioxide is stronger than that of nitrogen. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis of single-site copper catalysts for methane partial oxidation

DOE PAGES

Grundner, S.; Luo, W.; Sanchez-Sanchez, M.; ...

2015-12-24

Cu-Exchanged zeolites are known as active materials for methane oxidation to methanol. However, understanding of the formation of Cu active species during synthesis, dehydration and activation is fragmented and rudimentary. We show here how a synthesis protocol guided by insight in the ion exchange elementary steps leads to highly uniform Cu species in mordenite (MOR).

Influence from Surrounding Land on the Turbulence Measurements Above a Lake

NASA Astrophysics Data System (ADS)

Sahlée, Erik; Rutgersson, Anna; Podgrajsek, Eva; Bergström, Hans

2014-02-01

Turbulence measurements taken at a Swedish lake are analyzed. Although the measurements took place over a relatively large lake with several km of undisturbed fetch, the turbulence structure was found to be highly influenced by the surrounding land during daytime. Variance spectra of both horizontal velocity and scalars during both unstable and stable stratification displayed a low frequency peak. The energy at lower frequencies showed a daily variation, increasing in the morning and decreasing in the afternoon. This behaviour is explained by spectral lag, where the low frequency energy due to large eddies that originate from the convective boundary layer above the surrounding land. When the air is advected over the lake the small eddies rapidly equilibrate with the new surface forcing. However, the large eddies remain for an appreciable distance and influence the turbulence in the developing lake boundary layer. The variances of the horizontal velocity and scalars are increased by these large eddies, while the turbulent fluxes are mainly unaffected. The drag coefficient, Stanton number and Dalton number used to parametrize the momentum flux, heat flux and latent heat flux respectively all compare well with current parametrizations developed for open sea conditions. The diurnal cycle of the partial pressure of methane, pCH4, observed at this site is closely related to the diurnal cycle of the lake-air methane flux. An idealized two-dimensional model simulation of the boundary layer at a lake site indicates that the strong response of pCH4 to the surface methane flux is due to the shallow internal boundary layer that develops above the lake, allowing methane to accumulate in a relatively small volume.

Dense ceramic membranes for converting methane to syngas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balachandran, U.; Dusek, J.T.; Picciolo, J.J.

1995-07-01

Dense mixed-oxide ceramics capable of conducting both electrons and oxygen ions are promising materials for partial oxygenation of methane to syngas. We are particularly interested in an oxide based on the Sr-Fe-Co-O system. Dense ceramic membrane tubes have been fabricated by a plastic extrusion technique. The sintered tubes were then used to selectively transport oxygen from air through the membrane to make syngas without the use of external electrodes. The sintered tubes have operated for >1000 h, and methane conversion efficiencies of >98% have been observed. Mechanical properties, structural integrity of the tubes during reactor operation, results of methane conversion,more » selectivity of methane conversion products, oxygen permeation, and fabrication of multichannel configurations for large-scale production of syngas will be presented.« less

Isolation of Succinivibrionaceae implicated in low methane emissions from Tammar wallabies.

PubMed

Pope, P B; Smith, W; Denman, S E; Tringe, S G; Barry, K; Hugenholtz, P; McSweeney, C S; McHardy, A C; Morrison, M

2011-07-29

The Tammar wallaby (Macropus eugenii) harbors unique gut bacteria and produces only one-fifth the amount of methane produced by ruminants per unit of digestible energy intake. We have isolated a dominant bacterial species (WG-1) from the wallaby microbiota affiliated with the family Succinivibrionaceae and implicated in lower methane emissions from starch-containing diets. This was achieved by using a partial reconstruction of the bacterium's metabolism from binned metagenomic data (nitrogen and carbohydrate utilization pathways and antibiotic resistance) to devise cultivation-based strategies that produced axenic WG-1 cultures. Pure-culture studies confirm that the bacterium is capnophilic and produces succinate, further explaining a microbiological basis for lower methane emissions from macropodids. This knowledge also provides new strategic targets for redirecting fermentation and reducing methane production in livestock.

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

In spite of the massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Here we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases, and we usemore » molecular simulations to demonstrate it. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Finally, our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.« less

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

PubMed Central

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

2016-01-01

Despite massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Using molecular simulations, we here show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release. PMID:27306967

Nanostructural control of methane release in kerogen and its implications to wellbore production decline

DOE PAGES

Ho, Tuan Anh; Criscenti, Louise J.; Wang, Yifeng

2016-06-16

In spite of the massive success of shale gas production in the US in the last few decades there are still major concerns with the steep decline in wellbore production and the large uncertainty in a long-term projection of decline curves. A reliable projection must rely on a mechanistic understanding of methane release in shale matrix–a limiting step in shale gas extraction. Here we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~30–47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases, and we usemore » molecular simulations to demonstrate it. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3–35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. Finally, our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs. The long-term production decline appears controlled by the second stage of gas release.« less

Process and apparatus for the production of hydrogen by steam reforming of hydrocarbon

DOEpatents

Sircar, Shivaji; Hufton, Jeffrey Raymond; Nataraj, Shankar

2000-01-01

In the steam reforming of hydrocarbon, particularly methane, under elevated temperature and pressure to produce hydrogen, a feed of steam and hydrocarbon is fed into a first reaction volume containing essentially only reforming catalyst to partially reform the feed. The balance of the feed and the reaction products of carbon dioxide and hydrogen are then fed into a second reaction volume containing a mixture of catalyst and adsorbent which removes the carbon dioxide from the reaction zone as it is formed. The process is conducted in a cycle which includes these reactions followed by countercurrent depressurization and purge of the adsorbent to regenerate it and repressurization of the reaction volumes preparatory to repeating the reaction-sorption phase of the cycle.

Spectral separation of gaseous fluorocarbon mixtures and measurement of diffusion constants by 19F gas phase DOSY NMR.

PubMed

Marchione, Alexander A; McCord, Elizabeth F

2009-11-01

Diffusion-ordered (DOSY) NMR techniques have for the first time been applied to the spectral separation of mixtures of fluorinated gases by diffusion rates. A mixture of linear perfluoroalkanes from methane to hexane was readily separated at 25 degrees C in an ordinary experimental setup with standard DOSY pulse sequences. Partial separation of variously fluorinated ethanes was also achieved. The constants of self-diffusion of a set of pure perfluoroalkanes were obtained at pressures from 0.25 to 1.34 atm and temperatures from 20 to 122 degrees C. Under all conditions there was agreement within 20% of experimental self-diffusion constant D and values calculated by the semiempirical Fuller method.

Vibrations At Surfaces During Heterogeneous Catalytic Reactions

NASA Astrophysics Data System (ADS)

Aragno, A.; Basini, Luca; Marchionna, M.; Raffaelli, A.

1989-12-01

FTIR spectroscopies can be used in a wide range of temperature and pressure conditions to investigate on the chemistry and the physics of heterogeneous catalytic reactions. In this paper we have shortly discussed the spectroscopic results obtained during the study of two different reactions; the skeletal isomerization of 1-butene to obtain 2-methylpropene and the surface aggregation and fragmentation of rhodium carbonyl complexes during thermal treatments in N2, H2, CO, CH4 atmospheres. In the first case high temperature proton tran-sfer reactions are proposed to be responsible for the skeletal isomerization reaction. In the second case our experiments have shown a partial reversibility of the nucleation processes at the surfaces and revealed a low temperature reactivity of methane on rhodium car-bonyl surface complexes.

Note: Nonpolar solute partial molar volume response to attractive interactions with water.

PubMed

Williams, Steven M; Ashbaugh, Henry S

2014-01-07

The impact of attractive interactions on the partial molar volumes of methane-like solutes in water is characterized using molecular simulations. Attractions account for a significant 20% volume drop between a repulsive Weeks-Chandler-Andersen and full Lennard-Jones description of methane interactions. The response of the volume to interaction perturbations is characterized by linear fits to our simulations and a rigorous statistical thermodynamic expression for the derivative of the volume to increasing attractions. While a weak non-linear response is observed, an average effective slope accurately captures the volume decrease. This response, however, is anticipated to become more non-linear with increasing solute size.

Note: Nonpolar solute partial molar volume response to attractive interactions with water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, Steven M.; Ashbaugh, Henry S., E-mail: hanka@tulane.edu

2014-01-07

The impact of attractive interactions on the partial molar volumes of methane-like solutes in water is characterized using molecular simulations. Attractions account for a significant 20% volume drop between a repulsive Weeks-Chandler-Andersen and full Lennard-Jones description of methane interactions. The response of the volume to interaction perturbations is characterized by linear fits to our simulations and a rigorous statistical thermodynamic expression for the derivative of the volume to increasing attractions. While a weak non-linear response is observed, an average effective slope accurately captures the volume decrease. This response, however, is anticipated to become more non-linear with increasing solute size.

Comet Impacts as a Source of Methane on Titan

NASA Astrophysics Data System (ADS)

Howard, Michael; Goldman, N.; Vitello, P. A.

2006-12-01

We model comet impacts on Titan as a possible source of atmospheric methane. That is, we study the formation of methane in comet impacts using chemical equilibrium calculations coupled with arbitrary Lagrange-Eulerian (ALE) hydrodynamics. That is, we study the chemical transformation of comet material under high pressure and temperature conditions as it impacts Titan. We assume that the comet is composed of ice, graphite, nitrogen and some hydrocarbons. For certain pressure and temperature regimes, in chemical equilibrium, a significant amount of ice and graphite can be transformed into methane. As a result, we find that a significant amount of methane can be formed in comet collisions on Titan. The methane is formed in the post-impact vapor clouds that form as the comet material expands and cools. We use molecular dynamics to construct an equation of state for the ice surface structures and the comet material. We also study kinetic processes for methane formation during the expansion and cooling phase. We discuss the implication of our results for comets as a possible source of abiotic methane on Titan and its implications on the origin of life. We also discuss the various uncertainties in our model. * This work was performed under the auspices of the U.S. Department of Energy by University of California, Lawrence Livermore National Laboratory under Contract W-7405-Eng-48.

Integrated Pressure-Fed Liquid Oxygen / Methane Propulsion Systems - Morpheus Experience, MARE, and Future Applications

NASA Technical Reports Server (NTRS)

Hurlbert, Eric; Morehead, Robert; Melcher, John C.; Atwell, Matt

2016-01-01

An integrated liquid oxygen (LOx) and methane propulsion system where common propellants are fed to the reaction control system and main engines offers advantages in performance, simplicity, reliability, and reusability. LOx/Methane provides new capabilities to use propellants that are manufactured on the Mars surface for ascent return and to integrate with power and life support systems. The clean burning, non-toxic, high vapor pressure propellants provide significant advantages for reliable ignition in a space vacuum, and for reliable safing or purging of a space-based vehicle. The NASA Advanced Exploration Systems (AES) Morpheus lander demonstrated many of these key attributes as it completed over 65 tests including 15 flights through 2014. Morpheus is a prototype of LOx/Methane propellant lander vehicle with a fully integrated propulsion system. The Morpheus lander flight demonstrations led to the proposal to use LOx/Methane for a Discovery class mission, named Moon Aging Regolith Experiment (MARE) to land an in-situ science payload for Southwest Research Institute on the Lunar surface. Lox/Methane is extensible to human spacecraft for many transportation elements of a Mars architecture. This paper discusses LOx/Methane propulsion systems in regards to trade studies, the Morpheus project experience, the MARE NAVIS (NASA Autonomous Vehicle for In-situ Science) lander, and future possible applications. The paper also discusses technology research and development needs for Lox/Methane propulsion systems.

Effect of Propellant Flowrate and Purity on Carbon Deposition in LO2/Methane Gas Generators

NASA Technical Reports Server (NTRS)

Bossard, J. A.; Burkhardt, W. M.; Niiya, K. Y.; Braam, F.

1989-01-01

The generation and deposition of carbon was studied in the Carbon Deposition Program using subscale hardware with LO2/Liquid Natural Gas (LNG) and LO2/Methane propellants at low mixture ratios. The purpose of the testing was to evaluate the effect of methane purity and full scale injection density on carbon deposition. The LO2/LNG gas generator/preburner testing was performed at mixture ratios between 0.24 and 0.58 and chamber pressures from 5.8 to 9.4 MPa (840 to 1370 psia). A total of seven 200 second duration tests were performed. The LNG testing occurred at low injection densities, similar to the previous LO2/RP-1, LO2/propane, and LO2/methane testing performed on the carbon deposition program. The current LO2/methane test series occurred at an injection density factor of approximately 10 times higher than the previous testing. The high injection density LO2/methane testing was performed at mixture ratios between from 0.23 to 0.81 and chamber pressures from 6.4 to 15.2 MPa (925 to 2210 psia). A total of nine high injection density tests were performed. The testing performed demonstrated that low purity methane (LNG) did not produce any detectable change in carbon deposition when compared to pure methane. In addition, the C* performance and the combustion gas temperatures measured were similar to those obtained for pure methane. Similar results were obtained testing pure methane at higher propellant injection densities with coarse injector elements.

High pressure shock tube ignition delay time measurements during oxy-methane combustion with high levels of CO 2 dilution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pryor, Owen; Barak, Samuel; Lopez, Joseph

For this study, ignition delay times and methane species time-histories were measured for methane/O 2 mixtures in a high CO 2 diluted environment using shock tube and laser absorption spectroscopy. The experiments were performed between 1300 K and 2000 K at pressures between 6 and 31 atm. The test mixtures were at an equivalence ratio of 1 with CH 4 mole fractions ranging from 3.5% -5% and up to 85% CO 2 with a bath of argon gas as necessary. The ignition delay times and methane time histories were measured using pressure, emission, and laser diagnostics. Predictive ability of twomore » literature kinetic mechanisms (GRI 3.0 and ARAMCO Mech 1.3) was tested against current data. In general, both mechanisms performed reasonably well against measured ignition delay time data. The methane time-histories showed good agreement with the mechanisms for most of the conditions measured. A correlation for ignition delay time was created taking into the different parameters showing that the ignition activation energy for the fuel to be 49.64 kcal/mol. Through a sensitivity analysis, CO 2 is shown to slow the overall reaction rate and increase the ignition delay time. To the best of our knowledge, we present the first shock tube data during ignition of methane/CO 2/O 2 under these conditions. In conclusion, current data provides crucial validation data needed for development of future kinetic mechanisms.« less

High pressure shock tube ignition delay time measurements during oxy-methane combustion with high levels of CO 2 dilution

DOE PAGES

Pryor, Owen; Barak, Samuel; Lopez, Joseph; ...

2017-03-30

For this study, ignition delay times and methane species time-histories were measured for methane/O 2 mixtures in a high CO 2 diluted environment using shock tube and laser absorption spectroscopy. The experiments were performed between 1300 K and 2000 K at pressures between 6 and 31 atm. The test mixtures were at an equivalence ratio of 1 with CH 4 mole fractions ranging from 3.5% -5% and up to 85% CO 2 with a bath of argon gas as necessary. The ignition delay times and methane time histories were measured using pressure, emission, and laser diagnostics. Predictive ability of twomore » literature kinetic mechanisms (GRI 3.0 and ARAMCO Mech 1.3) was tested against current data. In general, both mechanisms performed reasonably well against measured ignition delay time data. The methane time-histories showed good agreement with the mechanisms for most of the conditions measured. A correlation for ignition delay time was created taking into the different parameters showing that the ignition activation energy for the fuel to be 49.64 kcal/mol. Through a sensitivity analysis, CO 2 is shown to slow the overall reaction rate and increase the ignition delay time. To the best of our knowledge, we present the first shock tube data during ignition of methane/CO 2/O 2 under these conditions. In conclusion, current data provides crucial validation data needed for development of future kinetic mechanisms.« less

Towards eliminating systematic errors caused by the experimental conditions in Biochemical Methane Potential (BMP) tests.

PubMed

Strömberg, Sten; Nistor, Mihaela; Liu, Jing

2014-11-01

The Biochemical Methane Potential (BMP) test is increasingly recognised as a tool for selecting and pricing biomass material for production of biogas. However, the results for the same substrate often differ between laboratories and much work to standardise such tests is still needed. In the current study, the effects from four environmental factors (i.e. ambient temperature and pressure, water vapour content and initial gas composition of the reactor headspace) on the degradation kinetics and the determined methane potential were evaluated with a 2(4) full factorial design. Four substrates, with different biodegradation profiles, were investigated and the ambient temperature was found to be the most significant contributor to errors in the methane potential. Concerning the kinetics of the process, the environmental factors' impact on the calculated rate constants was negligible. The impact of the environmental factors on the kinetic parameters and methane potential from performing a BMP test at different geographical locations around the world was simulated by adjusting the data according to the ambient temperature and pressure of some chosen model sites. The largest effect on the methane potential was registered from tests performed at high altitudes due to a low ambient pressure. The results from this study illustrate the importance of considering the environmental factors' influence on volumetric gas measurement in BMP tests. This is essential to achieve trustworthy and standardised results that can be used by researchers and end users from all over the world. Copyright © 2014 Elsevier Ltd. All rights reserved.

Method of and system for producing electrical power

DOEpatents

Carabetta, Ralph A.; Staats, Gary E.; Cutting, John C.

1993-01-01

A method and system for converting the chemical energy of methane to electrical energy. Methane is thermally decomposed to hydrogen and carbon in a decomposing unit at a temperature not less than 1200.degree. K. and at a pressure above atmospheric pressure. Carbon and substantially pure oxygen and a cesium or potassium seed material is transmitted to a combustor which is maintained at a pressure of at least 50 atmospheres to combust the carbon and oxygen and provide an ionized plasma having a temperature not less than 2900.degree. K. The ionized plasma is accelerated to a velocity not less than 1000 m/sec and transported through an MHD generator having a magnetic field in the range of from 4 to 6 Tesla to generate dc power. The ionized plasma is decelerated and passed from the MHD generator in heat exchange relationship with the methane to heat the methane for decomposition, and thereafter any cesium or potassium seed material is recovered and transported to the combustor, and the dc power from the MHD generator is converted to ac power.

An empirical equation with tables of smoothed solubilities of methane in water and aqueous sodium chloride solutions up to 25 weight percent, 360 degrees C, and 138 MPa

USGS Publications Warehouse

Haas, John L.

1978-01-01

The total pressure for the system H2O-CH 4 is given by p(total) = P(H2O,t) + exp10[log x(CH 4) - a - b x(CH4)], where P(H2O,t) is the vapor pressure of H2O liquid at the temperature t (?C) and x(CH 4) is the molal concentration of methane in the solution. The terms a and b are functions of temperature only. Where the total pressure and temperature are known, the concentration of methane, x(CH4), is found by iteration. The concentration of methane in a sodium chloride brine, y(CH4), is estimated using the function log y(CH4) = log x(CH4) - A I, where A is the salting out constant and I is the ionic strength. For sodium chloride solutions, the ionic strength is equal to the molality of the salt. The equations are valid to 360?C, 138 MPa, and 25 weight percent sodium chloride.

The characteristics of gas hydrates recovered from the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope

USGS Publications Warehouse

Lu, H.; Lorenson, T.D.; Moudrakovski, I.L.; Ripmeester, J.A.; Collett, T.S.; Hunter, R.B.; Ratcliffe, C.I.

2011-01-01

Systematic analyses have been carried out on two gas hydrate-bearing sediment core samples, HYPV4, which was preserved by CH4 gas pressurization, and HYLN7, which was preserved in liquid-nitrogen, recovered from the BPXA-DOE-USGS Mount Elbert Stratigraphic Test Well. Gas hydrate in the studied core samples was found by observation to have developed in sediment pores, and the distribution of hydrate saturation in the cores imply that gas hydrate had experienced stepwise dissociation before it was stabilized by either liquid nitrogen or pressurizing gas. The gas hydrates were determined to be structure Type I hydrate with hydration numbers of approximately 6.1 by instrumentation methods such as powder X-ray diffraction, Raman spectroscopy and solid state 13C NMR. The hydrate gas composition was predominantly methane, and isotopic analysis showed that the methane was of thermogenic origin (mean ??13C=-48.6??? and ??D=-248??? for sample HYLN7). Isotopic analysis of methane from sample HYPV4 revealed secondary hydrate formation from the pressurizing methane gas during storage. ?? 2010 Elsevier Ltd.

Weak interactions between water and clathrate-forming gases at low pressures

DOE PAGES

Thürmer, Konrad; Yuan, Chunqing; Kimmel, Greg A.; ...

2015-07-17

Using scanning probe microscopy and temperature programed desorption we examined the interaction between water and two common clathrate-forming gases, methane and isobutane, at low temperature and low pressure. Water co-deposited with up to 10 –1 mbar methane or 10 –5 mbar isobutane at 140 K onto a Pt(111) substrate yielded pure crystalline ice, i.e., the exposure to up to ~ 10 7 gas molecules for each deposited water molecule did not have any detectable effect on the growing films. Exposing metastable, less than 2 molecular layers thick, water films to 10 –5 mbar methane does not alter their morphology, suggestingmore » that the presence of the Pt(111) surface is not a strong driver for hydrate formation. This weak water–gas interaction at low pressures is supported by our thermal desorption measurements from amorphous solid water and crystalline ice where 1 ML of methane desorbs near ~ 43 K and isobutane desorbs near ~ 100 K. As a result, similar desorption temperatures were observed for desorption from amorphous solid water.« less

Analysis of Percent On-Cell Reformation of Methane in SOFC Stacks: Thermal, Electrical and Stress Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Recknagle, Kurtis P.; Yokuda, Satoru T.; Jarboe, Daniel T.

2006-04-07

This report summarizes a parametric analysis performed to determine the effect of varying the percent on-cell reformation (OCR) of methane on the thermal and electrical performance for a generic, planar solid oxide fuel cell (SOFC) stack design. OCR of methane can be beneficial to an SOFC stack because the reaction (steam-methane reformation) is endothermic and can remove excess heat generated by the electrochemical reactions directly from the cell. The heat removed is proportional to the amount of methane reformed on the cell. Methane can be partially pre-reformed externally, then supplied to the stack, where rapid reaction kinetics on the anodemore » ensures complete conversion. Thus, the thermal load varies with methane concentration entering the stack, as does the coupled scalar distributions, including the temperature and electrical current density. The endotherm due to the reformation reaction can cause a temperature depression on the anode near the fuel inlet, resulting in large thermal gradients. This effect depends on factors that include methane concentration, local temperature, and stack geometry.« less

The effect of moisture on the methane adsorption capacity of shales: A study case in the eastern Qaidam Basin in China

NASA Astrophysics Data System (ADS)

Wang, Lu; Yu, Qingchun

2016-11-01

This study investigated the effects of moisture on high-pressure methane adsorption in carboniferous shales from the Qaidam Basin, China. The shale characteristics, including the organic/inorganic compositions and pore structure (volume and surface) distribution, were obtained using various techniques. Gibbs adsorption measurements were performed over a pressure range up to 6 MPa and temperatures of 308.15 K on dry samples and moisture-equilibrated samples to analyze the correlations between organic/inorganic matter, pore structure, and moisture content on the methane sorption capacity. Compared to dry samples, the sorption capacity of wet samples (0.44-2.52% of water content) is reduced from 19.7 ± 5.3% to 36.1% ± 6.1%. Langmuir fitting is conducted to investigate moisture-dependent variations of adsorbed methane density, Langmuir pressure, and volume. By combining the pore volume and surface distribution analyses, our observations suggested that the main competition sites for CH4-H2O covered pores of approximately 2-7 nm, whereas the effective sites for methane and water were predominantly distributed within smaller (<4 nm) and larger pores (>10 nm), respectively. Regarding the compositional correlations, the impact of moisture on the amount of adsorbed methane shows a roughly linearly decreasing trend with increasing TOC content ranging from 0.62 to 2.88%, whereas the correlation between the moisture effect and various inorganic components is more complicated. Further fitting results indicate that illite/smectite mixed formations are closely related to the methane capacity, whereas the illite content show an evident connection to the pore structural (volume and surface) variations in the presence of moisture.

Seismic reflections identify finite differences in gas hydrate resources

USGS Publications Warehouse

Dillon, William P.; Max, M.

1999-01-01

Gas hydrate is a gas-bearing, ice-like crystalline solid. The substance's build ing blocks consist of a gas molecule (generally methane) sur-rounded by a cage of water molecules. The total amount of methane in hydrate in the world is immense - the most recent speculative estimate centers on values of 21x1015 cu meters. Thus, it may represent a future energy resource. This estimate was presented by Keith Kvenvolden at the International Symposium on Methane Hydrates, Resources in the Near Future, sponsor ed by Japanese National Oil Company (Tokyo, October, 1998).But, as with any natural resource, there is a need to find naturally occurring concentrations in order to effectively extract gas. We need to answer four basic questions:Do methane hydrate concentrations suitable for methane extraction exist?How can we recognize these concentrations?Where are concentrations located?What processes control methane hydrate concentrations?Gas hydrate occurs naturally at the pressure/ temperature/chemical conditions that are present within ocean floor sediments at water depths greater than about 500 meters. The gas hydrate stability zone (GHSZ) extends from the sea bottom downward to a depth where the natural increase in temperature causes the hydrate to melt (dissociate), even though the downward pressure increase is working to increase gas hydrate stability.Thus, the base of the GHSZ tends to parallel the seafloor at any given water depth (pressure), because the sub-seafloor isotherms (depths of constant temperature) generally parallel the seafloor. The layer at which gas hydrate is stable commonly extends from the sea floor to several hundred meters below it. The gas in most gas hydrates is methane, generated by bacteria in the sediments. In some cases, it can be higher carbon-number, thermogenic hydrocarbon gases that rise from greater depths.

Theoretical Rocket Performance of Liquid Methane with Several Fluorine-Oxygen Mixtures Assuming Frozen Composition

NASA Technical Reports Server (NTRS)

Gordon, Sanford; Kastner, Michael E

1958-01-01

Theoretical rocket performance for frozen composition during expansion was calculated for liquid methane with several fluorine-oxygen mixtures for a range of pressure ratios and oxidant-fuel ratios. The parameters included are specific impulse, combustion-chamber temperature, nozzle-exit temperature molecular weight, characteristic velocity, coefficient of thrust, ratio of nozzle-exit area to throat area, specific heat at constant pressure, isentropic exponent, viscosity, and thermal conductivity. The maximum calculated value of specific impulse for a chamber pressure of 600 pounds per square inch absolute (40.827atm) and an exit pressure of 1 atmosphere is 315.3 for 79.67 percent fluorine in the oxidant.

Growth of 2D heterostructures of graphene/BN

NASA Astrophysics Data System (ADS)

Hwang, Jeonghyun; Calderon, Brian R.; Alsalman, Hussain A.; Kwak, Joon Young; Kim, Moonkyung; Spencer, Michael G.

2014-06-01

Metal free direct growth of graphene on h-BN using a high temperature (~1550°C) chemical vapor deposition technique was done under Ar environment. Growth temperature, methane partial pressure, hydrogen/methane flow ratio, and growth time were varied and optimized. Raman spectroscopy clearly showed the signature of graphene with G- (~1580cm-1) and 2D-mode (~2700cm-1). The smallest width of G- and 2D-peak was 30 and 55cm-1, respectively, and the Raman I2D/IG ratio varied between 0.7 and 1.8. Raman D-peak (~1350cm-1) shows a strong dependence on growth temperature with the smallest ID/IG value of 0.15 at 1550°C. In the case of long growth, nitrogen and boron doping were detected by x-ray photoelectron spectroscopy with a small Raman D'-peak. A continuous graphene film with the rms roughness (1×1 μm2 area) of 0.32nm was shown by atomic force microscopy. Early stage of growth revealed circular shaped nucleation islands, the density and heights of which are ~15/μm2 and 1-2 graphene monolayer (ML), respectively. The hydrogen/methane flow ratio was found to be a critical parameter to obtain smooth 2D growth. Growth of h-BN is performed with ammonia borane, hydrogen and Ar. The growth is found to be critically dependent on the conditions of the ammonia boran precursor. Reproducible continuous films of h-BN are reported.

Laboratory formation of non-cementing, methane hydrate-bearing sands

USGS Publications Warehouse

Waite, William F.; Bratton, Peter M.; Mason, David H.

2011-01-01

Naturally occurring hydrate-bearing sands often behave as though methane hydrate is acting as a load-bearing member of the sediment. Mimicking this behavior in laboratory samples with methane hydrate likely requires forming hydrate from methane dissolved in water. To hasten this formation process, we initially form hydrate in a free-gas-limited system, then form additional hydrate by circulating methane-supersaturated water through the sample. Though the dissolved-phase formation process can theoretically be enhanced by increasing the pore pressure and flow rate and lowering the sample temperature, a more fundamental concern is preventing clogs resulting from inadvertent methane bubble formation in the circulation lines. Clog prevention requires careful temperature control throughout the circulation loop.

Shining X-rays on catalysts at work

NASA Astrophysics Data System (ADS)

Grunwaldt, J.-D.

2009-11-01

Structure-performance relationships gained by studying catalysts at work are considered the key to further development of catalysts underlined here by a brief overview on our research in this area. The partial oxidation of methane to hydrogen and carbon monoxide over Pt- and Rh-based catalysts and the total combustion of hydrocarbons demonstrate the importance of structural identification of catalysts in its working state and the measurement of the catalytic performance at the same time. Moreover, proper cell design is a key both here and in liquid phase reactions including preparation or high pressure reactions. In several cases structural changes during preparation, activation and reaction occur on a subminute scale or the catalyst structure varies inside a reactor as a result of temperature or concentration gradients. This, additionally, requires time and spatial resolution. Examples from time-resolved QEXAFS studies during the partial oxidation of methane over Pt- and Rh-based catalysts demonstrate some of the recent developments of the technique (use not only of Si(111) but also Si(311) crystals, angular encoder, full EXAFS spectra at subsecond recording time, and modulation excitation spectroscopy). In order to obtain spectroscopic information on the oxidation state inside a microreactor, scanning and full field X-ray microscopy with X-ray absorption spectroscopic contrast were achieved under reaction conditions. If a microbeam is applied, fast scanning techniques like QEXAFS are required. In this way, even X-ray absorption spectroscopic tomographic images of a slice of a microreactor were obtained. The studies were recently extended to spatiotemporal studies that give important insight into the dynamics of the catalyst structure in a spatial manner with subsecond time-resolution.

Adsorbed Natural Gas Storage in Optimized High Surface Area Microporous Carbon

NASA Astrophysics Data System (ADS)

Romanos, Jimmy; Rash, Tyler; Nordwald, Erik; Shocklee, Joshua Shawn; Wexler, Carlos; Pfeifer, Peter

2011-03-01

Adsorbed natural gas (ANG) is an attractive alternative technology to compressed natural gas (CNG) or liquefied natural gas (LNG) for the efficient storage of natural gas, in particular for vehicular applications. In adsorbants engineered to have pores of a few molecular diameters, a strong van der Walls force allows reversible physisorption of methane at low pressures and room temperature. Activated carbons were optimized for storage by varying KOH:C ratio and activation temperature. We also consider the effect of mechanical compression of powders to further enhance the volumetric storage capacity. We will present standard porous material characterization (BET surface area and pore-size distribution from subcritical N2 adsorption) and methane isotherms up to 250 bar at 293K. At sufficiently high pressure, specific surface area, methane binding energy and film density can be extracted from supercritical methane adsorption isotherms. Research supported by the California Energy Commission (500-08-022).

Coal Seam Methane Pressure as a Parameter Determining the Level of the Outburst Risk - Laboratory and in Situ Research / Ciśnienie Złożowe Jako Parametr Określający Stan Zagrożenia Wyrzutami Metanu I Skał - Badania Laboratoryjne I Kopalniane

NASA Astrophysics Data System (ADS)

Skoczylas, Norbert

2012-12-01

Scarcity of research focusing on the evaluation of the coal seam methane pressure as a parameter determining the outburst risk makes it difficult to assess the value for which the level of this risk increases considerably. It is obvious that, apart from the gas factor, the evaluation of the threat should also take into account the strength factor. The research presented in this paper attempted at estimating the level of the outburst risk on the basis of the coal seam methane pressure value and firmness of coal. In this work, the author seeks to present both the relevant laboratory research and the measurements carried out in mines.

Metabolic activity of subterranean microbial communities in deep granitic groundwater supplemented with methane and H2

PubMed Central

Pedersen, Karsten

2013-01-01

It was previously concluded that opposing gradients of sulphate and methane, observations of 16S ribosomal DNA sequences displaying great similarity to those of anaerobic methane-oxidizing Archaea and a peak in sulphide concentration in groundwater from a depth of 250–350 m in Olkiluoto, Finland, indicated proper conditions for methane oxidation with sulphate. In the present research, pressure-resistant, gas-tight circulating systems were constructed to enable the investigation of attached and unattached anaerobic microbial populations from a depth of 327 m in Olkiluoto under in situ pressure (2.4 MPa), diversity, dissolved gas and chemistry conditions. Three parallel flow cell cabinets were configured to allow observation of the influence on microbial metabolic activity of 11 mℳ methane, 11 mℳ methane plus 10 mℳ H2 or 2.1 mℳ O2 plus 7.9 mℳ N2 (that is, air). The concentrations of these gases and of organic acids and carbon, sulphur chemistry, pH and Eh, ATP, numbers of cultivable micro-organisms, and total numbers of cells and bacteriophages were subsequently recorded under batch conditions for 105 days. The system containing H2 and methane displayed microbial reduction of 0.7 mℳ sulphate to sulphide, whereas the system containing only methane resulted in 0.2 mℳ reduced sulphate. The system containing added air became inhibited and displayed no signs of microbial activity. Added H2 and methane induced increasing numbers of lysogenic bacteriophages per cell. It appears likely that a microbial anaerobic methane-oxidizing process coupled to acetate formation and sulphate reduction may be ongoing in aquifers at a depth of 250–350 m in Olkiluoto. PMID:23235288

Impact of methane flow through deformable lake sediments on atmospheric release

NASA Astrophysics Data System (ADS)

Scandella, B.; Juanes, R.

2010-12-01

Methane is a potent greenhouse gas that is generated geothermally and biologically in lake and ocean sediments. Free gas bubbles may escape oxidative traps and contribute more to the atmospheric source than dissolved methane, but the details of the methane release depend on the interactions between the multiple fluid phases and the deformable porous medium. We present a model and supporting laboratory experiments of methane release through “breathing” dynamic flow conduits that open in response to drops in the hydrostatic load on lake sediments, which has been validated against a high-resolution record of free gas flux and hydrostatic pressure in Upper Mystic Lake, MA. In contrast to previous linear elastic fracture mechanics analysis of gassy sediments, the evolution of gas transport in a deformable compliant sediment is presented within the framework of multiphase poroplasticity. Experiments address how strongly the mode and rate of gas flow, captured by our model, impacts the size of bubbles released into the water column. A bubble's size in turn determines how efficiently it transports methane to the atmosphere, and integrating this effect will be critical to improving estimates of the atmospheric methane source from lakes. Cross-sectional schematic of lake sediments showing two venting sites: one open at left and one closed at right. The vertical release of gas bubbles (red) at the open venting site creates a local pressure drop, which drives both bubble formation from the methane-rich pore water (higher concentrations shaded darker red) and lateral advection of dissolved methane (purple arrows). Even as bubbles in the open site escape, those at the closed site remain trapped.

Cold Helium Pressurization for Liquid Oxygen/Liquid Methane Propulsion Systems: Fully-Integrated Hot-Fire Test Results

NASA Technical Reports Server (NTRS)

Morehead, R. L.; Atwell, M. J.; Melcher, J. C.; Hurlbert, E. A.

2016-01-01

Hot-fire test demonstrations were successfully conducted using a cold helium pressurization system fully integrated into a liquid oxygen (LOX) / liquid methane (LCH4) propulsion system (Figure 1). Cold helium pressurant storage at near liquid nitrogen (LN2) temperatures (-275 F and colder) and used as a heated tank pressurant provides a substantial density advantage compared to ambient temperature storage. The increased storage density reduces helium pressurant tank size and mass, creating payload increases of 35% for small lunar-lander sized applications. This degree of mass reduction also enables pressure-fed propulsion systems for human-rated Mars ascent vehicle designs. Hot-fire test results from the highly-instrumented test bed will be used to demonstrate system performance and validate integrated models of the helium and propulsion systems. A pressurization performance metric will also be developed as a means to compare different active pressurization schemes.

Numerical Study of Pressure Influence on Methane-Oxygen Laminar Counterflow Diffusion Flames

NASA Astrophysics Data System (ADS)

Iino, Kimio; Akamatsu, Fumiteru; Katsuki, Masashi

We carried out numerical studies on methane/oxygen diffusion flames of counter-flow configuration to elucidate the influence of pressure on flame structure, heat release rate and reaction mechanisms. The chemistry in gas-phase was based on GRI-Mech 3.0 database. The thickness of diffusion flame became thinner with increasing strain rate a , with its characteristic flame thickness varying inversely with √a, especially its relation became significant with increasing pressure. Flame temperature increased with increasing pressure. Enhanced H2O production reactions, especially chain terminal reactions for H2O production, were found to be important in determining the flame temperature at high pressures. The small reduction in the flame temperature with increasing strain rate at high pressures, compared to the atmospheric pressure, is caused by the capacitor effect of product dissociation. From QRPDs, the third body dependent reactions were enhanced in high pressure conditions, hence C2 pathway was enhanced.

Perovskite nanocomposites as effective CO2-splitting agents in a cyclic redox scheme

PubMed Central

Zhang, Junshe; Haribal, Vasudev; Li, Fanxing

2017-01-01

We report iron-containing mixed-oxide nanocomposites as highly effective redox materials for thermochemical CO2 splitting and methane partial oxidation in a cyclic redox scheme, where methane was introduced as an oxygen “sink” to promote the reduction of the redox materials followed by reoxidation through CO2 splitting. Up to 96% syngas selectivity in the methane partial oxidation step and close to complete conversion of CO2 to CO in the CO2-splitting step were achieved at 900° to 980°C with good redox stability. The productivity and production rate of CO in the CO2-splitting step were about seven times higher than those in state-of-the-art solar-thermal CO2-splitting processes, which are carried out at significantly higher temperatures. The proposed approach can potentially be applied for acetic acid synthesis with up to 84% reduction in CO2 emission when compared to state-of-the-art processes. PMID:28875171

A 3D Microphysical Model of Titan's Methane Cloud

NASA Astrophysics Data System (ADS)

Xiao, J.; Newman, C.; Inada, A.; Richardson, M.

2006-12-01

A time-dependent idealized 3D microphysical model for Titan's methane cloud is described. This new high resolution microphysical model nests in a Titan WRF GCM model. It assumes the vapor-liquid equilibria of methane-nitrogen mixtures which are based on the recent chemical experiments and thermodynamics models. In particular, the methane is condensed at a given temperature and pressure. Meanwhile nitrogen is dissolved in the methane liquid. The new model first uses the data from the thermodynamic model (Kouvaris et al. 1991), which involves saturation criteria, composition of condensate, and latent heat for a given pressure-temperature profile. For altitudes lower than 14 km, methane is saturated and condensed into liquid phase. However for altitudes from 14 km above to tropopause, methane is changed into supercooled liquid state. Then, we do some testing experiments with 1D model by varying the initial methane vapor mass mixing ratio profile and the initial mole fraction of methane in liquid phase. Based on the steady state results from 1D model, an idealized 3D microphysics model is developed to investigate the convection cloud in Titan's troposphere. Due to lower relative humidity at titan's surface (Samuelson et al. 1997) and the current estimated moist adiabatic lapse rate, convection is hardly to happen without lifting. For this reason, we apply a symmetry cosine ridge in a 100*100 grids box to force the air flow lifted at certain levels, which in turn drives the condensation of methane vapor. In addition to the abundance of methane clouds and its duration provided by the 3D model, our study demonstrates that vertical motion might be likely the major cause of convection clouds in Titan's troposphere. As the future work, we will further investigate size-resolved microphysical scheme to insight into the nature of methane cycle in Titan's atmosphere.

Aerobic and Anaerobic Methanotrophic Communities Associated with Methane Hydrates Exposed on the Seafloor: A High-Pressure Sampling and Stable Isotope-Incubation Experiment

PubMed Central

Case, David H.; Ijiri, Akira; Morono, Yuki; Tavormina, Patricia; Orphan, Victoria J.; Inagaki, Fumio

2017-01-01

High-pressure (HP) environments represent the largest volumetric majority of habitable space for microorganisms on the planet, including the deep-sea and subsurface biosphere. However, the importance of pressure as an environmental variable affecting deep microbial life and their biogeochemical functions in carbon cycling still remains poorly understood. Here, we designed a new high-volume HP-sediment core sampler that is deployable on the payload of a remotely operated vehicle and can maintain in situ HP conditions throughout multi-month enrichment incubations including daily amendments with liquid media and gases and daily effluent sampling for geochemical or microbiological analysis. Using the HP core device, we incubated sediment and overlying water associated with methane hydrate-exposed on the seafloor of the Joetsu Knoll, Japan, at 10 MPa and 4°C for 45 days in the laboratory. Diversity analyses based on 16S rRNA and methane-related functional genes, as well as carbon isotopic analysis of methane and bicarbonate, indicated the stimulation of both aerobic and anaerobic methanotrophy driven by members of the Methylococcales, and ANME, respectively: i.e., aerobic methanotrophy was observed upon addition of oxygen whereas anaerobic processes subsequently occurred after oxygen consumption. These laboratory-measured rates at 10 MPa were generally in agreement with previously reported rates of methane oxidation in other oceanographic locations. PMID:29312247

Investigation on heat transfer characteristics and flow performance of Methane at supercritical pressures

NASA Astrophysics Data System (ADS)

Xian, Hong Wei; Oumer, A. N.; Basrawi, F.; Mamat, Rizalman; Abdullah, A. A.

2018-04-01

The aim of this study is to investigate the heat transfer and flow characteristic of cryogenic methane in regenerative cooling system at supercritical pressures. The thermo-physical properties of supercritical methane were obtained from the National institute of Standards and Technology (NIST) webbook. The numerical model was developed based on the assumptions of steady, turbulent and Newtonian flow. For mesh independence test and model validation, the simulation results were compared with published experimental results. The effect of four different performance parameter ranges namely inlet pressure (5 to 8 MPa), inlet temperature (120 to 150 K), heat flux (2 to 5 MW/m2) and mass flux (7000 to 15000 kg/m2s) on heat transfer and flow performances were investigated. It was found that the simulation results showed good agreement with experimental data with maximum deviation of 10 % which indicates the validity of the developed model. At low inlet temperature, the change of specific heat capacity at near-wall region along the tube length was not significant while the pressure drop registered was high. However, significant variation was observed for the case of higher inlet temperature. It was also observed that the heat transfer performance and pressure drop penalty increased when the mass flux was increased. Regarding the effect of inlet pressure, the heat transfer performance and pressure drop results decreased when the inlet pressure is increased.

Spatial and temporal dependencies of structure II to structure I methane hydrate transformation in porous media under moderate pressure and temperature conditions

NASA Astrophysics Data System (ADS)

Dong, T.; Lin, J. F.; Gu, J. T.; Polito, P. J.; O'Connell, J.; Flemings, P. B.

2017-12-01

We used Raman spectroscopy to monitor methane hydrates transforming from structure II to structure I at the pore scale as a function of space and time. It is well documented that structure I hydrate is the thermodynamically stable phase for pure methane hydrate (<100 MPa, < 20 °C), but due to kinetic limitation, initial methane hydrate formation produces a mixture of structure I and structure II hydrates. We observed that the structure transformation originated around the porous medium grains and over time slowly migrated into the pore space. We synthesized methane hydrates in spherical glass beads (210-297 µm in diameter) in a pressure cell with a sapphire window to integrate optical observations with Raman measurements. We injected CH4 vapor into the cell and supplied only deionized water thereafter to maintain a constant pressure of 14.6 MPa at 3.5 °C, with 14.5 °C subcooling. We used Raman spectroscopy to map the methane hydrates in pore spaces at 5-25 µm resolution, in order to monitor the occupancy ratio of CH4 in large cages to CH4 in small cages, by their Raman peak intensity ratio, i.e., I( 2905 cm-1)/I( 2915 cm-1). We identified 3 stages of hydrate formation at the pore scale: (1) after the initial hydrate formation, Raman mapping revealed that the occupancy ratio ranged from 0.5 to 3, indicating a mixture of structure I and II hydrates; (2) within 1 week, we observed that all structure I hydrates occurred on the glass bead surfaces and structure II hydrates occupied the pore spaces; (3) over the following 2 weeks, structure II hydrates gradually recrystallized into structure I hydrates from glass bead surfaces towards the pore space. These results imply that (1) due to kinetics, the formation of methane hydrate in porous media is more complex than previously thought, and (2) the bulk physical and chemical properties of laboratory-synthesized methane hydrates in porous media may drift over time, as methane hydrates recrystallize from a metastable phase (structure II) to the thermodynamically stable phase (structure I).

Polycrystalline methane hydrate: Synthesis from superheated ice, and low-temperature mechanical properties

USGS Publications Warehouse

Stern, L.A.; Kirby, S.H.; Durham, W.B.

1998-01-01

We describe a new and efficient technique to grow aggregates of pure methane hydrate in quantities suitable for physical and material properties testing. Test specimens were grown under static conditions by combining cold, pressurized CH4 gas with granulated H2O ice, and then warming the reactants to promote the reaction CH4(g) + 6H2O(s???1) ??? CH4??6H2O (methane hydrate). Hydrate formation evidently occurs at the nascent ice/liquid water interface on ice grain surfaces, and complete reaction was achieved by warming the system above the ice melting point and up to 290 K, at 25-30 MPa, for approximately 8 h. The resulting material is pure, cohesive, polycrystalline methane hydrate with controlled grain size and random orientation. Synthesis conditions placed the H2O ice well above its melting temperature while reaction progressed, yet samples and run records showed no evidence for bulk melting of the unreacted portions of ice grains. Control experiments using Ne, a non-hydrate-forming gas, showed that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting are easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably to temperatures well above its ordinary melting point while reacting to form hydrate. Direct observations of the hydrate growth process in a small, high-pressure optical cell verified these conclusions and revealed additional details of the hydrate growth process. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T = 140-200 K, Pc = 50-100 MPa, and ?? = 10-4 10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to an unusually high degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; X-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

NASA Astrophysics Data System (ADS)

Loring, J.; Thompson, C.; Ilton, E. S.; McGrail, B. P.; Schaef, T.

2014-12-01

Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2 -enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of a Na-saturated montmorillonite (Na-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane and mixtures of methane and carbon dioxide were investigated usingCH4 IR spectroscopic titrations andCH4 XRD. The goals were to (1) determine if the hydration/expansion behavior of the clay in supercritical methane is different than in supercritical CO2, (2) determine if methane intercalates the clay, and (3) probe the effects of increasing CO2 concentrations. IR spectra were collected as Na-SWy-2 was titrated with water under several fluid exposures: pure methane, 25, 50, and 75 mole% CO2 in methane, and pure CO2. ComplementaryCH4 XRD experiments were conducted in the same fluids at discrete dissolved water concentrations to measure the d001 values of the clay and thus its volume change on hydration and CH4 and/or CO2 intercalation. In pure methane, no direct evidence of CH4 intercalation was detected in CH bending or stretching regions of the IR spectra. Similarly, in situ XRD indicated the montmorillonite structure was stable in the presence of CH4 and no measurable changes to the basal spacing were observed. However, under low water conditions where the montmorillonite structure was partially expanded (~sub 1W), the IR data indicated a rapid intercalation of CO2 into the interlayer, even with fluid mixtures containing the lowest concentrations of CO2. Likewise,CH4 XRD showed indirect evidence of CO2 intercalation from an increase in the basal spacing from 11.8 to 12.3 under identical conditions. These findings demonstrate that water and CO2 intercalation processes could lead to permeability changes that directly impact methane transmissivity in shales.

Study of Near-Threshold Fatigue Crack Propagation in Pipeline Steels in High Pressure Environments

NASA Technical Reports Server (NTRS)

Mitchell, M.

1981-01-01

Near threshold fatigue crack propagation in pipeline steels in high pressure environments was studied. The objective was to determine the level of threshold stress intensity for fatigue crack growth rate behavior in a high strength low alloy X60 pipeline-type steel. Complete results have been generated for gaseous hydrogen at ambient pressure, laboratory air at ambient pressure and approximately 60% relative humidity as well as vacuum of 0.000067 Pa ( 0.0000005 torr) at R-ratios = K(min)/K(max) of 0.1, 0.5, and 0.8. Fatigue crack growth rate behavior in gaseous hydrogen, methane, and methane plus 10 percent hydrogen at 6.89 MPa (100 psi) was determined.

Towards eliminating systematic errors caused by the experimental conditions in Biochemical Methane Potential (BMP) tests

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strömberg, Sten, E-mail: sten.stromberg@biotek.lu.se; Nistor, Mihaela, E-mail: mn@bioprocesscontrol.com; Liu, Jing, E-mail: jing.liu@biotek.lu.se

Highlights: • The evaluated factors introduce significant systematic errors (10–38%) in BMP tests. • Ambient temperature (T) has the most substantial impact (∼10%) at low altitude. • Ambient pressure (p) has the most substantial impact (∼68%) at high altitude. • Continuous monitoring of T and p is not necessary for kinetic calculations. - Abstract: The Biochemical Methane Potential (BMP) test is increasingly recognised as a tool for selecting and pricing biomass material for production of biogas. However, the results for the same substrate often differ between laboratories and much work to standardise such tests is still needed. In the currentmore » study, the effects from four environmental factors (i.e. ambient temperature and pressure, water vapour content and initial gas composition of the reactor headspace) on the degradation kinetics and the determined methane potential were evaluated with a 2{sup 4} full factorial design. Four substrates, with different biodegradation profiles, were investigated and the ambient temperature was found to be the most significant contributor to errors in the methane potential. Concerning the kinetics of the process, the environmental factors’ impact on the calculated rate constants was negligible. The impact of the environmental factors on the kinetic parameters and methane potential from performing a BMP test at different geographical locations around the world was simulated by adjusting the data according to the ambient temperature and pressure of some chosen model sites. The largest effect on the methane potential was registered from tests performed at high altitudes due to a low ambient pressure. The results from this study illustrate the importance of considering the environmental factors’ influence on volumetric gas measurement in BMP tests. This is essential to achieve trustworthy and standardised results that can be used by researchers and end users from all over the world.« less

Optimization of enhanced coal-bed methane recovery using numerical simulation

NASA Astrophysics Data System (ADS)

Perera, M. S. A.; Ranjith, P. G.; Ranathunga, A. S.; Koay, A. Y. J.; Zhao, J.; Choi, S. K.

2015-02-01

Although the enhanced coal-bed methane (ECBM) recovery process is one of the potential coal bed methane production enhancement techniques, the effectiveness of the process is greatly dependent on the seam and the injecting gas properties. This study has therefore aimed to obtain a comprehensive knowledge of all possible major ECBM process-enhancing techniques by developing a novel 3D numerical model by considering a typical coal seam using the COMET 3 reservoir simulator. Interestingly, according to the results of the model, the generally accepted concept that there is greater CBM (coal-bed methane) production enhancement from CO2 injection, compared to the traditional water removal technique, is true only for high CO2 injection pressures. Generally, the ECBM process can be accelerated by using increased CO2 injection pressures and reduced temperatures, which are mainly related to the coal seam pore space expansion and reduced CO2 adsorption capacity, respectively. The model shows the negative influences of increased coal seam depth and moisture content on ECBM process optimization due to the reduced pore space under these conditions. However, the injection pressure plays a dominant role in the process optimization. Although the addition of a small amount of N2 into the injecting CO2 can greatly enhance the methane production process, the safe N2 percentage in the injection gas should be carefully predetermined as it causes early breakthroughs in CO2 and N2 in the methane production well. An increased number of production wells may not have a significant influence on long-term CH4 production (50 years for the selected coal seam), although it significantly enhances short-term CH4 production (10 years for the selected coal seam). Interestingly, increasing the number of injection and production wells may have a negative influence on CBM production due to the coincidence of pressure contours created by each well and the mixing of injected CO2 with CH4.

Methane photochemistry and methane production on Neptune

NASA Technical Reports Server (NTRS)

Romani, P. N.; Atreya, S. K.

1988-01-01

The Neptune stratosphere's methane photochemistry is presently studied by means of a numerical model in which the observed mixing ratio of methane prompts photolysis near the CH4 homopause. Haze generation by methane photochemistry has its basis in the formation of hydrocarbon ices and polyacetylenes; the hazes can furnish the requisite aerosol haze at the appropriate pressure levels required by observations of Neptune in the visible and near-IR. Comparisons of model predictions with Uranus data indicate a lower ratio of polyacetylene production to hydrocarbon ice, as well as a lower likelihood of UV postprocessing of the acetylene ice to polymers on Neptune, compared to Uranus.

Carbon Dioxide Reduction Post-Processing Sub-System Development

NASA Technical Reports Server (NTRS)

Abney, Morgan B.; Miller, Lee A.; Greenwood, Zachary; Barton, Katherine

2012-01-01

The state-of-the-art Carbon Dioxide (CO2) Reduction Assembly (CRA) on the International Space Station (ISS) facilitates the recovery of oxygen from metabolic CO2. The CRA utilizes the Sabatier process to produce water with methane as a byproduct. The methane is currently vented overboard as a waste product. Because the CRA relies on hydrogen for oxygen recovery, the loss of methane ultimately results in a loss of oxygen. For missions beyond low earth orbit, it will prove essential to maximize oxygen recovery. For this purpose, NASA is exploring an integrated post-processor system to recover hydrogen from CRA methane. The post-processor, called a Plasma Pyrolysis Assembly (PPA) partially pyrolyzes methane to recover hydrogen with acetylene as a byproduct. In-flight operation of post-processor will require a Methane Purification Assembly (MePA) and an Acetylene Separation Assembly (ASepA). Recent efforts have focused on the design, fabrication, and testing of these components. The results and conclusions of these efforts will be discussed as well as future plans.

Semi-continuous methane production from undiluted brown algae using a halophilic marine microbial community.

PubMed

Miura, Toyokazu; Kita, Akihisa; Okamura, Yoshiko; Aki, Tsunehiro; Matsumura, Yukihiko; Tajima, Takahisa; Kato, Junichi; Nakashimada, Yutaka

2016-01-01

Acclimated marine sediment-derived culture was used for semi-continuous methane production from materials equivalent to raw brown algae, without dilution of salinity and without nutrient supply, under 3 consecutive conditions of varying organic loading rates (OLRs) and hydraulic retention time (HRT). Methane production was stable at 2.0gVS/kg/day (39-day HRT); however, it became unstable at 2.9gVS/kg/day (28-day HRT) due to acetate and propionate accumulation. OLR subsequently decreased to 1.7gVS/kg/day (46-day HRT), stabilizing methane production beyond steady state. Methane yield was above 300mL/g VS at all OLRs. These results indicated that the acclimated marine sediment culture was able to produce methane semi-continuously from raw brown algae without dilution and nutrient supply under steady state. Microbial community analysis suggested that hydrogenotrophic methanogens predominated among archaea during unstable methane production, implying a partial shift of the methanogenic pathway from acetoclastic methanogenesis to acetate oxidation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Thermal Modeling and Management of Solid Oxide Fuel Cells Operating with Internally Reformed Methane

NASA Astrophysics Data System (ADS)

Wu, Yiyang; Shi, Yixiang; Cai, Ningsheng; Ni, Meng

2018-06-01

A detailed three-dimensional mechanistic model of a large-scale solid oxide fuel cell (SOFC) unit running on partially pre-reformed methane is developed. The model considers the coupling effects of chemical and electrochemical reactions, mass transport, momentum and heat transfer in the SOFC unit. After model validation, parametric simulations are conducted to investigate how the methane pre-reforming ratio affects the transport and electrochemistry of the SOFC unit. It is found that the methane steam reforming reaction has a "smoothing effect", which can achieve more uniform distributions of gas compositions, current density and temperature among the cell plane. In the case of 1500 W/m2 power density output, adding 20% methane absorbs 50% of internal heat production inside the cell, reduces the maximum temperature difference inside the cell from 70 K to 22 K and reduces the cathode air supply by 75%, compared to the condition of completely pre-reforming of methane. Under specific operating conditions, the pre-reforming ratio of methane has an optimal range for obtaining a good temperature distribution and good cell performance.

Controllable growth of shaped graphene domains by atmospheric pressure chemical vapour deposition

NASA Astrophysics Data System (ADS)

Fan, Lili; Li, Zhen; Li, Xiao; Wang, Kunlin; Zhong, Minlin; Wei, Jinquan; Wu, Dehai; Zhu, Hongwei

2011-12-01

Graphene domains in different shapes have been grown on copper substrates via atmospheric pressure chemical vapour deposition by controlling the growth process parameters. Under stabilized conditions, graphene domains tend to be six-fold symmetric hexagons under low flow rate methane with some domains in an irregular hexagonal shape. After further varying the growth duration, methane flow rate, and temperature, graphene domains have developed shapes from hexagon to shovel and dendrite. Two connecting modes, through overlap and merging of adjacent graphene domains, are proposed.Graphene domains in different shapes have been grown on copper substrates via atmospheric pressure chemical vapour deposition by controlling the growth process parameters. Under stabilized conditions, graphene domains tend to be six-fold symmetric hexagons under low flow rate methane with some domains in an irregular hexagonal shape. After further varying the growth duration, methane flow rate, and temperature, graphene domains have developed shapes from hexagon to shovel and dendrite. Two connecting modes, through overlap and merging of adjacent graphene domains, are proposed. Electronic supplementary information (ESI) available: Schematics of CVD setups for graphene growth, Raman spectra and SEM images. See DOI: 10.1039/c1nr11480h

In-situ neutron imaging of hydrogenous fuels in combustion generated porous carbons under dynamic and steady state pressure conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ossler, Frederik; Santodonato, Louis J.; Bilheux, Hassina Z.

Here, we report results from experiments where we characterize the surface properties of soot particles interacting with high-pressure methane. We also found considerable differences in behavior of the soot material between static and dynamic pressure conditions that can be explained by multiscale correlations in the dynamics, from the micro to macro of the porous fractal-like carbon matrix. The measurements were possible utilizing cold neutron imaging of methane mixed with combustion generated carbon (soot) inside steel cells. The studies were performed under static and dynamic pressure conditions in the range 10-90 bar, and are of interest for applications of energy storagemore » of hydrogenous fuels. The very high cross sections for neutrons compared to hard X-ray photons, enabled us to find considerable amounts of native hydrogen in the soot and to see and quantify the presence of hydrogen atoms in the carbon soot matrix under different pressure conditions. Our work lays the base for more detailed in-situ investigations on the interaction of porous carbon materials with hydrogen in practical environments for hydrogen and methane storage.« less

In-situ neutron imaging of hydrogenous fuels in combustion generated porous carbons under dynamic and steady state pressure conditions

DOE PAGES

Ossler, Frederik; Santodonato, Louis J.; Bilheux, Hassina Z.

2017-02-12

Here, we report results from experiments where we characterize the surface properties of soot particles interacting with high-pressure methane. We also found considerable differences in behavior of the soot material between static and dynamic pressure conditions that can be explained by multiscale correlations in the dynamics, from the micro to macro of the porous fractal-like carbon matrix. The measurements were possible utilizing cold neutron imaging of methane mixed with combustion generated carbon (soot) inside steel cells. The studies were performed under static and dynamic pressure conditions in the range 10-90 bar, and are of interest for applications of energy storagemore » of hydrogenous fuels. The very high cross sections for neutrons compared to hard X-ray photons, enabled us to find considerable amounts of native hydrogen in the soot and to see and quantify the presence of hydrogen atoms in the carbon soot matrix under different pressure conditions. Our work lays the base for more detailed in-situ investigations on the interaction of porous carbon materials with hydrogen in practical environments for hydrogen and methane storage.« less

Selective anaerobic oxidation of methane enables direct synthesis of methanol.

PubMed

Sushkevich, Vitaly L; Palagin, Dennis; Ranocchiari, Marco; van Bokhoven, Jeroen A

2017-05-05

Direct functionalization of methane in natural gas remains a key challenge. We present a direct stepwise method for converting methane into methanol with high selectivity (~97%) over a copper-containing zeolite, based on partial oxidation with water. The activation in helium at 673 kelvin (K), followed by consecutive catalyst exposures to 7 bars of methane and then water at 473 K, consistently produced 0.204 mole of CH 3 OH per mole of copper in zeolite. Isotopic labeling confirmed water as the source of oxygen to regenerate the zeolite active centers and renders methanol desorption energetically favorable. On the basis of in situ x-ray absorption spectroscopy, infrared spectroscopy, and density functional theory calculations, we propose a mechanism involving methane oxidation at Cu II oxide active centers, followed by Cu I reoxidation by water with concurrent formation of hydrogen. Copyright © 2017, American Association for the Advancement of Science.

A conduit dilation model of methane venting from lake sediments

USGS Publications Warehouse

Scandella, B.P.; Varadharajan, C.; Hemond, Harold F.; Ruppel, C.; Juanes, R.

2011-01-01

Methane is a potent greenhouse gas, but its effects on Earth's climate remain poorly constrained, in part due to uncertainties in global methane fluxes to the atmosphere. An important source of atmospheric methane is the methane generated in organic-rich sediments underlying surface water bodies, including lakes, wetlands, and the ocean. The fraction of the methane that reaches the atmosphere depends critically on the mode and spatiotemporal characteristics of free-gas venting from the underlying sediments. Here we propose that methane transport in lake sediments is controlled by dynamic conduits, which dilate and release gas as the falling hydrostatic pressure reduces the effective stress below the tensile strength of the sediments. We test our model against a four-month record of hydrostatic load and methane flux in Upper Mystic Lake, Mass., USA, and show that it captures the complex episodicity of methane ebullition. Our quantitative conceptualization opens the door to integrated modeling of methane transport to constrain global methane release from lakes and other shallow-water, organic-rich sediment systems, and to assess its climate feedbacks.

Physical property changes in hydrate-bearing sediment due to depressurization and subsequent repressurization

USGS Publications Warehouse

Waite, W.F.; Kneafsey, T.J.; Winters, W.J.; Mason, D.H.

2008-01-01

Physical property measurements of sediment cores containing natural gas hydrate are typically performed on material exposed, at least briefly, to non-in situ conditions during recovery. To examine the effects of a brief excursion from the gas-hydrate stability field, as can occur when pressure cores are transferred to pressurized storage vessels, we measured physical properties on laboratory-formed sand packs containing methane hydrate and methane pore gas. After depressurizing samples to atmospheric pressure, we repressurized them into the methane-hydrate stability field and remeasured their physical properties. Thermal conductivity, shear strength, acoustic compressional and shear wave amplitudes, and speeds of the original and depressurized/repressurized samples are compared. X– ray computed tomography images track how the gas-hydrate distribution changes in the hydrate-cemented sands owing to the depressurizaton/repressurization process. Because depressurization-induced property changes can be substantial and are not easily predicted, particularly in water-saturated, hydrate-bearing sediment, maintaining pressure and temperature conditions throughout the core recovery and measurement process is critical for using laboratory measurements to estimate in situ properties.

Physical property changes in hydrate-bearing sediment due to depressurization and subsequent repressurization

USGS Publications Warehouse

Waite, W.F.; Kneafsey, T.J.; Winters, W.J.; Mason, D.H.

2008-01-01

Physical property measurements of sediment cores containing natural gas hydrate are typically performed on material exposed, at least briefly, to non-in situ conditions during recovery. To examine the effects of a brief excursion from the gas-hydrate stability field, as can occur when pressure cores are transferred to pressurized storage vessels, we measured physical properties on laboratory-formed sand packs containing methane hydrate and methane pore gas. After depressurizing samples to atmospheric pressure, we repressurized them into the methane-hydrate stability field and remeasured their physical properties. Thermal conductivity, shear strength, acoustic compressional and shear wave amplitudes, and speeds of the original and depressurized/repressurized samples are compared. X-ray computed tomography images track how the gas-hydrate distribution changes in the hydrate-cemented sands owing to the depressurizaton/repressurization process. Because depressurization-induced property changes can be substantial and are not easily predicted, particularly in water-saturated, hydrate-bearing sediment, maintaining pressure and temperature conditions throughout the core recovery and measurement process is critical for using laboratory measurements to estimate in situ properties.

Cold Helium Pressurization for Liquid Oxygen / Liquid Methane Propulsion Systems: Fully-Integrated Initial Hot-Fire Test Results

NASA Technical Reports Server (NTRS)

Morehead, R. L.; Atwell, M. J.; Melcher, J. C.; Hurlbert, E. A.

2016-01-01

A prototype cold helium active pressurization system was incorporated into an existing liquid oxygen (LOX) / liquid methane (LCH4) prototype planetary lander and hot-fire tested to collect vehicle-level performance data. Results from this hot-fire test series were used to validate integrated models of the vehicle helium and propulsion systems and demonstrate system effectiveness for a throttling lander. Pressurization systems vary greatly in complexity and efficiency between vehicles, so a pressurization performance metric was also developed as a means to compare different active pressurization schemes. This implementation of an active repress system is an initial sizing draft. Refined implementations will be tested in the future, improving the general knowledge base for a cryogenic lander-based cold helium system.

Fracturing Behavior of Methane-Hydrate-Bearing Sediment

NASA Astrophysics Data System (ADS)

Konno, Y.; Jin, Y.; Yoneda, J.; Uchiumi, T.; Shinjou, K.; Nagao, J.

2016-12-01

As a part of a Japanese national hydrate research program (MH21, funded by the Ministry of Economy, Trade, and Industry), we performed laboratory experiments of hydraulic fracturing in methane-hydrate-bearing sediment. Distilled water was injected into methane-hydrate-bearing sand which was artificially made in a tri-axial pressure cell. X-ray computed tomography revealed that tensile failure was occurred after a rapid drop in the injection pressure. It was found that generated fractures cause a significant increase in the effective water permeability of hydrate-bearing sand. The result contributes fundamental understanding of the accumulation mechanism of gas hydrates in sediments and shows that hydraulic fracturing is one of promising enhanced recovery methods for low-permeable gas hydrate reservoirs.

Joint Measurements Of Acoustic And Mechanical Properties For Methane Hydrate-Bearing Unconsolidated Sediments Synthesized In Laboratory

NASA Astrophysics Data System (ADS)

Yang, Z.; He, T.

2017-12-01

To more accurately explain geophysical exploration data of natural gas hydrate reservoir and to better assess the formation stability for geological or engineering hazards, it is important to comprehensively understand the geophysical and mechanical properties of hydrate-bearing unconsolidated marine sediments, which are significantly different from sea-water saturated ones. Compared to hard-to-control in-situ measurement, laboratory methods are important and feasible to investigate the parameter effects. With the new designed experimental apparatus, we measured ultrasonic velocity, resistivity and stress-strain relation of methane hydrate-bearing unconsolidated sediments. The experimental mineral mixture is prepared as the composition of sample HY-3 of core SH-7 from Shenhu area, South China Sea. It composed of 0.4 wt. % kaolinite, 23.5 wt. % silt (4 - 63 μm), 32.1 wt. % fine sand (63 - 250 μm), 29.2 wt. % medium sand (250 - 500 μm) and 14.8 wt. % coarse sand (500 - 2000 μm). The pure methane enters into the brine (NaCl salinity of 3.5%) saturated sample all around to synthesis methane hydrate. The methane hydrate saturation was calculated by methane consumption amount, which was in turn calculated by gas state equation using the measured methane pressure drop in high pressure reactor. The ultrasonic velocities and resistivity were measured frequently during methane hydrate saturation increasing to examine the velocity varying pattern, especially for S-wave velocities, which may reflect different hydrate occurrence states in sediment pores: load-bearing or not. The stress - strain curves of methane hydrate - bearing sediments showed typical elastic - plastic characteristics and were used to obtain Young's modulus, Poisson's ratio, failure strength and other mechanical parameters. With these results, we can know better about the hydrate reservoir at Shenhu area.

Hydrogen-bond symmetrization in methane and hydrogen hydrates in the Mbar range

NASA Astrophysics Data System (ADS)

Bove, L. E.; Ranieri, U.; Gaal, R.; Finocchi, F.; Kuhs, W. F.; Falenty, A.; Klotz, S.; Gillet, P.

2016-12-01

Ice-VII and ice-X phases are the most stable forms of ice at high temperature and extreme pressures, typical of the interiors of satellites and planets. The phase transition between them is a prototypical case of quantum-driven phenomenon, as it can be described as a quantum delocalization of protons in the middle of O-O distances. Recent studies on LiCl- and NaCl-doped ice 1-3 have shown that the presence of salt inclusions in the ice lattice suppresses the quantum behavior of protons, hindering the appearance of the symmetric phase, and possibly suppressing the predicted high temperature superionic phase. This finding stimulated the investigation of similar effects in other water-based compounds, which are thought to be present in icy bodies, namely hydrogen and methane high pressure hydrates. Few experiments have been performed in the past to identify signatures of the hydrogen-bond symmetrization in methane and hydrogen hydrates without reaching conclusive results4,5. Here we present new results on the hydrogen-bond symmetrization of methane and hydrogen hydrates using Raman scattering in the Mbar range and semiclassical simulations including nuclear quantum effects. 1 Bove L. E. et al., E_ect of salt on the H-bond symmetrization in ice, Proc. Natl. Acad. Sci. USA 112, 8216, 2015 ; 2. Bronstein Y. et al., Quantum versus classical protons in pure and salty ice under pressure, Phys. Rev. B 93, 024104, 2016. 3. Klotz S. et al., Ice VII from aqueous salt solutions: From a glass to a crystal with broken H-bonds, Nature Sci. Rep. , in press. 4. Tanaka T. et al., Phase changes of _lled ice Ih methane hydrate under low temperature and high pressure, J. Chem. Phys. 139, 104701, 2013 5. Hirai H. et al., Structural changes of _lled ice Ic hydrogen hydrate under low temperatures and high pressures from 5 to 50 GPa, J. Chem. Phys. 137, 074505, 2012

Catalytic reforming of methane to syngas in an oxygen-permeative membrane reactor

NASA Astrophysics Data System (ADS)

Urano, Takeshi; Kubo, Keiko; Saito, Tomoyuki; Hitomi, Atsushi

2011-05-01

For fuel cell applications, partial oxidative reforming of methane to syngas, hydrogen and carbon monoxide, was performed via a dense oxygen-permeative ceramic membrane composed by both ionic and electronic conductive materials. The modification of Ni-based catalyst by noble metals was investigated to increase oxygen permeation flux and decrease carbon deposition during reforming reaction. The role of each component in catalyst was also discussed.

The strength and rheology of methane clathrate hydrate

USGS Publications Warehouse

Durham, W.B.; Kirby, S.H.; Stern, L.A.; Zhang, W.

2003-01-01

Methane clathrate hydrate (structure I) is found to be very strong, based on laboratory triaxial deformation experiments we have carried out on samples of synthetic, high-purity, polycrystalline material. Samples were deformed in compressional creep tests (i.e., constant applied stress, ??), at conditions of confining pressure P = 50 and 100 MPa, strain rate 4.5 ?? 10-8 ??? ?? ??? 4.3 ?? 10-4 s-1, temperature 260 ??? T ??? 287 K, and internal methane pressure 10 ??? PCH4 ??? 15 MPa. At steady state, typically reached in a few percent strain, methane hydrate exhibited strength that was far higher than expected on the basis of published work. In terms of the standard high-temperature creep law, ?? = A??ne-(E*+PV*)/RT the rheology is described by the constants A = 108.55 MPa-n s-1, n = 2.2, E* = 90,000 J mol-1, and V* = 19 cm3 mol-1. For comparison at temperatures just below the ice point, methane hydrate at a given strain rate is over 20 times stronger than ice, and the contrast increases at lower temperatures. The possible occurrence of syntectonic dissociation of methane hydrate to methane plus free water in these experiments suggests that the high strength measured here may be only a lower bound. On Earth, high strength in hydrate-bearing formations implies higher energy release upon decomposition and subsequent failure. In the outer solar system, if Titan has a 100-km-thick near-surface layer of high-strength, low-thermal conductivity methane hydrate as has been suggested, its interior is likely to be considerably warmer than previously expected.

Experimental and modeling study on effects of N2 and CO2 on ignition characteristics of methane/air mixture

PubMed Central

Zeng, Wen; Ma, Hongan; Liang, Yuntao; Hu, Erjiang

2014-01-01

The ignition delay times of methane/air mixture diluted by N2 and CO2 were experimentally measured in a chemical shock tube. The experiments were performed over the temperature range of 1300–2100 K, pressure range of 0.1–1.0 MPa, equivalence ratio range of 0.5–2.0 and for the dilution coefficients of 0%, 20% and 50%. The results suggest that a linear relationship exists between the reciprocal of temperature and the logarithm of the ignition delay times. Meanwhile, with ignition temperature and pressure increasing, the measured ignition delay times of methane/air mixture are decreasing. Furthermore, an increase in the dilution coefficient of N2 or CO2 results in increasing ignition delays and the inhibition effect of CO2 on methane/air mixture ignition is stronger than that of N2. Simulated ignition delays of methane/air mixture using three kinetic models were compared to the experimental data. Results show that GRI_3.0 mechanism gives the best prediction on ignition delays of methane/air mixture and it was selected to identify the effects of N2 and CO2 on ignition delays and the key elementary reactions in the ignition chemistry of methane/air mixture. Comparisons of the calculated ignition delays with the experimental data of methane/air mixture diluted by N2 and CO2 show excellent agreement, and sensitivity coefficients of chain branching reactions which promote mixture ignition decrease with increasing dilution coefficient of N2 or CO2. PMID:25750753

Influence of coal particles on ignition delay times of methane-air mixture

NASA Astrophysics Data System (ADS)

Fedorov, A. V.; Tropin, D. A.

2018-03-01

The results of numerical investigation of the ignition of a stoichiometric methane-air mixture in the presence of carbon particles with diameters of 20-52 μm in the temperature range 950-1150 K and pressures of 1.5-2.0 MPa are presented. The calculated data of the ignition delay times of coal particles in the coal particles/air mixture and of the ignition delay times of methane and coal particles in the methane/coal particles /air mixture are compared with the experimental ones. A satisfactory agreement of the data on the coal particles ignition delay times and methane ignition delay times in all the mixtures considered is shown.

Post-Shock Sampling of Shock-Heated Hydrocarbon Fuels

DTIC Science & Technology

2016-07-07

on the ability to measure key hydrocarbon fragments (e.g. ethylene , methane, and acetylene) over a wide range of temperatures and pressures. The...series of experiments was conducted to validate the sampling system results and explore the thermal decomposition of ethylene and methane. Initially, a...1% ethylene /0.1% methane/balance argon fuel mixture was shock-heated to ~960 K – a temperature low enough that no reaction would occur. GC analysis

WATER LEVEL DRAWDOWN TRIGGERS SYSTEM-WIDE BUBBLE RELEASE FROM RESERVOIR SEDIMENTS

EPA Science Inventory

Reservoirs are an important anthropogenic source of methane and ebullition is a key pathway by which methane stored in reservoir sediments can be released to the atmosphere. Changes in hydrostatic pressure during periods of falling water levels can trigger bubbling events, sugge...

Water produced with coal-bed methane

USGS Publications Warehouse

,

2000-01-01

Natural gas produced from coal beds (coal-bed methane, CBM) accounts for about 7.5 percent of the total natural gas production in the United States. Along with this gas, water is also brought to the surface. The amount of water produced from most CBM wells is relatively high compared to conventional natural gas wells because coal beds contain many fractures and pores that can contain and transmit large volumes of water. In some areas, coal beds may function as regional or local aquifers and important sources for ground water. The water in coal beds contributes to pressure in the reservoir that keeps methane gas adsorbed to the surface of the coal. This water must be removed by pumping in order to lower the pressure in the reservoir and stimulate desorption of methane from the coal (fi g. 1). Over time, volumes of pumped water typically decrease and the production of gas increases as coal beds near the well bore are dewatered.

Anomalous preservation of pure methane hydrate at 1 atm

USGS Publications Warehouse

Stern, L.A.; Circone, S.; Kirby, S.H.; Durham, W.B.

2001-01-01

Direct measurement of decomposition rates of pure, polycrystalline methane hydrate reveals a thermal regime where methane hydrate metastably `preserves' in bulk by as much as 75 K above its nominal equilibrium temperature (193 K at 1 atm). Rapid release of the sample pore pressure at isothermal conditions between 242 and 271 K preserves up to 93% of the hydrate for at least 24 h, reflecting the greatly suppressed rates of dissociation that characterize this regime. Subsequent warming through the H2O ice point then induces rapid and complete dissociation, allowing controlled recovery of the total expected gas yield. This behavior is in marked contrast to that exhibited by methane hydrate at both colder (193-240 K) and warmer (272-290 K) test conditions, where dissociation rates increase monotonically with increasing temperature. Anomalous preservation has potential application for successful retrieval of natural gas hydrate or hydrate-bearing sediments from remote settings, as well as for temporary low-pressure transport and storage of natural gas.

High pressure thermal hydrolysis as pre-treatment to increase the methane yield during anaerobic digestion of microalgae.

PubMed

Keymer, Philip; Ruffell, Ian; Pratt, Steven; Lant, Paul

2013-03-01

Anaerobic digestion of algal biomass will be an essential component of algal biofuel production systems, yet the methane yield from digestion of algae is typically much lower than the theoretical potential. In this work, high pressure thermal hydrolysis (HPTH) is shown to enhance methane yield during algae digestion. HPTH pre-treatment was applied to both raw algae and algal residue resulting from lipid extraction. HPTH and even the lipid extraction process itself increased methane yield, by 81% and 33% respectively; in combination they increased yield by 110% over that of the raw algae (18L CH4 gVS(-1) substrate). HPTH had little effect on the rate of anaerobic digestion, however lipid extraction enhanced it by 33% over that for raw algae (0.21day(-1)). Digestion resulted in solubilisation of nitrogen (and phosphorous to a lesser degree) in all cases, showing that there is potential for nutrient recycling for algal growth. Copyright © 2013 Elsevier Ltd. All rights reserved.

Titan's missing ethane: From the atmosphere to the subsurface

NASA Astrophysics Data System (ADS)

Gilliam, Ashley E.; Lerman, Abraham

2016-09-01

The second most abundant component of the present-day Titan atmosphere, methane (CH4), is known to undergo photolytic conversion to ethane (C2H6) that accumulates as a liquid on Titan's surface. Condensation temperature of ethane is higher than that of methane, so that ethane "rain" may be expected to occur before the liquefaction of methane. At present, the partial pressure of ethane in the atmosphere is 1E-5 bar, much lower than 1E-1 bar of CH4. Estimated 8.46E17 kg or 1.37E6 km3 of C2H6 have been produced on Titan since accretion. The Titan surface reservoirs of ethane are lakes and craters, of estimated volume of 50,000 km3 and 61,000 km3, respectively. As these are smaller than the total volume of liquid ethane produced in the course of Titan's history, the excess may be stored in the subsurface of the crust, made primarily of water ice. The minimum porosity of the crust needed to accommodate all the liquid ethane would be only 0.9% of the uppermost 2 km of the crust. The occurrence of CH4 and liquid C2H6 on Titan has led to much speculation on the possibility of life on that satellite. The aggregation of organic molecules in a "primordial soup or bullion" depends in part on the viscosity of the medium, diffusivity of organic molecules in it, and rates of polymerization reactions. The temperatures on Titan, much lower than on primordial Earth, are less favorable to the "Second Coming of life" on Titan.

Enhancement of anaerobic sludge digestion by high-pressure homogenization.

PubMed

Zhang, Sheng; Zhang, Panyue; Zhang, Guangming; Fan, Jie; Zhang, Yuxuan

2012-08-01

To improve anaerobic sludge digestion efficiency, the effects of high-pressure homogenization (HPH) conditions on the anaerobic sludge digestion were investigated. The VS and TCOD were significantly removed with the anaerobic digestion, and the VS removal and TCOD removal increased with increasing the homogenization pressure and homogenization cycle number; correspondingly, the accumulative biogas production also increased with increasing the homogenization pressure and homogenization cycle number. The optimal homogenization pressure was 50 MPa for one homogenization cycle and 40 MPa for two homogenization cycles. The SCOD of the sludge supernatant significantly increased with increasing the homogenization pressure and homogenization cycle number due to the sludge disintegration. The relationship between the biogas production and the sludge disintegration showed that the accumulative biogas and methane production were mainly enhanced by the sludge disintegration, which accelerated the anaerobic digestion process and improved the methane content in the biogas. Copyright © 2012 Elsevier Ltd. All rights reserved.

Thermodynamic properties and diffusion of water + methane binary mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shvab, I.; Sadus, Richard J., E-mail: rsadus@swin.edu.au

2014-03-14

Thermodynamic and diffusion properties of water + methane mixtures in a single liquid phase are studied using NVT molecular dynamics. An extensive comparison is reported for the thermal pressure coefficient, compressibilities, expansion coefficients, heat capacities, Joule-Thomson coefficient, zero frequency speed of sound, and diffusion coefficient at methane concentrations up to 15% in the temperature range of 298–650 K. The simulations reveal a complex concentration dependence of the thermodynamic properties of water + methane mixtures. The compressibilities, heat capacities, and diffusion coefficients decrease with increasing methane concentration, whereas values of the thermal expansion coefficients and speed of sound increase. Increasing methanemore » concentration considerably retards the self-diffusion of both water and methane in the mixture. These effects are caused by changes in hydrogen bond network, solvation shell structure, and dynamics of water molecules induced by the solvation of methane at constant volume conditions.« less

Thermodynamic analysis on the CO2 conversion processes of methane dry reforming for hydrogen production and CO2 hydrogenation to dimethyl ether

NASA Astrophysics Data System (ADS)

He, Xinyi; Liu, Liping

2017-12-01

Based on the principle of Gibbs free energy minimization, the thermodynamic analysis on the CO2 conversion processes of dry reforming of methane for H2 and CO2 hydrogenation to dimethyl ether was carried out. The composition of the reaction system was determined on the basis of reaction mechanism. The effects of reaction temperature, pressure and raw material composition on the equilibrium conversion and the selectivity of products were analyzed. The results show that high temperature, low pressure, CO2/CH4 molar ratio of 1.0-1.5 and appropriate amount of oxygen are beneficial to the dry reforming of methane. For CO2 hydrogenation to dimethyl ether, low temperature, high pressure, the appropriate H2/CO2 and the proper CO addition in feed are favorable. The calculated results are compared with the relevant studies, indicating that industrial catalytic technology needs further improvement.

Analysis of operational methane emissions from pressure relief valves from biogas storages of biogas plants.

PubMed

Reinelt, Torsten; Liebetrau, Jan; Nelles, Michael

2016-10-01

The study presents the development of a method for the long term monitoring of methane emissions from pressure relief valves (PRV(1)) of biogas storages, which has been verified during test series at two PRVs of two agricultural biogas plants located in Germany. The determined methane emission factors are 0.12gCH4kWhel(-1) (0.06% CH4-loss, within 106days, 161 triggering events, winter season) from biogas plant A and 6.80/7.44gCH4kWhel(-1) (3.60/3.88% CH4-loss, within 66days, 452 triggering events, summer season) from biogas plant B. Besides the operational state of the biogas plant (e.g. malfunction of the combined heat and power unit), the mode of operation of the biogas flare, which can be manually or automatically operated as well as the atmospheric conditions (e.g. drop of the atmospheric pressure) can also affect the biogas emission from PRVs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pressure Response of Various Gases in a Pneumatic Resistance Capacitance System and Pipe

NASA Astrophysics Data System (ADS)

Peng, J.; Youn, C.; Tadano, K.; Kagawa, T.

2017-10-01

City gas, such as propane and methane, is widely used as a fuel in households and factories. Recently, hydrogen as a clean and efficient fuel has been proposed for fuel cell vehicles. However, few studies have investigated pressure control and response of gases considering their properties. This study investigated the static flow rate characteristics in an orifice with four gases—air, propane, methane, and hydrogen. Then, a pressure response experiment was performed using a pneumatic resistance capacitance system comprising an isothermal chamber and a nozzle flapper, and the time constant of the pressure response with various gases was analysed with a mathematical model. The simulation results agreed with the experimental data. Finally, the differences in pressure propagation in a pipe with various gases were explicated by a pressure response experiment. The results showed that the pressure response speed of hydrogen is faster than that of the other three gases because of its small molecular weight. Therefore, the pressure control equipment of hydrogen needs a high response speed.

Direct Measure of the Dense Methane Phase in Gas Shale Organic Porosity by Neutron Scattering

DOE PAGES

Eberle, Aaron P. R.; King, Hubert E.; Ravikovitch, Peter I.; ...

2016-08-30

Here, we report the first direct measurements of methane density in shale gas using small-angle neutron scattering. At a constant pressure, the density of methane in the inorganic pores is similar to the gas bulk density of the system conditions. Conversely, the methane density is 2.1 ± 0.2 times greater in the organic mesopores. Furthermore, classical density functional theory calculations show that this excess density in the organic pores persists to elevated temperatures, typical of shale gas reservoir conditions, providing new insight into the hydrocarbon storage mechanisms within these reservoirs.

Flow Field Measurements of Methane-Oxygen Turbulent Nonpremixed Flames at High Pressure

NASA Astrophysics Data System (ADS)

Iino, Kimio; Kikkawa, Hoshitaka; Akamatsu, Fumiteru; Katsuki, Masashi

We carried out the flow field measurement of methane-oxygen turbulent nonpremixed flame in non-combusting and combusting situations at high pressures using LDV. The main objectives are to study the influences of combustion on the turbulence structure at high pressures and to provide detailed data on which numerical predictions on such flows can rely. Direct observation and CH* chemiluminescence detection are conducted at high pressures up to 1.0MPa. It was found that the flame length at elevated pressures became constant. From flow field measurements, the following features of flames at elevated pressure were found: (1) the existence of flame suppressed turbulence in the upstream region of the jet and enhanced it in the downstream region with increasing pressure; (2) Turbulence in the flame was more anisotropic than in the corresponding cold jet in all regions of the flow with increasing pressure; (3) Reynolds shear stresses did not change at elevated pressure; (4) Combustion processes had a marked influence on the turbulence macroscale under high pressures, however, the turbulence macroscale was not changed even with the increase in pressure.

Methane on Titan: Photochemical-Meteorological-Hydrogeochemical Cycle

NASA Astrophysics Data System (ADS)

Atreya, S. K.; Niemann, H. B.; Owen, T. C.; Adams, E. Y.; Demick, J. E.; GCMS Team

2005-08-01

Photochemically driven destruction of methane in Titan's stratosphere leads to irreversible conversion to heavier hydrocarbons (1). The latter would largely condense out of the atmosphere (2). In the absence of recycling, Titan's methane would thus be destroyed in 10-100 million years (1). However, methane is key to the maintenance of Titan's nitrogen atmosphere. Without warming provided by CH4-generated hydrocarbon hazes in the stratosphere and pressure induced opacity in the infrared, particularly by H2-N2 and CH4-N2 collisions in the troposphere, the atmosphere would gradually diminish to tens of millibar pressure (3). Thus, the source-sink cycle of methane is crucial to the evolutionary history of Titan and its atmosphere. The GCMS measurements show that a ``methalogical" cycle with surface evaporation, cloud formation, followed by precipitation (rain) of methane exists. However, this ``closed" cycle does not recycle methane lost to heavy hydrocarbons. A source is required. Unlike the deep, hot, H2-rich interiors of the giant planets, Titan's interior is ill suited for thermochemical conversion of hydrocarbons back to methane. Instead we propose that serpentinization is an effective process for producing methane in Titan's interior (4). Hydration of ultramafic silicates, followed by reaction between the released H2 gas and CO2 or carbon grains can produce large quantities of CH4 at relatively mild (40-90oC) temperatures. Such thermal conditions are believed to exist below the purported water-ammonia ocean (5). Storage of methane produced via serpentinization can occur in form of clathrates. Evidence of outgassing from Titan's interior is provided by GCMS (6) and VIMS (7) data. (1) Wilson, Atreya, JGR 109, E06002, doi:10.1029/2003JE002181, 2004. (2) Wilson, Atreya, PSS 51, 1017, 2003. (3) Lorenz etal. Science 275, 642, 1997. (4) Owen etal. Phys. Uspekhi, in press. (5) Grasset, Pargamin, PSS 53, 371, 2005. (6) Niemann etal., Submitted to Nature, 2005. (7) Sotin etal., Nature 435, 786, 2005.

Ni-doped (CeO2- δ )-YSZ mesoarchitectured with nanocrystalline framework: the effect of thermal treatment on structure, surface chemistry and catalytic properties in the partial oxidation of methane (CPOM)

NASA Astrophysics Data System (ADS)

Somacescu, Simona; Florea, Mihaela; Osiceanu, Petre; Calderon-Moreno, Jose Maria; Ghica, Corneliu; Serra, Jose Manuel

2015-11-01

Ni-doped (CeO2- δ )-YSZ (5 mol% Ni oxide, 10 mol% ceria) mesoarchitectures (MA) with nanocrystalline framework have been synthesized by an original, facile and cheap approach based on Triton X100 nonionic surfactant as template and water as solvent at a strong basic pH value. Following the hydrothermal treatment under autogenous pressure ( 18 bars), Ni, Ce, Y, and Zr were well ordered as MA with nanocrystalline framework, assuring thermal stability. A comprehensive investigation of structure, texture, morphology, and surface chemistry was performed by means of a variety of complementary techniques (X-Ray Diffraction, XRD; Raman Spectroscopy, RS; Brunauer—Emmett—Teller, BET; Temperature—Programmed Reduction, TPR; Transmission Electron Microscopy, TEM and DF-STEM; X-ray Photoelectron Spectroscopy, XPS; Catalytic activity and selectivity). N2 sorption measurements highlighted that the mesoporous structure is formed at 600 °C and remains stable at 800 °C. At 900 °C, the MA collapses, favoring the formation of macropores. The XRD and Raman Spectroscopy of all samples showed the presence of a pure, single phase with fluorite-type structure. At 900 °C, an increased tetragonal distortion of the cubic lattice was observed. The surface chemistry probed by XPS exhibits a mixture of oxidation states (Ce3+ + Ce4+) with high percentage of Ce3+ valence state 35 % and (Ni3+ and Ni2+) oxidation states induced by the thermal treatment. These nanoparticles assembled into MA show high stability and selectivity over time in catalytic partial oxidation of methane (CPOM). These promising performances suggest an interesting prospect for introduction as anode within IT-SOFC assemblies.

Effects of pressure and fuel dilution on coflow laminar methane-air diffusion flames: A computational and experimental study

NASA Astrophysics Data System (ADS)

Cao, Su; Ma, Bin; Giassi, Davide; Bennett, Beth Anne V.; Long, Marshall B.; Smooke, Mitchell D.

2018-03-01

In this study, the influence of pressure and fuel dilution on the structure and geometry of coflow laminar methane-air diffusion flames is examined. A series of methane-fuelled, nitrogen-diluted flames has been investigated both computationally and experimentally, with pressure ranging from 1.0 to 2.7 atm and CH4 mole fraction ranging from 0.50 to 0.65. Computationally, the MC-Smooth vorticity-velocity formulation was employed to describe the reactive gaseous mixture, and soot evolution was modelled by sectional aerosol equations. The governing equations and boundary conditions were discretised on a two-dimensional computational domain by finite differences, and the resulting set of fully coupled, strongly nonlinear equations was solved simultaneously at all points using a damped, modified Newton's method. Experimentally, chemiluminescence measurements of CH* were taken to determine its relative concentration profile and the structure of the flame front. A thin-filament ratio pyrometry method using a colour digital camera was employed to determine the temperature profiles of the non-sooty, atmospheric pressure flames, while soot volume fraction was quantified, after evaluation of soot temperature, through an absolute light calibration using a thermocouple. For a broad spectrum of flames in atmospheric and elevated pressures, the computed and measured flame quantities were examined to characterise the influence of pressure and fuel dilution, and the major conclusions were as follows: (1) maximum temperature increases with increasing pressure or CH4 concentration; (2) lift-off height decreases significantly with increasing pressure, modified flame length is roughly independent of pressure, and flame radius decreases with pressure approximately as P-1/2; and (3) pressure and fuel stream dilution significantly affect the spatial distribution and the peak value of the soot volume fraction.

Greenhouse models of the atmosphere of Titan.

NASA Technical Reports Server (NTRS)

Pollack, J. B.

1973-01-01

The greenhouse effect is calculated for a series of Titanian atmosphere models with different proportions of methane, hydrogen, helium, and ammonia. A computer program is used in temperature-structure calculations based on radiative-convective thermal transfer considerations. A brightness temperature spectrum is derived for Titan and is compared with available observational data. It is concluded that the greenhouse effect on Titan is generated by pressure-induced transitions of methane and hydrogen. The helium-to-hydrogen ratio is found to have a maximum of about 1.5. The surface pressure is estimated to be at least 0.4 atm, with a daytime temperature of about 155 K at the surface. The presence of methane clouds in the upper troposphere is indicated. The clouds have a significant optical depth in the visible, but not in the thermal, infrared.

Determination of Methane Hydrate Solubility in the Absence of Vapor Phase by in-situ Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Lu, W.; Chou, I.; Burruss, R.

2006-12-01

Prediction of the occurrence, distribution, and evolution of methane hydrate in porous marine sediments requires information on solubilities of methane hydrate in water. Solubilities of methane hydrate in the presence of a vapor phase are well established, but those in the absence of a vapor phase are not well defined with differences up to 30%. We have measured methane concentrations in pure water in equilibrium with sI methane hydrate, in the absence of vapor phase, by in-situ Raman spectroscopy at temperatures (T) from 2 to 20 (± 0.3) °C and pressures (P) at 10, 20, 30, and 40 (± 0.4%) MPa. Methane hydrate was synthesized in a high-pressure capillary optical cell (Chou et al., 2005; Advances in High-Pressure Technology for Geophysical Applications. Ed. J. Chen et al., Chapter 24, p. 475, Elsevier). A small quantity of methane was first loaded in an evacuated cell and then pressurized by water. Hydrate crystals were formed near the liquid-vapor interface near the enclosed end of the optical tube at room T, and were then placed at the center of a USGS-type heating-cooling stage. By adjusting sample P and T, the crystals went through dissolution-formation cycles three to four times in three days until the vapor phase was completely consumed and several crystals (typically 40 x 40 x 10 μm) were formed. These crystals were located at about 200 μm from the enclosed end and were about 20 to 40 μm from each other. Raman spectra were collected for the liquid phase adjacent to hydrate crystals near the enclosed end of the tube. A volumetric decrease in crystal size was observed away from the sampling spot; however, no such volumetric decrease was observed in or near the sampling spot. Therefore, equilibrium was likely established locally within the sampling area. The results are represented by the following linear isobaric equations: 10 MPa: ln [X(CH4)] = 0.06175 T - 6.79507; r2 = 0.9991 (n = 6) 20 MPa: ln [X(CH4)] = 0.06170 T - 6.82816; r2 = 0.9985 (n = 6) 30 MPa: ln [X(CH4)] = 0.06186 T - 6.87463; r2 = 0.9971 (n = 10) 40 MPa: ln [X(CH4)] = 0.06147 T - 6.95384; r2 = 0.9983 (n = 22), where X(CH4) is the mole fraction of CH4 in solution and n is the number of observations. These results are in good agreement with measurements by Servio and Englezos (2002, J. Chem. Eng. Data., 47, p. 87) and Kim et al. (2003, Ind. Eng. Chem. Res., 42, p. 2409) and predictions by Glew et al. (2003, Can. J. of Chem., 81, p.1443). However, our solubilities are about 10 to 30% higher than those measured by Yang et al. (2001, Fluid Phase Equilibria, 185, p. 53) and those predicted by Davie et al. (2004, Marine Geol., 203, p. 177) and Zhang and Xu (2003, Earth and Planet. Sci. Lett., 213, p. 133). It should be noted that our solubilities are minimum values if an equilibrium state was not reached during our measurements. When compared with previous direct sampling method, the advantages of our method include: (1) the use of in-situ Raman signals for methane concentration measurements eliminates possible uncertainty caused by pressure drops during sampling; (2) simple and efficient; and (3) high-pressure data can be obtained without safety concern.

Permeability Prediction in Deep Coal Seam: A Case Study on the No. 3 Coal Seam of the Southern Qinshui Basin in China

PubMed Central

2013-01-01

The coal permeability is an important parameter in mine methane control and coal bed methane (CBM) exploitation, which determines the practicability of methane extraction. Permeability prediction in deep coal seam plays a significant role in evaluating the practicability of CBM exploitation. The coal permeability depends on the coal fractures controlled by strata stress, gas pressure, and strata temperature which change with depth. The effect of the strata stress, gas pressure, and strata temperature on the coal (the coal matrix and fracture) under triaxial stress and strain conditions was studied. Then we got the change of coal porosity with strata stress, gas pressure, and strata temperature and established a coal permeability model under tri-axial stress and strain conditions. The permeability of the No. 3 coal seam of the Southern Qinshui Basin in China was predicted, which is consistent with that tested in the field. The effect of the sorption swelling on porosity (permeability) firstly increases rapidly and then slowly with the increase of depth. However, the effect of thermal expansion and effective stress compression on porosity (permeability) increases linearly with the increase of depth. The most effective way to improve the permeability in exploiting CBM or extracting methane is to reduce the effective stress. PMID:24396293

Coal-Packed Methane Biofilter for Mitigation of Green House Gas Emissions from Coal Mine Ventilation Air

PubMed Central

Limbri, Hendy; Gunawan, Cindy; Thomas, Torsten; Smith, Andrew; Scott, Jason; Rosche, Bettina

2014-01-01

Methane emitted by coal mine ventilation air (MVA) is a significant greenhouse gas. A mitigation strategy is the oxidation of methane to carbon dioxide, which is approximately twenty-one times less effective at global warming than methane on a mass-basis. The low non-combustible methane concentrations at high MVA flow rates call for a catalytic strategy of oxidation. A laboratory-scale coal-packed biofilter was designed and partially removed methane from humidified air at flow rates between 0.2 and 2.4 L min−1 at 30°C with nutrient solution added every three days. Methane oxidation was catalysed by a complex community of naturally-occurring microorganisms, with the most abundant member being identified by 16S rRNA gene sequence as belonging to the methanotrophic genus Methylocystis. Additional inoculation with a laboratory-grown culture of Methylosinus sporium, as investigated in a parallel run, only enhanced methane consumption during the initial 12 weeks. The greatest level of methane removal of 27.2±0.66 g methane m−3 empty bed h−1 was attained for the non-inoculated system, which was equivalent to removing 19.7±2.9% methane from an inlet concentration of 1% v/v at an inlet gas flow rate of 1.6 L min−1 (2.4 min empty bed residence time). These results show that low-cost coal packing holds promising potential as a suitable growth surface and contains methanotrophic microorganisms for the catalytic oxidative removal of methane. PMID:24743729

Subarctic Lake Sediment Microbial Community Contributions to Methane Emission Patterns

NASA Astrophysics Data System (ADS)

Emerson, J. B.; Varner, R. K.; Parks, D.; Wik, M.; Neumann, R.; Johnson, J. E.; Singleton, C. M.; Woodcroft, B. J.; Tollerson, R., II; Owusu-Dommey, A.; Binder, M.; Freitas, N. L.; Crill, P. M.; Saleska, S. R.; Tyson, G. W.; Rich, V. I.

2017-12-01

Northern post-glacial lakes have recently been identified as a significant and increasing source of carbon to the atmosphere, largely through ebullition (bubbling) of microbially produced methane from the sediments. Ebullitive methane flux has been shown to correlate significantly with sediment surface temperatures, suggesting that solar radiation is the primary driver of methane emissions from these lakes. However, the slope of this relationship (i.e., the extent to which increasing temperature increases ebullitive methane emissions) differs spatially, both within and among lakes. As microbes are responsible for both methane generation and removal in lakes, we hypothesized that microbial communities—previously uncharacterized in post-glacial lake sediments—could be contributing to spatiotemporal differences in methane emission responses to temperature. We compared methane emission data with sediment microbial (metagenomic and amplicon), isotopic, and geochemical characterizations across two post-glacial lakes in Northern Sweden. With increasing temperatures, the increase in methane emissions was greater in lake middles (deeper water) than lake edges (shallower water), consistent with higher abundances of methanogens in sediments from lake middles than edges, along with significant differences in microbial community composition between these regions. Using sparse partial least squares statistical modeling, microbial abundances (including the abundances of methane-cycling microorganisms and of reconstructed population genomes, e.g., from Planctomycetes, Thermoplasmatales, and Candidate Phylum Aminicenantes) were better predictors of porewater methane concentrations than abiotic variables. These results suggest that, although temperature controls methane emissions, microbial community composition and function may drive the rate and magnitude of this temperature response in subarctic post-glacial lakes.

Effect of stress on the diffusion kinetics of methane during gas desorption in coal matrix under different equilibrium pressures

NASA Astrophysics Data System (ADS)

Li, Chengwu; Xue, Honglai; Hu, Po; Guan, Cheng; Liu, Wenbiao

2018-06-01

Stress has a significant influence on gas diffusion, which is a key factor for methane recovery in coal mines. In this study, a series of experiments were performed to investigate effect of stress on the gas diffusivity during desorption in tectonic coal. Additionally, the desorbed data were modeled using the unipore and bidisperse models. The results show that the bidisperse model better describes the diffusion kinetics than the unipore model in this study. Additionally, the modeling results using the bidisperse approach suggest that the stress impact on the macropore diffusivity is greater than the stress on the micropore diffusivity. Under the same equilibrium pressure, the diffusivity varies with stress according to a four-stage function, which shows an ‘M-shape’. As the equilibrium gas pressure increased from 0.6 to 1.7 MPa, the critical point between stage 2 and stage 3 and between stage 3 and stage 4 transferred to a low stress. This difference is attributed to the gas pressure effects on the physical and mechanical properties of coal. These observations indicate that both the stress and gas pressure can significantly impact gas diffusion and may have significant implications on methane recovery in coal mines.

Steam Methane Reformation Testing for Air-Independent Solid Oxide Fuel Cell Systems

NASA Technical Reports Server (NTRS)

Mwara, Kamwana N.

2015-01-01

Recently, NASA has been looking into utilizing landers that can be propelled by LOX-CH (sub 4), to be used for long duration missions. Using landers that utilize such propellants, also provides the opportunity to use solid oxide fuel cells as a power option, especially since they are able to process methane into a reactant through fuel reformation. One type of reformation, called steam methane reformation, is a process to reform methane into a hydrogen-rich product by reacting methane and steam (fuel cell exhaust) over a catalyst. A steam methane reformation system could potentially use the fuel cell's own exhaust to create a reactant stream that is hydrogen-rich, and requires less internal reforming of the incoming methane. Also, steam reformation may hold some advantages over other types of reforming, such as partial oxidation (PROX) reformation. Steam reformation does not require oxygen, while up to 25 percent can be lost in PROX reformation due to unusable CO (sub 2) reformation. NASA's Johnson Space Center has conducted various phases of steam methane reformation testing, as a viable solution for in-space reformation. This has included using two different types of catalysts, developing a custom reformer, and optimizing the test system to find the optimal performance parameters and operating conditions.

The Application of a Jet Fan for the Control of Air and Methane Streams Mixing at the Excavations Cross - The Results of Numerical Simulation

NASA Astrophysics Data System (ADS)

Wrona, Paweł; Różański, Zenon; Pach, Grzegorz; Domagała, Lech

2016-09-01

The paper presents the results of numerical simulations into the distribution of methane concentration at the intersection of two excavations with a fan (turned on) giving the air stream to the area of the crossing. Assumed case represents emergency situation related to the unexpected flow of methane from an excavation and its mixing with fresh air. It is possible when sudden gas outburst takes place, methane leaks from methane drainage system or gas leaks out the pipelines of underground coal gasification devices. Three options were considered - corresponding to three different speeds of the jet fan. They represent three stages of fan work. First - low air speed is forced by a pneumatic fan, when electricity is cut off after high methane concentration detection. Medium speed can be forced by pneumatic-electric device when methane concentration allows to turn on the electricity. Third, the highest speed is for electric fans. Simulations were carried out in the Fire Dynamics Simulator (FDS) belongs to the group of programs Computational Fluid Dynamics (CFD). The governing equations are being solved in a numerical way. It was shown that proposed solution allows partial dilution of methane in every variant of speed what should allow escape of the miners from hazardous area.

Seasonal variability of stratospheric methane: implications for constraining tropospheric methane budgets using total column observations

NASA Astrophysics Data System (ADS)

Saad, Katherine M.; Wunch, Debra; Deutscher, Nicholas M.; Griffith, David W. T.; Hase, Frank; De Mazière, Martine; Notholt, Justus; Pollard, David F.; Roehl, Coleen M.; Schneider, Matthias; Sussmann, Ralf; Warneke, Thorsten; Wennberg, Paul O.

2016-11-01

Global and regional methane budgets are markedly uncertain. Conventionally, estimates of methane sources are derived by bridging emissions inventories with atmospheric observations employing chemical transport models. The accuracy of this approach requires correctly simulating advection and chemical loss such that modeled methane concentrations scale with surface fluxes. When total column measurements are assimilated into this framework, modeled stratospheric methane introduces additional potential for error. To evaluate the impact of such errors, we compare Total Carbon Column Observing Network (TCCON) and GEOS-Chem total and tropospheric column-averaged dry-air mole fractions of methane. We find that the model's stratospheric contribution to the total column is insensitive to perturbations to the seasonality or distribution of tropospheric emissions or loss. In the Northern Hemisphere, we identify disagreement between the measured and modeled stratospheric contribution, which increases as the tropopause altitude decreases, and a temporal phase lag in the model's tropospheric seasonality driven by transport errors. Within the context of GEOS-Chem, we find that the errors in tropospheric advection partially compensate for the stratospheric methane errors, masking inconsistencies between the modeled and measured tropospheric methane. These seasonally varying errors alias into source attributions resulting from model inversions. In particular, we suggest that the tropospheric phase lag error leads to large misdiagnoses of wetland emissions in the high latitudes of the Northern Hemisphere.

Catalytic generation of methane at 60-100 °C and 0.1-300 MPa from source rocks containing kerogen Types I, II, and III

NASA Astrophysics Data System (ADS)

Wei, Lin; Schimmelmann, Arndt; Mastalerz, Maria; Lahann, Richard W.; Sauer, Peter E.; Drobniak, Agnieszka; Strąpoć, Dariusz; Mango, Frank D.

2018-06-01

Low temperature (60 and 100 °C) and long-term (6 months to 5 years) heating of pre-evacuated and sterilized shales and coals containing kerogen Types I (Mahogany Shale), II (Mowry Shale and New Albany Shale), and III (Springfield Coal and Wilcox Lignite) with low initial maturities (vitrinite reflectance Ro 0.39-0.62%) demonstrates that catalytically generated hydrocarbons may explain the occurrence of some non-biogenic natural gas accumulations where insufficient thermal maturity contradicts the conventional thermal cracking paradigm. Extrapolation of the observed rate of catalytic methanogenesis in the laboratory suggests that significant amounts of sedimentary organic carbon can be converted to relatively dry natural gas over tens of thousands of years in sedimentary basins at temperatures as low as 60 °C. Our laboratory experiments utilized source rock (shale and coal) chips sealed in gold and Pyrex® glass tubes in the presence of hydrogen-isotopically contrasting waters. Parallel heating experiments applied hydrostatic pressures from 0.1 to 300 MPa. Control experiments constrained the influence of pre-existing and residual methane in closed pores of rock chips that was unrelated to newly generated methane. This study's experimental methane yields at 60 and 100 °C are 5-11 orders of magnitude higher than the theoretically predicted yields from kinetic models of thermogenic methane generation, which strongly suggests a contribution of catalytic methanogenesis. Higher temperature, longer heating time, and lower hydrostatic pressure enhanced catalytic methanogenesis. No clear relationships were observed between kerogen type or total organic carbon content and methane yields via catalysis. Catalytic methanogenesis was strongest in Mowry Shale where methane yields at 60 °C amounted to ∼2.5 μmol per gram of organic carbon after one year of hydrous heating at ambient pressure. In stark contrast to the earlier findings of hydrogen isotopic exchange between water and thermogenic methane in hydrous pyrolysis experiments above 300 °C, the hydrogen isotopic composition of added water exerted limited influence on the δ2H value of methane generated catalytically at low temperatures. We hypothesize that the catalytic sites responsible for methanogenesis are located in hydrophobic microenvironments with limited access to water. The δ13CCH4 values of methane generated catalytically at 60-100 °C range from ∼-57.6 to -41.4‰ and are thus similar to typical thermogenic methane (δ13CCH4 >-50‰) and microbially generated methane (<-55‰). Future studies need to evaluate the possibility that clumped isotope characteristics of catalytically generated methane can diagnose the low-temperature regime of catalytic methanogenesis. Furthermore, testing of freshly cored anoxic rocks is needed to determine whether the use of archived, oxygen-exposed rocks in geochemical maturation/catalysis studies introduces artifacts in experimental hydrocarbon yields.

Extending lean operating limit and reducing emissions of methane spark-ignited engines using a microwave-assisted spark plug

DOE PAGES

Rapp, Vi H.; DeFilippo, Anthony; Saxena, Samveg; ...

2012-01-01

Amore » microwave-assisted spark plug was used to extend the lean operating limit (lean limit) and reduce emissions of an engine burning methane-air. In-cylinder pressure data were collected at normalized air-fuel ratios of λ = 1.46, λ = 1.51, λ = 1.57, λ = 1.68, and λ = 1.75. For each λ , microwave energy (power supplied to the magnetron per engine cycle) was varied from 0 mJ (spark discharge alone) to 1600 mJ. At lean conditions, the results showed adding microwave energy to a standard spark plug discharge increased the number of complete combustion cycles, improving engine stability as compared to spark-only operation. Addition of microwave energy also increased the indicated thermal efficiency by 4% at λ = 1.68. At λ = 1.75, the spark discharge alone was unable to consistently ignite the air-fuel mixture, resulting in frequent misfires. Although microwave energy produced more consistent ignition than spark discharge alone at λ = 1.75, 59% of the cycles only partially burned. Overall, the microwave-assisted spark plug increased engine performance under lean operating conditions (λ = 1.68) but did not affect operation at conditions closer to stoichiometric.« less

[In situ Raman spectroscopic observation of micro-processes of methane hydrate formation and dissociation].

PubMed

Liu, Chang-Ling; Ye, Yu-Guang; Meng, Qing-Guo; Lü, Wan-Jun; Wang, Fei-Fei

2011-06-01

Micro laser Raman spectroscopic technique was used for in situ observation of the micro-processes of methane hydrate formed and decomposed in a high pressure transparent capillary. The changes in clathrate structure of methane hydrate were investigated during these processes. The results show that, during hydrate formation, the Raman peak (2 917 cm(-1)) of methane gas gradually splits into two peaks (2 905 and 2 915 cm(-1)) representing large and small cages, respectively, suggesting that the dissolved methane molecules go into two different chemical environments. In the meantime, the hydrogen bonds interaction is strengthened because water is changing from liquid to solid state gradually. As a result, the O-H stretching vibrations of water shift to lower wavenumber. During the decomposition process of methane hydrates, the Raman peaks of the methane molecules both in the large and small cages gradually clear up, and finally turn into a single peak of methane gas. The experimental results show that laser Raman spectroscopy can accurately demonstrate some relevant information of hydrate crystal structure changes during the formation and dissociation processes of methane hydrate.

GASP: A computer code for calculating the thermodynamic and transport properties for ten fluids: Parahydrogen, helium, neon, methane, nitrogen, carbon monoxide, oxygen, fluorine, argon, and carbon dioxide. [enthalpy, entropy, thermal conductivity, and specific heat

NASA Technical Reports Server (NTRS)

Hendricks, R. C.; Baron, A. K.; Peller, I. C.

1975-01-01

A FORTRAN IV subprogram called GASP is discussed which calculates the thermodynamic and transport properties for 10 pure fluids: parahydrogen, helium, neon, methane, nitrogen, carbon monoxide, oxygen, fluorine, argon, and carbon dioxide. The pressure range is generally from 0.1 to 400 atmospheres (to 100 atm for helium and to 1000 atm for hydrogen). The temperature ranges are from the triple point to 300 K for neon; to 500 K for carbon monoxide, oxygen, and fluorine; to 600 K for methane and nitrogen; to 1000 K for argon and carbon dioxide; to 2000 K for hydrogen; and from 6 to 500 K for helium. GASP accepts any two of pressure, temperature and density as input conditions along with pressure, and either entropy or enthalpy. The properties available in any combination as output include temperature, density, pressure, entropy, enthalpy, specific heats, sonic velocity, viscosity, thermal conductivity, and surface tension. The subprogram design is modular so that the user can choose only those subroutines necessary to the calculations.

Gram-scale, high-yield synthesis of a robust metal-organic framework for storing methane and other gases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilmer, CE; Farha, OK; Yildirim, T

We have synthesized and characterized a new metal-organic framework (MOF) material, NU-125, that, in the single-crystal limit, achieves a methane storage density at 58 bar (840 psi) and 298 K corresponding to 86% of that obtained with compressed natural gas tanks (CNG) used in vehicles today, when the latter are pressurized to 248 bar (3600 psi). More importantly, the deliverable capacity (58 bar to 5.8 bar) for NU-125 is 67% of the deliverable capacity of a CNG tank that starts at 248 bar. (For crystalline granules or powders, particle packing inefficiencies will yield densities and deliverable capacities lower than 86%more » and 67% of high-pressure CNG.) This material was synthesized in high yield on a gram-scale in a single-batch synthesis. Methane adsorption isotherms were measured over a wide pressure range (0.1-58 bar) and repeated over twelve cycles on the same sample, which showed no detectable degradation. Adsorption of CO2 and H-2 over a broad range of pressures and temperatures are also reported and agree with our computational findings.« less

Laser-Induced Fluorescence Measurements and Modeling of Nitric Oxide in Counterflow Diffusion Flames

NASA Technical Reports Server (NTRS)

Ravikrishna, Rayavarapu V.

2000-01-01

The feasibility of making quantitative nonintrusive NO concentration ([NO]) measurements in nonpremixed flames has been assessed by obtaining laser-induced fluorescence (LIF) measurements of [NO] in counterflow diffusion flames at atmospheric and higher pressures. Comparisons at atmospheric pressure between laser-saturated fluorescence (LSF) and linear LIF measurements in four diluted ethane-air counterflow diffusion flames with strain rates from 5 to 48/s yielded excellent agreement from fuel-lean to moderately fuel-rich conditions, thus indicating the utility of a model-based quenching correction technique, which was then extended to higher pressures. Quantitative LIF measurements of [NO] in three diluted methane-air counterflow diffusion flames with strain rates from 5 to 35/s were compared with OPPDIF model predictions using the GRI (version 2.11) chemical kinetic mechanism. The comparisons revealed that the GRI mechanism underpredicts prompt-NO by 30-50% at atmospheric pressure. Based on these measurements, a modified reaction rate coefficient for the prompt-NO initiation reaction was proposed which causes the predictions to match experimental data. Temperature measurements using thin filament pyrometry (TFP) in conjunction with a new calibration method utilizing a near-adiabatic H2-air Hencken burner gave very good comparisons with model predictions in these counterflow diffusion flames. Quantitative LIF measurements of [NO] were also obtained in four methane-air counterflow partially-premixed flames with fuel-side equivalence ratios (phi(sub B)) of 1.45, 1.6, 1.8 and 2.0. The measurements were in excellent agreement with model predictions when accounting for radiative heat loss. Spatial separation between regions dominated by the prompt and thermal NO mechanisms was observed in the phi(sub B) = 1.45 flame. The modified rate coefficient proposed earlier for the prompt-NO initiation reaction improved agreement between code predictions and measurements in the region where prompt-NO dominates. Finally, LIF measurements of NO were obtained in counterflow diffusion flames at 2 to 5 atm. Comparisons between [NO] measurements and predictions show that the GRI mechanism underpredicts prompt-NO by a factor of two to three at all pressures. In general, the results indicate a need for refinement of the CH chemistry, especially the pressure-dependent CH formation and destruction reactions.

Monodeuterated Methane, an Isotopic Tool To Assess Biological Methane Metabolism Rates

PubMed Central

Steele, Joshua A.; Ziebis, Wiebke; Scheller, Silvan; Case, David; Reynard, Linda M.; Orphan, Victoria J.

2017-01-01

ABSTRACT Biological methane oxidation is a globally relevant process that mediates the flux of an important greenhouse gas through both aerobic and anaerobic metabolic pathways. However, measuring these metabolic rates presents many obstacles, from logistical barriers to regulatory hurdles and poor precision. Here we present a new approach for investigating microbial methane metabolism based on hydrogen atom dynamics, which is complementary to carbon-focused assessments of methanotrophy. The method uses monodeuterated methane (CH3D) as a metabolic substrate, quantifying the aqueous D/H ratio over time using off-axis integrated cavity output spectroscopy. This approach represents a nontoxic, comparatively rapid, and straightforward approach that supplements existing radiotopic and stable carbon isotopic methods; by probing hydrogen atoms, it offers an additional dimension for examining rates and pathways of methane metabolism. We provide direct comparisons between the CH3D procedure and the well-established 14CH4 radiotracer method for several methanotrophic systems, including type I and II aerobic methanotroph cultures and methane-seep sediment slurries and carbonate rocks under anoxic and oxic incubation conditions. In all applications tested, methane consumption values calculated via the CH3D method were directly and consistently proportional to 14C radiolabel-derived methane oxidation rates. We also employed this method in a nontraditional experimental setup, using flexible, gas-impermeable bags to investigate the role of pressure on seep sediment methane oxidation rates. Results revealed an 80% increase over atmospheric pressure in methanotrophic rates the equivalent of ~900-m water depth, highlighting the importance of this parameter on methane metabolism and exhibiting the flexibility of the newly described method. IMPORTANCE Microbial methane consumption is a critical component of the global carbon cycle, with wide-ranging implications for climate regulation and hydrocarbon exploitation. Nonetheless, quantifying methane metabolism typically involves logistically challenging methods and/or specialized equipment; these impediments have limited our understanding of methane fluxes and reservoirs in natural systems, making effective management difficult. Here, we offer an easily implementable, precise method using monodeuterated methane (CH3D) that advances three specific aims. First, it allows users to directly compare methane consumption rates between different experimental treatments of the same inoculum. Second, by empirically linking the CH3D procedure with the well-established 14C radiocarbon approach, we determine absolute scaling factors that facilitate rate measurements for several aerobic and anaerobic systems of interest. Third, CH3D represents a helpful tool in evaluating the relationship between methane activation and full oxidation in methanotrophic metabolisms. The procedural advantages, consistency, and novel research questions enabled by the CH3D method should prove useful in a wide range of culture-based and environmental microbial systems to further elucidate methane metabolism dynamics. PMID:28861523

Monodeuterated Methane, an Isotopic Tool To Assess Biological Methane Metabolism Rates.

PubMed

Marlow, Jeffrey J; Steele, Joshua A; Ziebis, Wiebke; Scheller, Silvan; Case, David; Reynard, Linda M; Orphan, Victoria J

2017-01-01

Biological methane oxidation is a globally relevant process that mediates the flux of an important greenhouse gas through both aerobic and anaerobic metabolic pathways. However, measuring these metabolic rates presents many obstacles, from logistical barriers to regulatory hurdles and poor precision. Here we present a new approach for investigating microbial methane metabolism based on hydrogen atom dynamics, which is complementary to carbon-focused assessments of methanotrophy. The method uses monodeuterated methane (CH 3 D) as a metabolic substrate, quantifying the aqueous D/H ratio over time using off-axis integrated cavity output spectroscopy. This approach represents a nontoxic, comparatively rapid, and straightforward approach that supplements existing radiotopic and stable carbon isotopic methods; by probing hydrogen atoms, it offers an additional dimension for examining rates and pathways of methane metabolism. We provide direct comparisons between the CH 3 D procedure and the well-established 14 CH 4 radiotracer method for several methanotrophic systems, including type I and II aerobic methanotroph cultures and methane-seep sediment slurries and carbonate rocks under anoxic and oxic incubation conditions. In all applications tested, methane consumption values calculated via the CH 3 D method were directly and consistently proportional to 14 C radiolabel-derived methane oxidation rates. We also employed this method in a nontraditional experimental setup, using flexible, gas-impermeable bags to investigate the role of pressure on seep sediment methane oxidation rates. Results revealed an 80% increase over atmospheric pressure in methanotrophic rates the equivalent of ~900-m water depth, highlighting the importance of this parameter on methane metabolism and exhibiting the flexibility of the newly described method. IMPORTANCE Microbial methane consumption is a critical component of the global carbon cycle, with wide-ranging implications for climate regulation and hydrocarbon exploitation. Nonetheless, quantifying methane metabolism typically involves logistically challenging methods and/or specialized equipment; these impediments have limited our understanding of methane fluxes and reservoirs in natural systems, making effective management difficult. Here, we offer an easily implementable, precise method using monodeuterated methane (CH 3 D) that advances three specific aims. First, it allows users to directly compare methane consumption rates between different experimental treatments of the same inoculum. Second, by empirically linking the CH 3 D procedure with the well-established 14 C radiocarbon approach, we determine absolute scaling factors that facilitate rate measurements for several aerobic and anaerobic systems of interest. Third, CH 3 D represents a helpful tool in evaluating the relationship between methane activation and full oxidation in methanotrophic metabolisms. The procedural advantages, consistency, and novel research questions enabled by the CH 3 D method should prove useful in a wide range of culture-based and environmental microbial systems to further elucidate methane metabolism dynamics.

Hydrogen production by reforming of liquid hydrocarbons in a membrane reactor for portable power generation-Experimental studies

NASA Astrophysics Data System (ADS)

Damle, Ashok S.

One of the most promising technologies for lightweight, compact, portable power generation is proton exchange membrane (PEM) fuel cells. PEM fuel cells, however, require a source of pure hydrogen. Steam reforming of hydrocarbons in an integrated membrane reactor has potential to provide pure hydrogen in a compact system. Continuous separation of product hydrogen from the reforming gas mixture is expected to increase the yield of hydrogen significantly as predicted by model simulations. In the laboratory-scale experimental studies reported here steam reforming of liquid hydrocarbon fuels, butane, methanol and Clearlite ® was conducted to produce pure hydrogen in a single step membrane reformer using commercially available Pd-Ag foil membranes and reforming/WGS catalysts. All of the experimental results demonstrated increase in hydrocarbon conversion due to hydrogen separation when compared with the hydrocarbon conversion without any hydrogen separation. Increase in hydrogen recovery was also shown to result in corresponding increase in hydrocarbon conversion in these studies demonstrating the basic concept. The experiments also provided insight into the effect of individual variables such as pressure, temperature, gas space velocity, and steam to carbon ratio. Steam reforming of butane was found to be limited by reaction kinetics for the experimental conditions used: catalysts used, average gas space velocity, and the reactor characteristics of surface area to volume ratio. Steam reforming of methanol in the presence of only WGS catalyst on the other hand indicated that the membrane reactor performance was limited by membrane permeation, especially at lower temperatures and lower feed pressures due to slower reconstitution of CO and H 2 into methane thus maintaining high hydrogen partial pressures in the reacting gas mixture. The limited amount of data collected with steam reforming of Clearlite ® indicated very good match between theoretical predictions and experimental results indicating that the underlying assumption of the simple model of conversion of hydrocarbons to CO and H 2 followed by equilibrium reconstitution to methane appears to be reasonable one.

Precise methane absorption measurements in the 1.64 μm spectral region for the MERLIN mission.

PubMed

Delahaye, T; Maxwell, S E; Reed, Z D; Lin, H; Hodges, J T; Sung, K; Devi, V M; Warneke, T; Spietz, P; Tran, H

2016-06-27

In this article we describe a high-precision laboratory measurement targeting the R(6) manifold of the 2 ν 3 band of 12 CH 4 . Accurate physical models of this absorption spectrum will be required by the Franco-German, Methane Remote Sensing LIDAR (MERLIN) space mission for retrievals of atmospheric methane. The analysis uses the Hartmann-Tran profile for modeling line shape and also includes line-mixing effects. To this end, six high-resolution and high signal-to-noise absorption spectra of air-broadened methane were recorded using a frequency-stabilized cavity ring-down spectroscopy apparatus. Sample conditions corresponded to room temperature and spanned total sample pressures of 40 hPa - 1013 hPa with methane molar fractions between 1 μmol mol -1 and 12 μmol mol -1 . All spectroscopic model parameters were simultaneously adjusted in a multispectrum nonlinear least-squares fit to the six measured spectra. Comparison of the fitted model to the measured spectra reveals the ability to calculate the room-temperature, methane absorption coefficient to better than 0.1% at the on-line position of the MERLIN mission. This is the first time that such fidelity has been reached in modeling methane absorption in the investigated spectral region, fulfilling the accuracy requirements of the MERLIN mission. We also found excellent agreement when comparing the present results with measurements obtained over different pressure conditions and using other laboratory techniques. Finally, we also evaluated the impact of these new spectral parameters on atmospheric transmissions spectra calculations.

Precise methane absorption measurements in the 1.64 μm spectral region for the MERLIN mission

PubMed Central

Delahaye, T.; Maxwell, S.E.; Reed, Z.D.; Lin, H.; Hodges, J.T.; Sung, K.; Devi, V.M.; Warneke, T.; Spietz, P.; Tran, H.

2016-01-01

In this article we describe a high-precision laboratory measurement targeting the R(6) manifold of the 2ν3 band of 12CH4. Accurate physical models of this absorption spectrum will be required by the Franco-German, Methane Remote Sensing LIDAR (MERLIN) space mission for retrievals of atmospheric methane. The analysis uses the Hartmann-Tran profile for modeling line shape and also includes line-mixing effects. To this end, six high-resolution and high signal-to-noise absorption spectra of air-broadened methane were recorded using a frequency-stabilized cavity ring-down spectroscopy apparatus. Sample conditions corresponded to room temperature and spanned total sample pressures of 40 hPa – 1013 hPa with methane molar fractions between 1 μmol mol−1 and 12 μmol mol−1. All spectroscopic model parameters were simultaneously adjusted in a multispectrum nonlinear least-squares fit to the six measured spectra. Comparison of the fitted model to the measured spectra reveals the ability to calculate the room-temperature, methane absorption coefficient to better than 0.1% at the on-line position of the MERLIN mission. This is the first time that such fidelity has been reached in modeling methane absorption in the investigated spectral region, fulfilling the accuracy requirements of the MERLIN mission. We also found excellent agreement when comparing the present results with measurements obtained over different pressure conditions and using other laboratory techniques. Finally, we also evaluated the impact of these new spectral parameters on atmospheric transmissions spectra calculations. PMID:27551656

Combination volumetric and gravimetric sorption instrument for high accuracy measurements of methane adsorption

NASA Astrophysics Data System (ADS)

Burress, Jacob; Bethea, Donald; Troub, Brandon

2017-05-01

The accurate measurement of adsorbed gas up to high pressures (˜100 bars) is critical for the development of new materials for adsorbed gas storage. The typical Sievert-type volumetric method introduces accumulating errors that can become large at maximum pressures. Alternatively, gravimetric methods employing microbalances require careful buoyancy corrections. In this paper, we present a combination gravimetric and volumetric system for methane sorption measurements on samples between ˜0.5 and 1 g. The gravimetric method described requires no buoyancy corrections. The tandem use of the gravimetric method allows for a check on the highest uncertainty volumetric measurements. The sources and proper calculation of uncertainties are discussed. Results from methane measurements on activated carbon MSC-30 and metal-organic framework HKUST-1 are compared across methods and within the literature.

Combination volumetric and gravimetric sorption instrument for high accuracy measurements of methane adsorption.

PubMed

Burress, Jacob; Bethea, Donald; Troub, Brandon

2017-05-01

The accurate measurement of adsorbed gas up to high pressures (∼100 bars) is critical for the development of new materials for adsorbed gas storage. The typical Sievert-type volumetric method introduces accumulating errors that can become large at maximum pressures. Alternatively, gravimetric methods employing microbalances require careful buoyancy corrections. In this paper, we present a combination gravimetric and volumetric system for methane sorption measurements on samples between ∼0.5 and 1 g. The gravimetric method described requires no buoyancy corrections. The tandem use of the gravimetric method allows for a check on the highest uncertainty volumetric measurements. The sources and proper calculation of uncertainties are discussed. Results from methane measurements on activated carbon MSC-30 and metal-organic framework HKUST-1 are compared across methods and within the literature.

Structural transformations of sVI tert-butylamine hydrates to sII binary hydrates with methane.

PubMed

Prasad, Pinnelli S R; Sugahara, Takeshi; Sloan, E Dendy; Sum, Amadeu K; Koh, Carolyn A

2009-10-22

Binary clathrate hydrates with methane (CH(4), 4.36 A) and tert-butylamine (t-BuNH(2), 6.72 A) as guest molecules were synthesized at different molar concentrations of t-BuNH(2) (1.00-9.31 mol %) with methane at 7.0 MPa and 250 K, and were characterized by powder X-ray diffraction (PXRD) and Raman microscopy. A structural transformation from sVI to sII of t-BuNH(2) hydrate was clearly observed on pressurizing with methane. The PXRD showed sII signatures and the remnant sVI signatures were insignificant, implying the metastable nature of sVI binary hydrates. Raman spectroscopic data on these binary hydrates suggest that the methane molecules occupy the small cages and vacant large cages. The methane storage capacity in this system was nearly doubled to approximately 6.86 wt % for 5.56 mol % > t-BuNH(2) > 1.0 mol %.

Methane Hydrate in Confined Spaces: An Alternative Storage System.

PubMed

Borchardt, Lars; Casco, Mirian Elizabeth; Silvestre-Albero, Joaquin

2018-06-05

Methane hydrate inheres the great potential to be a nature-inspired alternative for chemical energy storage, as it allows to store large amounts of methane in a dense solid phase. The embedment of methane hydrate in the confined environment of porous materials can be capitalized for potential applications as its physicochemical properties, such as the formation kinetics or pressure and temperature stability, are significantly changed compared to the bulk system. We review this topic from a materials scientific perspective by considering porous carbons, silica, clays, zeolites, and polymers as host structures for methane hydrate formation. We discuss the contribution of advanced characterization techniques and theoretical simulations towards the elucidation of the methane hydrate formation and dissociation process within the confined space. We outline the scientific challenges this system is currently facing and look on possible future applications for this technology. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fundamental challenges to methane recovery from gas hydrates

USGS Publications Warehouse

Servio, P.; Eaton, M.W.; Mahajan, D.; Winters, W.J.

2005-01-01

The fundamental challenges, the location, magnitude, and feasibility of recovery, which must be addressed to recover methane from dispersed hydrate sources, are presented. To induce dissociation of gas hydrate prior to methane recovery, two potential methods are typically considered. Because thermal stimulation requires a large energy input, it is less economically feasible than depressurization. The new data will allow the study of the effect of pressure, temperature, diffusion, porosity, tortuosity, composition of gas and water, and porous media on gas-hydrate production. These data also will allow one to improve existing models related to the stability and dissociation of sea floor hydrates. The reproducible kinetic data from the planned runs together with sediment properties will aid in developing a process to economically recover methane from a potential untapped hydrate source. The availability of plentiful methane will allow economical and large-scale production of methane-derived clean fuels to help avert future energy crises.

METHOD FOR PRODUCING ISOTOPIC METHANES FROM LITHIUM CARBONATE AND LITHIUM HYDRIDE

DOEpatents

Frazer, J.W.

1959-10-27

A process is descrlbed for the production of methane and for the production of methane containing isotopes of hydrogen and/or carbon. Finely divided lithium hydrlde and litldum carbonate reactants are mixed in intimate contact and subsequently compacted under pressures of from 5000 to 60,000 psl. The compacted lithium hydride and lithium carbenate reactunts are dispised in a gas collecting apparatus. Subsequently, the compact is heated to a temperature in the range 350 to 400 deg C whereupon a solid-solid reaction takes place and gaseous methane is evolved. The evolved methane is contaminated with gaseous hydrogen and a very small amount of CO/sub 2/; however, the desired methane product is separated from sald impurities by well known chemical processes, e.g., condensation in a cold trap. The product methane contalns isotopes of carbon and hydrogen, the Isotopic composition being determined by the carbon isotopes originally present In the lithium carbonate and the hydrogen isotopes originally present in the lithium hydride.

Methane seeps along boundaries of arctic permafrost thaw and melting glaciers

NASA Astrophysics Data System (ADS)

Anthony, P.; Walter Anthony, K. M.; Grosse, G.; Chanton, J.

2014-12-01

Methane, a potent greenhouse gas, accumulates in subsurface hydrocarbon reservoirs. In the Arctic, impermeable icy permafrost and glacial overburden form a 'cryosphere cap' that traps gas leaking from these reservoirs, restricting flow to the atmosphere. We document the release of geologic methane to the atmosphere from abundant gas seeps concentrated along boundaries of permafrost thaw and receding glaciers in Alaska. Through aerial and ground surveys we mapped >150,000 seeps identified as bubbling-induced open holes in lake ice. Subcap methane seeps had anomalously high fluxes, 14C-depletion, and stable isotope values matching known coalbed and thermogenic methane accumulations in Alaska. Additionally, we observed younger subcap methane seeps in Greenland that were associated with ice-sheet retreat since the Little Ice Age. These correlations suggest that in a warming climate, continued disintegration of permafrost, glaciers, and parts of the polar ice sheets will relax pressure on subsurface seals and further open conduits, allowing a transient expulsion of geologic methane currently trapped by the cryosphere cap.

Binary gaseous mixture and single component adsorption of methane and argon on exfoliated graphite

NASA Astrophysics Data System (ADS)

Russell, Brice Adam

Exfoliated graphite was used as a substrate for adsorption of argon and methane. Adsorption experiments were conducted for both equal parts mixtures of argon and methane and for each gas species independently. The purpose of this was to compare mixture adsorption to single component adsorption and to investigate theoretical predictions concerning the kinetics of adsorption made by Burde and Calbi.6 In particular, time to reach pressure equilibrium of a single dose at a constant temperature for the equal parts mixture was compared to time of adsorption for each species by itself. It was shown that mixture adsorption is a much more complex and time consuming process than single component adsorption and requires a much longer amount of time to reach equilibrium. Information about the composition evolution of the mixture during the times when pressure was going toward equilibrium was obtained using a quadrupole mass spectrometer. Evidence for initial higher rate of adsorption for the weaker binding energy species (argon) was found as well as overall composition change which clearly indicated a higher coverage of methane on the graphite sample by the time equilibration was reached. Effective specific surface area of graphite for both argon and methane was also determined using the Point-B method.2

Colors of Alien Worlds from Direct Imaging Exoplanet Missions

NASA Astrophysics Data System (ADS)

Hu, Renyu

2016-01-01

Future direct-imaging exoplanet missions such as WFIRST will measure the reflectivity of exoplanets at visible wavelengths. Most of the exoplanets to be observed will be located further away from their parent stars than is Earth from the Sun. These "cold" exoplanets have atmospheric environments conducive for the formation of water and/or ammonia clouds, like Jupiter in the Solar System. I find the mixing ratio of methane and the pressure level of the uppermost cloud deck on these planets can be uniquely determined from their reflection spectra, with moderate spectral resolution, if the cloud deck is between 0.6 and 1.5 bars. The existence of this unique solution is useful for exoplanet direct imaging missions for several reasons. First, the weak bands and strong bands of methane enable the measurement of the methane mixing ratio and the cloud pressure, although an overlying haze layer can bias the estimate of the latter. Second, the cloud pressure, once derived, yields an important constraint on the internal heat flux from the planet, and thus indicating its thermal evolution. Third, water worlds having H2O-dominated atmospheres are likely to have water clouds located higher than the 10-3 bar pressure level, and muted spectral absorption features. These planets would occupy a confined phase space in the color-color diagrams, likely distinguishable from H2-rich giant exoplanets by broadband observations. Therefore, direct-imaging exoplanet missions may offer the capability to broadly distinguish H2-rich giant exoplanets versus H2O-rich super-Earth exoplanets, and to detect ammonia and/or water clouds and methane gas in their atmospheres.

Massive production of abiotic methane during subduction evidenced in metamorphosed ophicarbonates from the Italian Alps

PubMed Central

Vitale Brovarone, Alberto; Martinez, Isabelle; Elmaleh, Agnès; Compagnoni, Roberto; Chaduteau, Carine; Ferraris, Cristiano; Esteve, Imène

2017-01-01

Alteration of ultramafic rocks plays a major role in the production of hydrocarbons and organic compounds via abiotic processes on Earth and beyond and contributes to the redistribution of C between solid and fluid reservoirs over geological cycles. Abiotic methanogenesis in ultramafic rocks is well documented at shallow conditions, whereas natural evidence at greater depths is scarce. Here we provide evidence for intense high-pressure abiotic methanogenesis by reduction of subducted ophicarbonates. Protracted (≥0.5–1 Ma), probably episodic infiltration of reduced fluids in the ophicarbonates and methanogenesis occurred from at least ∼40 km depth to ∼15–20 km depth. Textural, petrological and isotopic data indicate that methane reached saturation triggering the precipitation of graphitic C accompanied by dissolution of the precursor antigorite. Continuous infiltration of external reducing fluids caused additional methane production by interaction with the newly formed graphite. Alteration of high-pressure carbonate-bearing ultramafic rocks may represent an important source of abiotic methane, with strong implications for the mobility of deep C reservoirs. PMID:28223715

Information-rich spectral channels for simulated retrievals of partial column-averaged methane

NASA Astrophysics Data System (ADS)

Su, Zhan; Xi, Xi; Natraj, Vijay; Li, King-Fai; Shia, Run-Lie; Miller, Charles E.; Yung, Yuk L.

2016-01-01

Space-based remote sensing of the column-averaged methane dry air mole fraction (XCH4) has greatly increased our understanding of the spatiotemporal patterns in the global methane cycle. The potential to retrieve multiple pieces of vertical profile information would further improve the quantification of CH4 across space-time scales. We conduct information analysis for channel selection and evaluate the prospects of retrieving multiple pieces of information as well as total column CH4 from both ground-based and space-based near-infrared remote sensing spectra. We analyze the degrees of freedom of signal (DOF) in the CH4 absorption bands near 2.3 μm and 1.6 μm and select ˜1% of the channels that contain >95% of the information about the CH4 profile. The DOF is around 4 for fine ground-based spectra (resolution = 0.01 cm-1) and 3 for coarse space-based spectra (resolution = 0.20 cm-1) based on channel selection and a signal-to-noise ratio (SNR) of 300. The DOF varies from 2.2 to 3.2 when SNR is between 100 and 300, and spectral resolution is 0.20 cm-1. Simulated retrieval tests in clear-sky conditions using the selected channels reveal that the retrieved partial column-averaged CH4 values are not sensitive to the a priori profiles and can reflect local enhancements of CH4 in different partial air columns. Both the total and partial column-averaged retrieval errors in all tests are within 1% of the true state. These simulated tests highlight the possibility to retrieve up to three to four pieces of information about the vertical distribution of CH4 in reality.

Computing gas solubility in reservoir waters for environmental chemistry applications: the role of satellite observations

NASA Astrophysics Data System (ADS)

Rosa, R.; Lima, I.; Ramos, F.; Bambace, L.; Assireu, A.; Stech, J.; Novo, E.; Lorenzeti, L.

Atmospheric greenhouse gases concentration has increased during the past centuries basically due to biogenic and pyrogenic anthopogenic emissions Recent investigations have shown that gas emission methane as an important example from tropical hydroelectric reservoirs may comprise a considerable fraction of the total anthropogenic bulk In order to evaluate the concentration of gases of potential importance in environmental chemistry the solubility of such gases have been collected and converted into a uniform format using the Henry s law which states that the solubility of a gas in a liquid is directly proportional to its partial pressure However the Henry s law can be derived as a function of temperature density molar mixing ratio in the aqueous phase and molar mass of water In this paper we show that due to the complex temperature variation and water composition measured in brazilian tropical reservoirs as Serra da Mesa and Manso expressive secular variation on the traditional solubility constants concentration of a species in the aqueous phase by the partial pressure of that species in the gas phase can change in a rate of approximately 30 in 6 decades This estimation comes from a computational analysis of temperature variation measured during 6 months in Serra da Mesa and Manso reservoirs taking into account a simulated density and molar mass variation of the aqueous composition in these environments As an important global change issue from this preliminary analysis we discuss its role in the current estimations on the concentration emission rates

Method of and system for producing electrical power

DOEpatents

Carabetta, Ralph A.; Staats, Gary E.; Cutting, John C.

1993-01-01

A method and system for converting the chemical energy of methane to electrical energy. Methane is thermally decomposed to hydrogen and carbon in a decomposing unit at a temperature not less than about 1200.degree. K. and at a pressure at least slightly above atmospheric pressure. Carbon and substantially pure oxygen and a cesium or potassium seed material is transmitted to a combustor which is maintained at a pressure of at least about 50 atmospheres to combust the carbon and oxygen and provide an ionized plasma having a temperature not less than about 2800.degree. K. The ionized plasma is accelerated to a velocity not less than about 1000 m/sec and transported through an MHD generator having a magnetic field in the range of from about 4 to about 6 Tesla to generate dc power. The ionized plasma is de-accelerated and passed from the MHD generator in heat exchange relationship with the methane to heat same for decomposition and or reaction, and thereafter any cesium or potassium seed material is recovered and transported to the combustor, and the dc power from the MHD generator is converted to ac power.

Fourier Transform Spectroscopy of two trace gases namely Methane and Carbon monoxide for planetary and atmospheric research application

NASA Astrophysics Data System (ADS)

Hashemi, R.; Dudaryonok, A. S.; Lavrentieva, N. N.; Vandaele, A. C.; Vander Auwera, J.; Tyuterev, AV Nikitin G., VI; Sung, K.; Smith, M. A. H.; Devi, V. M.; Predoi-Cross, A.

2017-02-01

Two atmospheric trace gases, namely methane and carbon monoxide have been considered in this study. Fourier transform absorption spectra of the 2-0 band of 12C16O mixed with CO2 have been recorded at total pressures from 156 to 1212 hPa and at 4 different temperatures between 240 K and 283 K. CO2 pressure-induced line broadening and line shift coefficients, and the associated temperature dependence have been measured in an multi-spectrum non-linear least squares analysis using Voigt profiles with an asymmetric profile due to line mixing. The measured CO2-broadening and CO2-shift parameters were compared with theoretical values, calculated by collaborators. In addition, the CO2-broadening and shift coefficients have been calculated for individual temperatures using the Exponential Power Gap (EPG) semi-empirical method. We also discuss the retrieved line shape parameters for Methane transitions in the spectral range known as the Methane Octad. We used high resolution spectra of pure methane and of dilute mixtures of methane in dry air, recorded with high signal to noise ratio at temperatures between 148 K and room temperature using the Bruker IFS 125 HR Fourier transform spectrometer (FTS) at the Jet Propulsion Laboratory, Pasadena, California. Theoretical calculations for line parameters have been performed and the results are compared with the previously published values and with the line parameters available in the GEISA2015 [1] and HITRAN2012 [2] databases.

Flash crystallization kinetics of methane (sI) hydrate in a thermoelectrically-cooled microreactor.

PubMed

Chen, Weiqi; Pinho, Bruno; Hartman, Ryan L

2017-09-12

The crystallization kinetics of methane (sI) hydrate were investigated in a thermoelectrically-cooled microreactor with in situ Raman spectroscopy. Step-wise and precise control of the temperature allowed acquisition of reproducible data within minutes, while the nucleation of methane hydrates can take up to 24 h in traditional batch reactors. The propagation rates of methane hydrate (from 3.1-196.3 μm s -1 ) at the gas-liquid interface were measured for different Reynolds' numbers (0.7-68.9), pressures (30.0-80.9 bar), and sub-cooling temperatures (1.0-4.0 K). The precise measurement of the propagation rates and their subsequent analyses revealed a transition from mixed heat-transfer-crystallization-rate-limited to mixed heat-transfer-mass-transfer-crystallization-rate-limited kinetics. A theoretical model, based on heat transfer, mass transfer, and intrinsic crystallization kinetics, was derived for the first time to understand the non-linear relationship between the propagation rate and sub-cooling temperature. The molecular diffusivity of methane within a stagnant film (ahead of the propagation front) was discovered to follow Stokes-Einstein, while calculated Hatta (0.50-0.68), Lewis (128-207), and beta (0.79-116) numbers also confirmed that the diffusive flux influences crystal growth. Understanding methane hydrate crystal growth is important to the atmospheric, oceanic, and planetary sciences and to energy production, storage, and transportation. Our discoveries could someday advance the science of other multiphase, high-pressure, and sub-cooled crystallizations.

Formation of Gas Traps in the Martian Soil and Implications for Methane Variability on Mars.

NASA Astrophysics Data System (ADS)

Pavlov, A.; Davis, J.; Redwing, E.; Trainer, M. G.; Johnson, C.

2017-12-01

Several independent groups have reported on the detection of methane in the Martian atmosphere. Mars Science Laboratory (MSL) methane observations display rapid increase of the atmospheric methane abundance from 1 ppb to 7 ppb levels followed by an abrupt disappearance suggest the possibility of small, local, near-surface sources of methane. Such sources may take the form of shallow subsurface cemented soil caps which can trap gases and are readily activated by either motion of the MSL rover itself, by impacts of small meteorites, or even annual climate oscillations. We have simulated the formation of such soil caps in the shallow subsurface Martian-like condition. We show that the initially uniform sample of icy soil (JSC-Mars-1A) with Mg perchlorate exhibit quick stratification on the scale of several cm under Martian pressures over the period of several days. Briny water migrates towards the top of the sample resulting in the enhanced abundance of perchlorates in the top few cm. As water evaporates and ice sublimates from the top of the sample, perchlorate remains in the top layer of soil causing soil cementation and formation of the cap. The observed caps were solid, ice-free and effectively shut off sublimation of ice from underneath the cap. We tested whether similar soil caps can trap various gases (including methane) in the shallow subsurface of Mars. We injected neon gas at the bottom of the soil sample and monitored neon gas permeability through the soil sample by measuring gas pressure differential above and below the soil sample. We found that a mixture of JSC-Mars-1A and 5% of Mg perchlorate produce gas impermeable soil cap capable of withstanding an excess of 5 mbars of neon under the cap at the soil temperatures +0.5 C - +9 C. The cap remained gas impermeable after subsequent cooling of the sample soil sample to the subzero temperatures. Gas permeability of the soil caps under various temperatures and atmospheric pressures will be reported. Our results suggest that the formation of cemented soil caps can be widespread phenomena on Mars in the areas of shallow permafrost and abundant perchlorates or RSL slopes. Potentially, soil caps can form gas pockets for trace species (like methane) which can be relatively easily disturbed causing abrupt changes in the atmospheric methane abundance detected by MSL's Curiosity rover.

Biogas Laminar Burning Velocity and Flammability Characteristics in Spark Ignited Premix Combustion

NASA Astrophysics Data System (ADS)

Anggono, Willyanto; Wardana, I. N. G.; Lawes, M.; Hughes, K. J.; Wahyudi, Slamet; Hamidi, Nurkholis; Hayakawa, Akihiro

2013-04-01

Spherically expanding flames propagating at constant pressure were employed to determine the laminar burning velocity and flammability characteristics of biogas-air mixtures in premixed combustion to uncover the fundamental flame propagation characteristics of a new alternative and renewable fuel. The results are compared with those from a methane-air flame. Biogas is a sustainable and renewable fuel that is produced in digestion facilities. The composition of biogas discussed in this paper consists of 66.4% methane, 30.6% carbon dioxide and 3% nitrogen. Burning velocity was measured at various equivalence ratios (phi) using a photographic technique in a high pressure fan-stirred bomb, the initial condition being at room temperature and atmospheric pressure. The flame for methane-air mixtures propagates from phi=0.6 till phi=1.3. The flame at phi >= 1.4 does not propagate because the combustion reaction is quenched by the larger mass of fuel. At phi<=0.5, it does not propagate as well since the heat of reaction is insufficient to burn the mixtures. The flame for biogas-air mixtures propagates in a narrower range, that is from phi=0.6 to phi=1.2. Different from the methane flame, the biogas flame does not propagate at phi>=1.3 because the heat absorbed by inhibitors strengthens the quenching effect by the larger mass of fuel. As in the methane flame, the biogas flame at phi<=0.5 does not propagate. This shows that the effect of inhibitors in extremely lean mixtures is small. Compared to a methane-air mixture, the flammability characteristic (flammable region) of biogas becomes narrower in the presence of inhibitors (carbon dioxide and nitrogen) and the presence of inhibitors causes a reduction in the laminar burning velocity. The inhibitor gases work more effectively at rich mixtures because the rich biogas-air mixtures have a higher fraction of carbon dioxide and nitrogen components compared to the lean biogas-air mixtures.

Constraining the relationships between anaerobic oxidation of methane and sulfate reduction under in situ methane concentrations

NASA Astrophysics Data System (ADS)

Zhuang, G.; Wegener, G.; Joye, S. B.

2017-12-01

The anaerobic oxidation of methane (AOM) is an important microbial metabolism in the global carbon cycle. In marine methane seeps sediment, this process is mediated by syntrophic consortium that includes anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). Stoichiometrically in AOM methane oxidation should be coupled to sulfate reduction (SR) in a 1:1 ratio. However, weak coupling of AOM and SR in seep sediments was frequently observed from the ex situ rate measurements, and the metabolic dynamics of AOM and SR under in situ conditions remain poorly understood. Here we investigated the metabolic activity of AOM and SR with radiotracers by restoring in situ methane concentrations under pressure to constrain the in situ relationships between AOM and SR in the cold seep sediments of Gulf of Mexico as well as the sediment-free AOM enrichments cultivated from cold seep of Italian Island Elba or hydrothermal vent of Guaymas Basin5. Surprisingly, we found that AOM rates strongly exceeded those of SR when high pressures and methane concentrations were applied at seep sites of GC600 and GC767 in Gulf of Mexico. With the addition of molybdate, SR was inhibited but AOM was not affected, suggesting the potential coupling of AOM with other terminal processes. Amendments of nitrate, iron, manganese and AQDS to the SR-inhibited slurries did not stimulate or inhibit the AOM activity, indicating either those electron acceptors were not limiting for AOM in the sediments or AOM was coupled to other process (e.g., organic matter). In the ANME enrichments, higher AOM rates were also observed with the addition of high concentrations of methane (10mM and 50 mM). The tracer transfer of CO2 to methane, i.e., the back reaction of AOM, increased with increasing methane concentrations and accounted for 1%-5% of the AOM rates. AOM rates at 10 mM and 50 mM methane concentration were much higher than the SR rates, suggesting those two processes were not tightly coupled. Collectively, our results provided evidence for the possible decoupling of AOM and SR under in situconditions. This decoupling appears to be widespread in methane-rich marine sediment, motivating a wide variety of future research endeavors.

Combustion Stability Characteristics of the Project Morpheus Liquid Oxygen / Liquid Methane Main Engine

NASA Technical Reports Server (NTRS)

Melcher, John C.; Morehead, Robert L.

2014-01-01

The project Morpheus liquid oxygen (LOX) / liquid methane (LCH4) main engine is a Johnson Space Center (JSC) designed 5,000 lbf-thrust, 4:1 throttling, pressure-fed cryogenic engine using an impinging element injector design. The engine met or exceeded all performance requirements without experiencing any in- ight failures, but the engine exhibited acoustic-coupled combustion instabilities during sea-level ground-based testing. First tangential (1T), rst radial (1R), 1T1R, and higher order modes were triggered by conditions during the Morpheus vehicle derived low chamber pressure startup sequence. The instability was never observed to initiate during mainstage, even at low power levels. Ground-interaction acoustics aggravated the instability in vehicle tests. Analysis of more than 200 hot re tests on the Morpheus vehicle and Stennis Space Center (SSC) test stand showed a relationship between ignition stability and injector/chamber pressure. The instability had the distinct characteristic of initiating at high relative injection pressure drop at low chamber pressure during the start sequence. Data analysis suggests that the two-phase density during engine start results in a high injection velocity, possibly triggering the instabilities predicted by the Hewitt stability curves. Engine ignition instability was successfully mitigated via a higher-chamber pressure start sequence (e.g., 50% power level vs 30%) and operational propellant start temperature limits that maintained \\cold LOX" and \\warm methane" at the engine inlet. The main engine successfully demonstrated 4:1 throttling without chugging during mainstage, but chug instabilities were observed during some engine shutdown sequences at low injector pressure drop, especially during vehicle landing.

Small Molecule Catalysts for Harvesting Methane Gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, S. E.; Ceron-Hernandez, M.; Oakdale, J.

As the average temperature of the earth increases the impact of these changes are becoming apparent. One of the most dramatic changes to the environment is the melting of arctic permafrost. The disappearance of the permafrost has resulted in release of streams of methane that was trapped in remote areas as gas hydrates in ice. Additionally, the use of fracking has also increased emission of methane. Currently, the methane is either lost to the atmosphere or flared. If these streams of methane could be brought to market, this would be an abundant source of revenue. A cheap conversion of gaseousmore » methane to a more convenient form for transport would be necessary to economical. Conversion of methane is a difficult reaction since the C-H bond is very stable (104 kcal/mole). At the industrial scale, the Fischer-Tropsch reaction can be used to convert gaseous methane to liquid methanol but is this method is impractical for these streams that have low pressures and are located in remote areas. Additionally, the Fischer-Tropsch reaction results in over oxidation of the methane leading to many products that would need to be separated.« less

Prospects in straw disintegration for biogas production.

PubMed

Maroušek, Josef

2013-10-01

The pretreatment methods for enhancing biogas production from oat straw under study include hot maceration, steam explosion, and pressure shockwaves. The micropore area (9, 55, and 64 m(2) g(-1)) inhibitor formations (0, 15, and 0 mL L(-1)) as well as the overall methane yields (67, 179, and 255 CH4 VS t(-1)) were robustly analyzed. It was confirmed that the operating conditions of the steam explosion must be precisely tailored to the substrate. Furthermore, it was beneficial to prepend the hot maceration before the steam explosion and the pressure shockwaves. The second alternative may give increased methane yields (246 in comparison to 273 CH4 VS t(-1)); however, the application of pressure shockwaves still faces limitations for deployment on a commercial scale.

Analysis of Screen Channel LAD Bubble Point Tests in Liquid Methane at Elevated Temperature

NASA Technical Reports Server (NTRS)

Hartwig, Jason; McQuillen, John

2012-01-01

This paper examines the effect of varying the liquid temperature and pressure on the bubble point pressure for screen channel Liquid Acquisition Devices in cryogenic liquid methane using gaseous helium across a wide range of elevated pressures and temperatures. Testing of a 325 x 2300 Dutch Twill screen sample was conducted in the Cryogenic Components Lab 7 facility at the NASA Glenn Research Center in Cleveland, Ohio. Test conditions ranged from 105 to 160K and 0.0965 - 1.78 MPa. Bubble point is shown to be a strong function of the liquid temperature and a weak function of the amount of subcooling at the LAD screen. The model predicts well for saturated liquid but under predicts the subcooled data.

Direct methane solid oxide fuel cells and their related applications

NASA Astrophysics Data System (ADS)

Lin, Yuanbo

Solid oxide fuel cells (SOFCs), renowned for their high electrical generation efficiency with low pollutant production, are promising for reducing global energy and environmental concerns. However, there are major barriers for SOFC commercialization. A primary challenge is reducing the capital cost of SOFC power plants to levels that can compete with other generation methods. While the focus of this thesis research was on operation of SOFCs directly with methane fuel, the underlying motivation was to make SOFCs more competitive by reducing their cost. This can be achieved by making SOFCs that reduce the size and complexity of the required "balance of plant". Firstly, direct operation of SOFCs on methane is desirable since it can eliminate the external reformer. However, effective means must be found to suppress deleterious anode coking in methane. In this thesis, the operating conditions under which SOFCs can operate stably and without anode coking were investigated in detail, and the underlying mechanisms of coking and degradation were determined. Furthermore, a novel design utilizing an inert anode barrier layer was developed and shown to substantially improve stability against coking. Secondly, the direct methane SOFCs were investigated for use as electrochemical partial oxidation (EPOx) reactors that can co-generate electricity and synthesis gas (CO+H2) from methane. The results indicated that conventional SOFCs work quite well as methane partial oxidation reactors, producing syngas at relatively high rates. While this approach would not decrease the cost of SOFC power plant, it would improve prospects for commercialization by increasing the value of the power plant, because two products, electricity and syngas, can be sold. Thirdly, SOFCs utilizing thin (La,Sr)(Ga,Mg)O3 electrolytes were demonstrated. This highly conductive material allows lower SOFC operation temperature, leading to the use of lower-cost materials for sealing, interconnection, and balance of plant. Deleterious electrolyte/electrode reactions and electrolyte La loss were avoided during high-temperature co-firing by using thin La-doped ceria barrier layers, allowing very high power densities at moderate operating temperatures. (La,Sr)(Ga,Mg)O3-(La,Sr)(Fe,Co)O3 composite cathodes were investigated and optimal processing parameters that yield low interfacial polarization resistance at intermediate temperature were determined.

Methane Decomposition and Carbon Growth on Y2O3, Yttria-Stabilized Zirconia, and ZrO2

PubMed Central

2014-01-01

Carbon deposition following thermal methane decomposition under dry and steam reforming conditions has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 by a range of different chemical, structural, and spectroscopic characterization techniques, including aberration-corrected electron microscopy, Raman spectroscopy, electric impedance spectroscopy, and volumetric adsorption techniques. Concordantly, all experimental techniques reveal the formation of a conducting layer of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in dry methane at temperatures T ≥ 1000 K. In addition, treatment under moist methane conditions causes additional formation of carbon-nanotube-like architectures by partial detachment of the graphite layers. All experiments show that during carbon growth, no substantial reduction of any of the oxides takes place. Our results, therefore, indicate that these pure oxides can act as efficient nonmetallic substrates for methane-induced growth of different carbon species with potentially important implications regarding their use in solid oxide fuel cells. Moreover, by comparing the three oxides, we could elucidate differences in the methane reactivities of the respective SOFC-relevant purely oxidic surfaces under typical SOFC operation conditions without the presence of metallic constituents. PMID:24587591

LES/PDF studies of joint statistics of mixture fraction and progress variable in piloted methane jet flames with inhomogeneous inlet flows

NASA Astrophysics Data System (ADS)

Zhang, Pei; Barlow, Robert; Masri, Assaad; Wang, Haifeng

2016-11-01

The mixture fraction and progress variable are often used as independent variables for describing turbulent premixed and non-premixed flames. There is a growing interest in using these two variables for describing partially premixed flames. The joint statistical distribution of the mixture fraction and progress variable is of great interest in developing models for partially premixed flames. In this work, we conduct predictive studies of the joint statistics of mixture fraction and progress variable in a series of piloted methane jet flames with inhomogeneous inlet flows. The employed models combine large eddy simulations with the Monte Carlo probability density function (PDF) method. The joint PDFs and marginal PDFs are examined in detail by comparing the model predictions and the measurements. Different presumed shapes of the joint PDFs are also evaluated.

Method for catalytic destruction of organic materials

DOEpatents

Sealock, Jr., L. John; Baker, Eddie G.; Elliott, Douglas C.

1997-01-01

A method is disclosed for converting waste organic materials into an innocuous product gas. The method comprises maintaining, in a pressure vessel, in the absence of oxygen, at a temperature of 250.degree. C. to 500.degree. C. and a pressure of at least 50 atmospheres, a fluid organic waste material, water, and a catalyst consisting essentially of reduced nickel in an amount sufficient to catalyze a reaction of the organic waste material to produce an innocuous product gas composed primarily of methane and carbon dioxide. The methane in the product gas may be burned to preheat the organic materials.

Method for catalytic destruction of organic materials

DOEpatents

Sealock, L.J. Jr.; Baker, E.G.; Elliott, D.C.

1997-05-20

A method is disclosed for converting waste organic materials into an innocuous product gas. The method comprises maintaining, in a pressure vessel, in the absence of oxygen, at a temperature of 250 to 500 C and a pressure of at least 50 atmospheres, a fluid organic waste material, water, and a catalyst consisting essentially of reduced nickel in an amount sufficient to catalyze a reaction of the organic waste material to produce an innocuous product gas composed primarily of methane and carbon dioxide. The methane in the product gas may be burned to preheat the organic materials. 7 figs.

Evidence of Methane Outgassing During MIS3 in the Bering Sea

NASA Astrophysics Data System (ADS)

Cook, M. S.; Keigwin, L. D.

2005-12-01

There are multiple negative excursions in planktonic and benthic foraminifer δ13C in a core from 1467m in the southeast Bering Sea. These excursions occur episodically during the last glacial period, and may coincide with Dansgaard-Oeschger (D-O) events. Measured foraminifer δ13C during the excursions is as low as -14‰ and are probably the result of overgrowths of diagenetic calcium carbonate. We estimate overgrowth δ13C is -23‰, and hypothesize that the occurrence of overgrowths is associated with anaerobic oxidation of biogenic methane. The likely pressure and temperature conditions at this site and during the last glacial period were well within the zone of methane-hydrate stability, so the source of methane is probably not from destabilization of methane hydrate at this depth. The methane may have originated from increased in-situ methanogenesis resulting from greater burial of organic carbon, or from destabilization of methane hydrate at shallower sites near the methane-hydrate stability threshold. Both these scenarios could be active, consistent with the ``Clathrate Gun Hypothesis'' (Kennett et al., 2003), in which there is widespread destabilization of marine methane hydrates during D-O events, where methane gas both is oxidized within the water column and escapes to the atmosphere.

Method of making improved gas storage carbon with enhanced thermal conductivity

DOEpatents

Burchell, Timothy D [Oak Ridge, TN; Rogers, Michael R [Knoxville, TN

2002-11-05

A method of making an adsorbent carbon fiber based monolith having improved methane gas storage capabilities is disclosed. Additionally, the monolithic nature of the storage carbon allows it to exhibit greater thermal conductivity than conventional granular activated carbon or powdered activated carbon storage beds. The storage of methane gas is achieved through the process of physical adsorption in the micropores that are developed in the structure of the adsorbent monolith. The disclosed monolith is capable of storing greater than 150 V/V of methane [i.e., >150 STP (101.325 KPa, 298K) volumes of methane per unit volume of storage vessel internal volume] at a pressure of 3.5 MPa (500 psi).

Kinetics of oxygen atom formation during the oxidation of methane behind shock waves

NASA Technical Reports Server (NTRS)

Jachimowski, C. J.

1974-01-01

An experimental and analytical study of the formation of oxygen atoms during the oxidation of methane and methane-hydrogen mixtures behind incident shock waves was carried out over the temperature range 1790-2584 K at reaction pressures between 1.2 and 1.7 atm. Oxygen atom levels were determined indirectly by measurement of emission from reaction of O with CO. On the basis of these data and ignition-delay data reported in the literature, a kinetic scheme for methane oxidation was assembled. The proposed kinetic mechanism, in general, predicts higher peak oxygen atom levels than the current oxidation mechanisms proposed by Bowman and Seery and by Skinner and his co-workers.

Constructive Activation of Reservoir-Resident Microbes for Enhanced Oil Recovery

NASA Astrophysics Data System (ADS)

DeBruyn, R. P.

2017-12-01

Microbial communities living in subsurface oil reservoirs biodegrade oil, producing methane. If this process could create methane within the waterflooded pore spaces of an oilfield, the methane would be expected to remain and occupy pore space, decreasing water relative permeability, diverting water flow, and increasing oil recovery by expanding the swept zone of the waterflood. This approach was tested in an oilfield in northern Montana. Preliminary assessments were made of geochemical conditions and microbiological habitations. Then, a formulation of microbial activators, with composition tailored for the reservoir's conditions, was metered at low rates into the existing injection water system for one year. In the field, the responses observed included improved oil production performance; a slight increase in injection pressure; and increased time needed for tracers to move between injection and producing wells. We interpret these results to confirm that successful stimulation of the microbial community caused more methane to be created within the swept zone of the waterflooded reservoir. When the methane exsolved as water flowed between high-pressure injection and low-pressure production wells, the bubbles occupied pore space, reducing water saturation and relative permeability, and re-directing some water flow to "slower" unswept rock with lower permeability and higher oil saturation. In total, the waterflood's swept zone had been expanded to include previously-unflooded rock. This technology was applied in this field after screening based on careful anaerobic sampling, advanced microbiological analysis, and the ongoing success of its waterflood. No reservoir or geological or geophysical simulation models were employed, and physical modifications to field facilities were minor. This technology of utilizing existing microbial populations for enhanced oil recovery can therefore be considered for deployment into waterfloods where small scale, advanced maturity, or insufficiency of data make other technologies too expensive.

A Heat Transfer Investigation of Liquid and Two-Phase Methane

NASA Technical Reports Server (NTRS)

VanNoord, Jonathan

2010-01-01

A heat transfer investigation was conducted for liquid and two-phase methane. The tests were conducted at the NASA Glenn Research Center Heated Tube Facility (HTF) using resistively heated tube sections to simulate conditions encountered in regeneratively cooled rocket engines. This testing is part of NASA s Propulsion and Cryogenics Advanced Development (PCAD) project. Nontoxic propellants, such as liquid oxygen/liquid methane (LO2/LCH4), offer potential benefits in both performance and safety over equivalently sized hypergolic propulsion systems in spacecraft applications. Regeneratively cooled thrust chambers are one solution for high performance, robust LO2/LCH4 engines, but cooling data on methane is limited. Several test runs were conducted using three different diameter Inconel 600 tubes, with nominal inner diameters of 0.0225-, 0.054-, and 0.075-in. The mass flow rate was varied from 0.005 to 0.07 lbm/sec. As the current focus of the PCAD project is on pressure fed engines for LO2/LCH4, the average test section outlet pressures were targeted to be 200 psia or 500 psia. The heat flux was incrementally increased for each test condition while the test section wall temperatures were monitored. A maximum average heat flux of 6.2 Btu/in.2 sec was achieved and, at times, the temperatures of the test sections reached in excess of 1800 R. The primary objective of the tests was to produce heat transfer correlations for methane in the liquid and two-phase regime. For two-phase flow testing, the critical heat flux values were determined where the fluid transitions from nucleate boiling to film boiling. A secondary goal of the testing was to measure system pressure drops in the two-phase regime.

Cryogenic Technology Development for Exploration Missions

NASA Technical Reports Server (NTRS)

Chato, David J.

2007-01-01

This paper reports the status and findings of different cryogenic technology research projects in support of the President s Vision for Space Exploration. The exploration systems architecture study is reviewed for cryogenic fluid management needs. It is shown that the exploration architecture is reliant on the cryogenic propellants of liquid hydrogen, liquid oxygen and liquid methane. Needs identified include: the key technologies of liquid acquisition devices, passive thermal and pressure control, low gravity mass gauging, prototype pressure vessel demonstration, active thermal control; as well as feed system testing, and Cryogenic Fluid Management integrated system demonstration. Then five NASA technology projects are reviewed to show how these needs are being addressed by technology research. Projects reviewed include: In-Space Cryogenic Propellant Depot; Experimentation for the Maturation of Deep Space Cryogenic Refueling Technology; Cryogenic Propellant Operations Demonstrator; Zero Boil-Off Technology Experiment; and Propulsion and Cryogenic Advanced Development. Advances are found in the areas of liquid acquisition of liquid oxygen, mass gauging of liquid oxygen via radio frequency techniques, computational modeling of thermal and pressure control, broad area cooling thermal control strategies, flight experiments for resolving low gravity issues of cryogenic fluid management. Promising results are also seen for Joule-Thomson pressure control devices in liquid oxygen and liquid methane and liquid acquisition of methane, although these findings are still preliminary.

Computation of the properties of liquid neon, methane, and gas helium at low temperature by the Feynman-Hibbs approach.

PubMed

Tchouar, N; Ould-Kaddour, F; Levesque, D

2004-10-15

The properties of liquid methane, liquid neon, and gas helium are calculated at low temperatures over a large range of pressure from the classical molecular-dynamics simulations. The molecular interactions are represented by the Lennard-Jones pair potentials supplemented by quantum corrections following the Feynman-Hibbs approach. The equations of state, diffusion, and shear viscosity coefficients are determined for neon at 45 K, helium at 80 K, and methane at 110 K. A comparison is made with the existing experimental data and for thermodynamical quantities, with results computed from quantum numerical simulations when they are available. The theoretical variation of the viscosity coefficient with pressure is in good agreement with the experimental data when the quantum corrections are taken into account, thus reducing considerably the 60% discrepancy between the simulations and experiments in the absence of these corrections.

Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

USGS Publications Warehouse

Circone, S.; Kirby, S.H.; Stern, L.A.

2006-01-01

Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H 2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within ??2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol-1 K-1 for 1/n CH4??H 2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled. ?? 2006 American Chemical Society.

40 CFR 63.457 - Test methods and procedures.

Code of Federal Regulations, 2013 CFR

2013-07-01

... volume of hydrocarbon in air); and (ii) A mixture of methane or n-hexane and air at a concentration of approximately, but less than, 10,000 parts per million by volume methane or n-hexane. (e) Negative pressure... between 6.95 and 7.05. (4) To prepare the 0.1 normality (N) sodium thiosulfate solution, dissolve 25 g of...

Spatial distribution of CH3 and CH2 radicals in a methane rf discharge

NASA Astrophysics Data System (ADS)

Sugai, H.; Kojima, H.; Ishida, A.; Toyoda, H.

1990-06-01

Spatial distributions of neutral radicals CH3 and CH2 in a capacitively coupled rf glow discharge of methane were measured by threshold ionization mass spectrometry. A strong asymmetry of the density profile was found for the CH2 radical in the high-pressure (˜100 mTorr) discharge. In addition, comprehensive measurements of electron energy distribution, ionic composition, and radical sticking coefficient were made to use as inputs to theoretical modeling of radicals in the methane plasma. The model predictions agree substantially with the measured radical distributions.

Methane and hydrogen ignition with ethanol and butanol admixtures

NASA Astrophysics Data System (ADS)

Eremin, A. V.; Matveeva, N. A.; Mikheyeva, E. Yu

2018-01-01

This work is devoted to the investigation of combustion of simple and complex gaseous fuels: methane and hydrogen with admixtures of the most promising alcohols: ethanol and butanol. The process of ignition of investigated blends behind reflected shock waves in the temperature range of 1000-1600 K and pressure range of 4.5-6 bar was studied. The temperature dependences of ignition delay times for stoichiometric methane-oxygen-ethanol (or butanol) and hydrogen-oxygen-ethanol (or butanol) mixtures diluted in argon were obtained. The possible kinetic description is discussed.

Analysis of Subsurface Clathrates in the Upper Crust of Titan

NASA Technical Reports Server (NTRS)

Elliott, John

2011-01-01

Titan has an atmosphere rich in methane, which should have long since been depleted unless a mechanism exists for storing this molecule below the surface. One hypothesis is that methane could be stored in the form of a clathrate hydrate, which is a structure with an ice lattice forming molecular cages in which gases are trapped. It is stable at low temperatures and over a wide range of pressures, suggesting that a clathrate hydrate may have stored methane on Titan from the beginning of its history.

Combustion of Methane Hydrate

NASA Astrophysics Data System (ADS)

Roshandell, Melika

A significant methane storehouse is in the form of methane hydrates on the sea floor and in the arctic permafrost. Methane hydrates are ice-like structures composed of water cages housing a guest methane molecule. This caged methane represents a resource of energy and a potential source of strong greenhouse gas. Most research related to methane hydrates has been focused on their formation and dissociation because they can form solid plugs that complicate transport of oil and gas in pipelines. This dissertation explores the direct burning of these methane hydrates where heat from the combustion process dissociates the hydrate into water and methane, and the released methane fuels the methane/air diffusion flame heat source. In contrast to the pipeline applications, very little research has been done on the combustion and burning characteristics of methane hydrates. This is the first dissertation on this subject. In this study, energy release and combustion characteristics of methane hydrates were investigated both theoretically and experimentally. The experimental study involved collaboration with another research group, particularly in the creation of methane hydrate samples. The experiments were difficult because hydrates form at high pressure within a narrow temperature range. The process can be slow and the resulting hydrate can have somewhat variable properties (e.g., extent of clathration, shape, compactness). The experimental study examined broad characteristics of hydrate combustion, including flame appearance, burning time, conditions leading to flame extinguishment, the amount of hydrate water melted versus evaporated, and flame temperature. These properties were observed for samples of different physical size. Hydrate formation is a very slow process with pure water and methane. The addition of small amounts of surfactant increased substantially the hydrate formation rate. The effects of surfactant on burning characteristics were also studied. One finding from the experimental component of the research was that hydrates can burn completely, and that they burn most rapidly just after ignition and then burn steadily when some of the water in the dissociated zone is allowed to drain away. Excessive surfactant in the water creates a foam layer around the hydrate that acts as an insulator. The layer prevents sufficient heat flux from reaching the hydrate surface below the foam to release additional methane and the hydrate flame extinguishes. No self-healing or ice-freezing processes were observed in any of the combustion experiments. There is some variability, but a typical hydrate flame is receiving between one and two moles of water vapor from the liquid dissociated zone of the hydrate for each mole of methane it receives from the dissociating solid region. This limits the flame temperature to approximately 1800 K. In the theoretical portion of the study, a physical model using an energy balance from methane combustion was developed to understand the energy transfer between the three phases of gas, liquid and solid during the hydrate burn. Also this study provides an understanding of the different factors impacting the hydrate's continuous burn, such as the amount of water vapor in the flame. The theoretical study revealed how the water layer thickness on the hydrate surface, and its effect on the temperature gradient through the dissociated zone, plays a significant role in the hydrate dissociation rate and methane release rate. Motivated by the above mentioned observation from the theoretical analysis, a 1-D two-phase numerical simulation based on a moving front model for hydrate dissociation from a thermal source was developed. This model was focused on the dynamic growth of the dissociated zone and its effect on the dissociation rate. The model indicated that the rate of hydrate dissociation with a thermal source is a function of the dissociated zone thickness. It shows that in order for a continuous dissociation and methane release, some of the water from the dissociated zone needs to be drained. The results are consistent with the experimental observations. The understanding derived from the experiments and the numerical model permitted a brief exploration into the potential effects of pressure on the combustion of methane hydrates. The prediction is that combustion should improve under high pressure conditions because the evaporation of water is suppressed allowing more energy into the dissociation. Future experiments are needed to validate these initial findings.

Activation of methane by transition metal-substituted aluminophosphate molecular sieves

DOEpatents

Iton, Lennox E.; Maroni, Victor A.

1991-01-01

Aluminophosphate molecular sieves substituted with cobalt, manganese or iron and having the AlPO.sub.4 -34 or AlPO.sub.4 -5, or related AlPO.sub.4 structure activate methane starting at approximately 350.degree. C. Between 400.degree. and 500.degree. C. and at methane pressures .ltoreq.1 atmosphere the rate of methane conversion increases steadily with typical conversion efficiencies at 500.degree. C. approaching 50% and selectivity to the production of C.sub.2+ hydrocarbons approaching 100%. The activation mechanism is based on reduction of the transition metal(III) form of the molecular sieve to the transition metal(II) form with accompanying oxidative dehydrogenation of the methane. Reoxidation of the - transition metal(II) form to the transition metal(III) form can be done either chemically (e.g., using O.sub.2) or electrochemically.

Plasma catalytic reforming of methane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bromberg, L.; Cohn, D.R.; Rabinovich, A.

1998-08-01

Thermal plasma technology can be efficiently used in the production of hydrogen and hydrogen-rich gases from methane and a variety of fuels. This paper describes progress in plasma reforming experiments and calculations of high temperature conversion of methane using heterogeneous processes. The thermal plasma is a highly energetic state of matter that is characterized by extremely high temperatures (several thousand degrees Celsius) and high degree of dissociation and substantial degree of ionization. The high temperatures accelerate the reactions involved in the reforming process. Hydrogen-rich gas (50% H{sub 2}, 17% CO and 33% N{sub 2}, for partial oxidation/water shifting) can bemore » efficiently made in compact plasma reformers. Experiments have been carried out in a small device (2--3 kW) and without the use of efficient heat regeneration. For partial oxidation/water shifting, it was determined that the specific energy consumption in the plasma reforming processes is 16 MJ/kg H{sub 2} with high conversion efficiencies. Larger plasmatrons, better reactor thermal insulation, efficient heat regeneration and improved plasma catalysis could also play a major role in specific energy consumption reduction and increasing the methane conversion. A system has been demonstrated for hydrogen production with low CO content ({approximately} 1.5%) with power densities of {approximately} 30 kW (H{sub 2} HHV)/liter of reactor, or {approximately} 10 m{sup 3}/hr H{sub 2} per liter of reactor. Power density should further increase with increased power and improved design.« less

Partial oxidative conversion of methane to methanol through selective inhibition of methanol dehydrogenase in methanotrophic consortium from landfill cover soil.

PubMed

Han, Ji-Sun; Ahn, Chang-Min; Mahanty, Biswanath; Kim, Chang-Gyun

2013-11-01

Using a methanotrophic consortium (that includes Methylosinus sporium NCIMB 11126, Methylosinus trichosporium OB3b, and Methylococcus capsulatus Bath) isolated from a landfill site, the potential for partial oxidation of methane into methanol through selective inhibition of methanol dehydrogenase (MDH) over soluble methane monooxygenase (sMMO) with some selected MDH inhibitors at varied concentration range, was evaluated in batch serum bottle and bioreactor experiments. Our result suggests that MDH activity could effectively be inhibited either at 40 mM of phosphate, 100 mM of NaCl, 40 mM of NH4Cl or 50 μM of EDTA with conversion ratios (moles of CH3OH produced per mole CH4 consumed) of 58, 80, 80, and 43 %, respectively. The difference between extent of inhibition in MDH activity and sMMO activity was significantly correlated (n = 6, p < 0.05) with resultant methane to methanol conversion ratio. In bioreactor study with 100 mM of NaCl, a maximum specific methanol production rate of 9 μmol/mg h was detected. A further insight with qPCR analysis of MDH and sMMO coding genes revealed that the gene copy number continued to increase along with biomass during reactor operation irrespective of presence or absence of inhibitor, and differential inhibition among two enzymes was rather the key for methanol production.

Contribution of tropical wetland and biomass burning emissions to the methane growth rate: new insights from lower tropospheric partial column retrievals

NASA Astrophysics Data System (ADS)

Yin, Y.; Worden, J. R.; Bloom, A. A.; Frankenberg, C.

2017-12-01

Atmospheric CH4 concentration stabilized in the early 2000s and began to increase again since 2007. Recent literature has explored various explanations for possible causes of the growth rate change in CH4 with considerable contradictions among each other, suggesting this problem being ill-conditioned with currently available observations. Satellite observations of CH4 in the near infrared (NIR) with full column sensitivity began with SCIAMACHY (2003-2012) and extend to the present with GOSAT (2009-). Observations in the thermal infrared (TIR) such as from TES (2004-2011) and CrIS (2012-) provide data in the free troposphere. Combining the information pieces from TIR and NIR, we could resolve the lower tropospheric partial column of CH4 that is more sensitive to the surface methane fluxes. Here, using a newly developed lower tropospheric partial column retrieval and supplemented by MOPITT CO retrievals, we discuss the interannual variations of tropical CH4 emissions from wetland and biomass burning respectively, and further, we explore the relationship between those fluxes and climate variability.

Hydrogenation catalysts were derived from Mo(Co)/sub 6//alumina

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bowman, R.G.

1979-01-01

Alumina hydrogenation catalysts were derived from mo(CO)/sub 6//alumina with characteristics dependent upon the activation temperature, degree of alumina hydroxylation, and carrier gas used. Decomposition of Mo(CO)/sub 6/ at 100/sup 0/C on partially hydroxylated alumina in helium or hydrogen yielded Mo(CO)/sub 3//alumina, which catalyzed olefin metathesis in helium carrier and both metathesis and hydrogenation in hydrogen carrier. Decomposition of Mo(CO)/sub 6/ on dehydroxylated alumina at 100/sup 0/C in helium and in hydrogen resulted in complete decarbonylation and partial oxidation of molybdenum; this catalyst was 10 times as active as Mo(CO)/sub 3//alumina for hydrogenation. Decomposition of Mo(CO)/sub 6/ on dehydroxylated alumina atmore » 500/sup 0/C in helium gave essentially Mo(0)/alumina, which catalyzed hydrogenation, methanation, and hydrogenolysis in hydrogen. Catalysts activated on dehydroxylated alumina were ten times more active for methanation at 300/sup 0/C than catalyst activated on partially hydroxylated alumina and showed differences in selectivity for cyclopropane hydrogenolysis at 100/sup 0/C.« less

Time-Resolved and Operando XAS Studies on Heterogeneous Catalysts - From the Gas Phase Towards Reactions in Supercritical Fluids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grunwaldt, Jan-Dierk; Baiker, Alfons

2007-02-02

x-ray absorption spectroscopy is a well-suited technique to uncover the structure of heterogeneous catalysts under reaction conditions. Different aspects of in situ cell design suitable for dynamic and catalytic studies are discussed. In addition, criteria are presented that allow estimating the influence external and internal mass transfer. Starting with studies on gas-solid reactions, including structure-activity relationships, this concept is extended to liquid-solid reactions, reactions at high pressure and in supercritical fluids. The following examples are discussed in more detail: partial oxidation of methane over Pt-Rh/Al2O3, reduction of a Cu/ZnO catalyst, alcohol oxidation over Bi-promoted Pd/Al2O3 in liquid phase and overmore » Pd/Al2O3 in supercritical CO2, and batch reactions (e.g. CO2-fixation over zinc-based catalysts)« less

Methane production by attached film

DOEpatents

Jewell, William J.

1981-01-01

A method for purifying wastewater of biodegradable organics by converting the organics to methane and carbon dioxide gases is disclosed, characterized by the use of an anaerobic attached film expanded bed reactor for the reaction process. Dilute organic waste material is initially seeded with a heterogeneous anaerobic bacteria population including a methane-producing bacteria. The seeded organic waste material is introduced into the bottom of the expanded bed reactor which includes a particulate support media coated with a polysaccharide film. A low-velocity upward flow of the organic waste material is established through the bed during which the attached bacterial film reacts with the organic material to produce methane and carbon dioxide gases, purified water, and a small amount of residual effluent material. The residual effluent material is filtered by the film as it flows upwardly through the reactor bed. In a preferred embodiment, partially treated effluent material is recycled from the top of the bed to the bottom of the bed for further treatment. The methane and carbon dioxide gases are then separated from the residual effluent material and purified water.

Processes and Parameters Controlling the Extent of Methanogenic Conditions in the Unsaturated Zone of a Crude Oil Spill Site

NASA Astrophysics Data System (ADS)

Molins, S.; Mayer, K.

2007-12-01

Gas concentrations measured in the vadose zone at a crude oil spill site near Bemidji, MN, show that a large area near the oil body is currently dominated by methanogenic conditions. Away from the oil body methane concentrations decrease as it is degraded by methanotrophic bacteria under aerobic conditions. Numerical simulations have been conducted to quantify the contributions of the relevant transport and reaction processes to the production and attenuation of methane in the vadose zone. Methane is generated in the vadose zone by anaerobic degradation of oil and is also added by fluxes from the capillary fringe and the saturated zone. Gas diffusion and advection contribute to the transport of methane in the lateral direction and towards the ground surface. Attenuation of methane concentrations occurs through aerobic oxidation in the presence of methanotrophic bacteria. Critical parameters were varied within bounds provided by field data and previous studies. Simulation results confirm that the layered sediment structure present at the site plays a significant role in explaining the observed distribution of gases in the vadose zone. The presence of a low permeability lens in the area upgradient from the source results in higher moisture contents, limiting diffusion of oxygen into the zone of methane production, and contributes to the spread of methane. Diffusion was identified as the most significant transport mechanism for gases in the vadose zone. However, field-observed zones of depleted and enriched N2 and Ar concentrations could only be explained by the development of advective fluxes induced by reactive processes (methanogenesis and methanotrophy). The zones of gas production are characterized by slightly increased total gas pressures and low concentrations of N2 and Ar, while zones of gas consumption show slightly depressed total gas pressures and high concentrations of N2 and Ar. The simulations suggest that the advective flux that develops between these zones contributes up to 15% of the total methane flux.

Colors of Alien Worlds from Direct Imaging Exoplanet Missions

NASA Astrophysics Data System (ADS)

Hu, Renyu

2015-08-01

Future direct-imaging exoplanet missions such as WFIRST/AFTA, Exo-C, and Exo-S will measure the reflectivity of exoplanets at visible wavelengths. Most of the exoplanets to be observed will be located further away from their parent stars than is Earth from the Sun. These “cold” exoplanets have atmospheric environments conducive for the formation of water and/or ammonia clouds, like Jupiter in the Solar System. I find the mixing ratio of methane and the pressure level of the uppermost cloud deck on these planets can be uniquely determined from their reflection spectra, with moderate spectral resolution, if the cloud deck is between 0.6 and 1.5 bars. The existence of this unique solution is useful for exoplanet direct imaging missions for several reasons. First, the weak bands and strong bands of methane enable the measurement of the methane mixing ratio and the cloud pressure, although an overlying haze layer can bias the estimate of the latter. Second, the cloud pressure, once derived, yields an important constraint on the internal heat flux from the planet, and thus indicating its thermal evolution. Third, water worlds having H2O-dominated atmospheres are likely to have water clouds located higher than the 10-3 bar pressure level, and muted spectral absorption features. These planets would occupy a confined phase space in the color-color diagrams, likely distinguishable from H2-rich giant exoplanets by broadband observations. Therefore, direct-imaging exoplanet missions may offer the capability to broadly distinguish H2-rich giant exoplanets versus H2O-rich super-Earth exoplanets, and to detect ammonia and/or water clouds and methane gas in their atmospheres.

Numerical Modeling of Methane Leakage from a Faulty Natural Gas Well into Fractured Tight Formations.

PubMed

Moortgat, Joachim; Schwartz, Franklin W; Darrah, Thomas H

2018-03-01

Horizontal drilling and hydraulic fracturing have enabled hydrocarbon recovery from unconventional reservoirs, but led to natural gas contamination of shallow groundwaters. We describe and apply numerical models of gas-phase migration associated with leaking natural gas wells. Three leakage scenarios are simulated: (1) high-pressure natural gas pulse released into a fractured aquifer; (2) continuous slow leakage into a tilted fractured formation; and (3) continuous slow leakage into an unfractured aquifer with fluvial channels, to facilitate a generalized evaluation of natural gas transport from faulty natural gas wells. High-pressure pulses of gas leakage into sparsely fractured media are needed to produce the extensive and rapid lateral spreading of free gas previously observed in field studies. Transport in fractures explains how methane can travel vastly different distances and directions laterally away from a leaking well, which leads to variable levels of methane contamination in nearby groundwater wells. Lower rates of methane leakage (≤1 Mcf/day) produce shorter length scales of gas transport than determined by the high-pressure scenario or field studies, unless aquifers have low vertical permeabilities (≤1 millidarcy) and fractures and bedding planes have sufficient tilt (∼10°) to allow a lateral buoyancy component. Similarly, in fractured rock aquifers or where permeability is controlled by channelized fluvial deposits, lateral flow is not sufficiently developed to explain fast-developing gas contamination (0-3 months) or large length scales (∼1 km) documented in field studies. Thus, current efforts to evaluate the frequency, mechanism, and impacts of natural gas leakage from faulty natural gas wells likely underestimate contributions from small-volume, low-pressure leakage events. © 2018, National Ground Water Association.

Performance of a passively vented field-scale biofilter for the microbial oxidation of landfill methane.

PubMed

Gebert, J; Gröngröft, A

2006-01-01

An upflow biofilter system was operated on a passively vented landfill for the treatment of residual landfill methane. Biofilter methane emissions as a basis for determining methane removal rates were assessed by manual and automated chamber measurements, by measuring methane concentrations in the top layer gaseous phase in combination with gas flow rates, and by evaluating the methane load in the reverse gas flow following the change of landfill gas flux direction as governed by the course of barometric pressure. Methane removal rates were very high with maximum values of 80 g h(-1) m(-3). For the observed cases, the limit of biofilter methane oxidation capacity was not reached and absolute removal rates were thus linearly correlated to the amount of methane entering the filter. The analysis of methane loads flowing back from the biofilter following phases of longer, continuous and non-oscillating landfill gas emission, however, revealed that in these situations biofilter performance is restricted by deficient oxygen supply. At the oxygen-restricted capacity limit, removal rates are influenced by temperature (positively), methane influx (negatively) and flow rate (negatively) as a measure for the displacement of oxygen. These situations, however, account for only 12% of all emission phases. The investigated biofilter capacity, as derived from laboratory analyses of methanotrophic activities, is sufficient to oxidise 62% of the methane load emitted annually. Field and laboratory data provide a stable basis for the dimensioning of filters in future applications.

Planning and Execution of a Marine Methane Hydrate Pressure Coring Program for the Walker Ridge and Green Canyon Areas of the Gulf of Mexico

DOE Office of Scientific and Technical Information (OSTI.GOV)

Humphrey, Gary

The objective of this project (and report) is to produce a guide to developing scientific, operational, and logistical plans for a future methane hydrate-focused offshore pressure coring program. This report focuses primarily on a potential coring program in the Walker Ridge 313 and Green Canyon 955 blocks where previous investigations were undertaken as part of the 2009 Department of Energy JIP Leg II expedition, however, the approach to designing a pressure coring program that was utilized for this project may also serve as a useful model for planning pressure coring programs for hydrates in other areas. The initial portion ofmore » the report provides a brief overview of prior investigations related to gas hydrates in general and at the Walker Ridge 313 and Green Canyon 955 blocks in particular. The main content of the report provides guidance for various criteria that will come into play when designing a pressure coring program.« less

Influence of different substrates on the performance of a two-stage high pressure anaerobic digestion system.

PubMed

Lemmer, A; Chen, Y; Lindner, J; Wonneberger, A M; Zielonka, S; Oechsner, H; Jungbluth, T

2015-02-01

The two-stage autogenerative high-pressure digestion technique is a novel and promising approach for the production of gaseous fuels or upgraded biogas. This new technique is described in the patent DE 10 2011 015415 A1 and integrates biogas production, its upgrading and pressure boosting in one process. Anaerobic digestion under elevated pressure conditions leads to decreasing pH-values in the digestate due to the augmented formation of carboxylic acid. Model calculations carried out to evaluate the two-stage design showed that the pH-value in the pressurized anaerobic filter has a major influence on the methane content of the biogas produced. Within this study, the influence of the nitrogen content as one of the most important buffering substances on the performance of the system has been tested. The results show that higher NH4 contents lead to higher pH-values in the digester and as a consequence to higher methane contents. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermodynamic properties of methane hydrate in quartz powder.

PubMed

Voronov, Vitaly P; Gorodetskii, Evgeny E; Safonov, Sergey S

2007-10-04

Using the experimental method of precision adiabatic calorimetry, the thermodynamic (equilibrium) properties of methane hydrate in quartz sand with a grain size of 90-100 microm have been studied in the temperature range of 260-290 K and at pressures up to 10 MPa. The equilibrium curves for the water-methane hydrate-gas and ice-methane hydrate-gas transitions, hydration number, latent heat of hydrate decomposition along the equilibrium three-phase curves, and the specific heat capacity of the hydrate have been obtained. It has been experimentally shown that the equilibrium three-phase curves of the methane hydrate in porous media are shifted to the lower temperature and high pressure with respect to the equilibrium curves of the bulk hydrate. In these experiments, we have found that the specific heat capacity of the hydrate, within the accuracy of our measurements, coincides with the heat capacity of ice. The latent heat of the hydrate dissociation for the ice-hydrate-gas transition is equal to 143 +/- 10 J/g, whereas, for the transition from hydrate to water and gas, the latent heat is 415 +/- 15 J/g. The hydration number has been evaluated in the different hydrate conditions and has been found to be equal to n = 6.16 +/- 0.06. In addition, the influence of the water saturation of the porous media and its distribution over the porous space on the measured parameters has been experimentally studied.

Methane release from the southern Brazilian margin during the last glacial.

PubMed

Portilho-Ramos, R C; Cruz, A P S; Barbosa, C F; Rathburn, A E; Mulitza, S; Venancio, I M; Schwenk, T; Rühlemann, C; Vidal, L; Chiessi, C M; Silveira, C S

2018-04-13

Seafloor methane release can significantly affect the global carbon cycle and climate. Appreciable quantities of methane are stored in continental margin sediments as shallow gas and hydrate deposits, and changes in pressure, temperature and/or bottom-currents can liberate significant amounts of this greenhouse gas. Understanding the spatial and temporal dynamics of marine methane deposits and their relationships to environmental change are critical for assessing past and future carbon cycle and climate change. Here we present foraminiferal stable carbon isotope and sediment mineralogy records suggesting for the first time that seafloor methane release occurred along the southern Brazilian margin during the last glacial period (40-20 cal ka BP). Our results show that shallow gas deposits on the southern Brazilian margin responded to glacial-interglacial paleoceanographic changes releasing methane due to the synergy of sea level lowstand, warmer bottom waters and vigorous bottom currents during the last glacial period. High sea level during the Holocene resulted in an upslope shift of the Brazil Current, cooling the bottom waters and reducing bottom current strength, reducing methane emissions from the southern Brazilian margin.

Methane oxidation behind reflected shock waves: Ignition delay times measured by pressure and flame band emission

NASA Technical Reports Server (NTRS)

Brabbs, T. A.; Robertson, T. F.

1986-01-01

Ignition delay data were recorded for three methane-oxygen-argon mixtures (phi = 0.5, 1.0, 2.0) for the temperature range 1500 to 1920 K. Quiet pressure trances enabled us to obtain delay times for the start of the experimental pressure rise. These times were in good agreement with those obtained from the flame band emission at 3700 A. The data correlated well with the oxygen and methane dependence of Lifshitz, but showed a much stronger temperature dependence (phi = 0.5 delta E = 51.9, phi = 1.0 delta = 58.8, phi = 2.0 delta E = 58.7 Kcal). The effect of probe location on the delay time measurement was studied. It appears that the probe located 83 mm from the reflecting surface measured delay times which may not be related to the initial temperature and pressure. It was estimated that for a probe located 7 mm from the reflecting surface, the measured delay time would be about 10 microseconds too short, and it was suggested that delay times less than 100 microsecond should not be used. The ignition period was defined as the time interval between start of the experimental pressure rise and 50 percent of the ignition pressure. This time interval was measured for three gas mixtures and found to be similar (40 to 60 micro sec) for phi = 1.0 and 0.5 but much longer (100 to 120) microsecond for phi = 2.0. It was suggested that the ignition period would be very useful to the kinetic modeler in judging the agreement between experimental and calculated delay times.

Timescales of methane seepage on the Norwegian margin following collapse of the Scandinavian Ice Sheet

PubMed Central

Crémière, Antoine; Lepland, Aivo; Chand, Shyam; Sahy, Diana; Condon, Daniel J.; Noble, Stephen R.; Martma, Tõnu; Thorsnes, Terje; Sauer, Simone; Brunstad, Harald

2016-01-01

Gas hydrates stored on continental shelves are susceptible to dissociation triggered by environmental changes. Knowledge of the timescales of gas hydrate dissociation and subsequent methane release are critical in understanding the impact of marine gas hydrates on the ocean–atmosphere system. Here we report a methane efflux chronology from five sites, at depths of 220–400 m, in the southwest Barents and Norwegian seas where grounded ice sheets led to thickening of the gas hydrate stability zone during the last glaciation. The onset of methane release was coincident with deglaciation-induced pressure release and thinning of the hydrate stability zone. Methane efflux continued for 7–10 kyr, tracking hydrate stability changes controlled by relative sea-level rise, bottom water warming and fluid pathway evolution in response to changing stress fields. The protracted nature of seafloor methane emissions probably attenuated the impact of hydrate dissociation on the climate system. PMID:27167635

A synthesis of methane emissions from 71 northern, temperate, and subtropical wetlands.

PubMed

Turetsky, Merritt R; Kotowska, Agnieszka; Bubier, Jill; Dise, Nancy B; Crill, Patrick; Hornibrook, Ed R C; Minkkinen, Kari; Moore, Tim R; Myers-Smith, Isla H; Nykänen, Hannu; Olefeldt, David; Rinne, Janne; Saarnio, Sanna; Shurpali, Narasinha; Tuittila, Eeva-Stiina; Waddington, J Michael; White, Jeffrey R; Wickland, Kimberly P; Wilmking, Martin

2014-07-01

Wetlands are the largest natural source of atmospheric methane. Here, we assess controls on methane flux using a database of approximately 19 000 instantaneous measurements from 71 wetland sites located across subtropical, temperate, and northern high latitude regions. Our analyses confirm general controls on wetland methane emissions from soil temperature, water table, and vegetation, but also show that these relationships are modified depending on wetland type (bog, fen, or swamp), region (subarctic to temperate), and disturbance. Fen methane flux was more sensitive to vegetation and less sensitive to temperature than bog or swamp fluxes. The optimal water table for methane flux was consistently below the peat surface in bogs, close to the peat surface in poor fens, and above the peat surface in rich fens. However, the largest flux in bogs occurred when dry 30-day averaged antecedent conditions were followed by wet conditions, while in fens and swamps, the largest flux occurred when both 30-day averaged antecedent and current conditions were wet. Drained wetlands exhibited distinct characteristics, e.g. the absence of large flux following wet and warm conditions, suggesting that the same functional relationships between methane flux and environmental conditions cannot be used across pristine and disturbed wetlands. Together, our results suggest that water table and temperature are dominant controls on methane flux in pristine bogs and swamps, while other processes, such as vascular transport in pristine fens, have the potential to partially override the effect of these controls in other wetland types. Because wetland types vary in methane emissions and have distinct controls, these ecosystems need to be considered separately to yield reliable estimates of global wetland methane release. © 2014 John Wiley & Sons Ltd.

A synthesis of methane emissions from 71 northern, temperate, and subtropical wetlands

USGS Publications Warehouse

Turetsky, Merritt R.; Kotowska, Agnieszka; Bubier, Jill; Dise, Nancy B.; Crill, Patrick; Hornibrook, Ed R.C.; Minkkinen, Kari; Moore, Tim R.; Myers-Smith, Isla H.; Nykanen, Hannu; Olefeldt, David; Rinne, Janne; Saarnio, Sanna; Shurpali, Narasinha; Tuittila, Eeva-Stiina; Waddington, J. Michael; White, Jeffrey R.; Wickland, Kimberly P.; Wilmking, Martin

2014-01-01

Wetlands are the largest natural source of atmospheric methane. Here, we assess controls on methane flux using a database of approximately 19 000 instantaneous measurements from 71 wetland sites located across subtropical, temperate, and northern high latitude regions. Our analyses confirm general controls on wetland methane emissions from soil temperature, water table, and vegetation, but also show that these relationships are modified depending on wetland type (bog, fen, or swamp), region (subarctic to temperate), and disturbance. Fen methane flux was more sensitive to vegetation and less sensitive to temperature than bog or swamp fluxes. The optimal water table for methane flux was consistently below the peat surface in bogs, close to the peat surface in poor fens, and above the peat surface in rich fens. However, the largest flux in bogs occurred when dry 30-day averaged antecedent conditions were followed by wet conditions, while in fens and swamps, the largest flux occurred when both 30-day averaged antecedent and current conditions were wet. Drained wetlands exhibited distinct characteristics, e.g. the absence of large flux following wet and warm conditions, suggesting that the same functional relationships between methane flux and environmental conditions cannot be used across pristine and disturbed wetlands. Together, our results suggest that water table and temperature are dominant controls on methane flux in pristine bogs and swamps, while other processes, such as vascular transport in pristine fens, have the potential to partially override the effect of these controls in other wetland types. Because wetland types vary in methane emissions and have distinct controls, these ecosystems need to be considered separately to yield reliable estimates of global wetland methane release.

Quantitative degassing of gas hydrate-bearing pressure cores from Green Canyon 955, Gulf of Mexico

NASA Astrophysics Data System (ADS)

Phillips, S. C.; Holland, M. E.; Flemings, P. B.; Schultheiss, P. J.; Waite, W. F.; Petrou, E. G.; Jang, J.; Polito, P. J.; O'Connell, J.; Dong, T.; Meazell, K.

2017-12-01

We present results from 20 quantitative degassing experiments of pressure-core sections collected during Expedition UT-GOM2-1 from Green Canyon 955 in the northern Gulf of Mexico. These experiments highlight an average pore-space methane hydrate saturation, Sh, of 59% (min: 12%; max 87%) in sediments between 413 and 440 mbsf in 2032 m water depth. There is a strong lithofacies control of hydrate saturation within the reservoir, with a high saturation sandy silt facies (Sh of 65 to 87%) interbedded with a low saturation clayey silt facies (Sh of 12 to 30%). Bedding occurs on the scale of tens of centimeters. Outside of the main hydrate reservoir, methane hydrate occurs in low saturations (Sh of 0.8 to 3%). Hydrate saturations exhibit a strong correlation (R2=0.89) with the average P-wave velocity measured through the degassed sections. These preliminary hydrate saturations were calculated assuming a porosity of 40% with core filling the full internal diameter of the core liner. Gas recovered during these experiments is composed of almost entirely methane, with an average of 94 ppm ethane and detectable, but not quantifiable, propane. Degassed pressure cores were depressurized through a manifold by the stepwise release of fluid, and the volumes of produced gas and water were monitored. The core's hydrostatic pressure was measured and recorded continuously at the manifold. Pressure and temperature were also measured by data storage tags within the sample chambers. Two slow, multi-day degassing experiments were performed to estimate the in situ salinity within core sections. Based on temperature and pressure observations at the point of the initial pressure rebound due to hydrate dissociation, we estimate the salinity within these samples to be between 33 and 42 g kg-1.

Stable acetate production in extreme-thermophilic (70°C) mixed culture fermentation by selective enrichment of hydrogenotrophic methanogens

NASA Astrophysics Data System (ADS)

Zhang, Fang; Zhang, Yan; Ding, Jing; Dai, Kun; van Loosdrecht, Mark C. M.; Zeng, Raymond J.

2014-06-01

The control of metabolite production is difficult in mixed culture fermentation. This is particularly related to hydrogen inhibition. In this work, hydrogenotrophic methanogens were selectively enriched to reduce the hydrogen partial pressure and to realize efficient acetate production in extreme-thermophilic (70°C) mixed culture fermentation. The continuous stirred tank reactor (CSTR) was stable operated during 100 days, in which acetate accounted for more than 90% of metabolites in liquid solutions. The yields of acetate, methane and biomass in CSTR were 1.5 +/- 0.06, 1.0 +/- 0.13 and 0.4 +/- 0.05 mol/mol glucose, respectively, close to the theoretical expected values. The CSTR effluent was stable and no further conversion occurred when incubated for 14 days in a batch reactor. In fed-batch experiments, acetate could be produced up to 34.4 g/L, significantly higher than observed in common hydrogen producing fermentations. Acetate also accounted for more than 90% of soluble products formed in these fed-batch fermentations. The microbial community analysis revealed hydrogenotrophic methanogens (mainly Methanothermobacter thermautotrophicus and Methanobacterium thermoaggregans) as 98% of Archaea, confirming that high temperature will select hydrogenotrophic methanogens over aceticlastic methanogens effectively. This work demonstrated a potential application to effectively produce acetate as a value chemical and methane as an energy gas together via mixed culture fermentation.

Stable acetate production in extreme-thermophilic (70°C) mixed culture fermentation by selective enrichment of hydrogenotrophic methanogens

PubMed Central

Zhang, Fang; Zhang, Yan; Ding, Jing; Dai, Kun; van Loosdrecht, Mark C. M.; Zeng, Raymond J.

2014-01-01

The control of metabolite production is difficult in mixed culture fermentation. This is particularly related to hydrogen inhibition. In this work, hydrogenotrophic methanogens were selectively enriched to reduce the hydrogen partial pressure and to realize efficient acetate production in extreme-thermophilic (70°C) mixed culture fermentation. The continuous stirred tank reactor (CSTR) was stable operated during 100 days, in which acetate accounted for more than 90% of metabolites in liquid solutions. The yields of acetate, methane and biomass in CSTR were 1.5 ± 0.06, 1.0 ± 0.13 and 0.4 ± 0.05 mol/mol glucose, respectively, close to the theoretical expected values. The CSTR effluent was stable and no further conversion occurred when incubated for 14 days in a batch reactor. In fed-batch experiments, acetate could be produced up to 34.4 g/L, significantly higher than observed in common hydrogen producing fermentations. Acetate also accounted for more than 90% of soluble products formed in these fed-batch fermentations. The microbial community analysis revealed hydrogenotrophic methanogens (mainly Methanothermobacter thermautotrophicus and Methanobacterium thermoaggregans) as 98% of Archaea, confirming that high temperature will select hydrogenotrophic methanogens over aceticlastic methanogens effectively. This work demonstrated a potential application to effectively produce acetate as a value chemical and methane as an energy gas together via mixed culture fermentation. PMID:24920064

Pre-treatment of thickened waste activated sludge (TWAS) for enhanced biogas production via the application of a novel radial horn sonication technology.

PubMed

Suhartini, Sri; Melville, Lynsey; Amato, Tony

2017-05-01

The efficacy of sonication as a pre-treatment to anaerobic digestion (AD) was assessed using thickened waste activated sludge (TWAS). Efficiency was measured in relation to solubilisation, dewaterability, and AD performance. Eighteen experimental conditions were evaluated at low frequency (20 kHz), duration (2-10 s), amplitude (∼8-12 μm) and applied pressure (0.5-3.0 barg), using a sonix™ patented titanium sonoprobe capable of delivering an instantaneous power of ∼6 kW provided by Doosan Enpure Ltd (DEL). An optimised experimental protocol was used as a pre-treatment for biochemical methane potential (BMP) testing and semi-continuous trials. Four digesters, with a 2-L working volume were operated mesophilically (37 ± 0.5 °C) over 22 days. The results showed that the sonix™ technology delivers effective sonication at very short retention times compared to conventional system. Results demonstrate that the technology effectively disrupts the floc structures and filaments within the TWAS, causing an increase in solubilisation and fine readily digestible material. Both BMP tests and semi-continuous trials demonstrated that sonicated TWAS gave higher biodegradability and methane potential compared to untreated TWAS. Partial-stream sonication (30:70 sonicated to untreated TWAS) resulted in a proportionate increase in biogas production illustrating the benefits of full-stream sonication.

Composite plasma polymerized sulfonated polystyrene membrane for PEMFC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nath, Bhabesh Kumar; Khan, Aziz; Chutia, Joyanti, E-mail: jchutiaiasst@gmail.com

2015-10-15

Highlights: • Methyl methane sulfonate (MMS) is used as the sulfonating agent. • The proton conductivity of the membrane is found to be 0.141 S cm{sup −1}. • Power density of fuel cell with styrene/MMS membrane is 0.5 W cm{sup −2}. • The membrane exhibits thermal stability up to 140 °C. - Abstract: This work presents the introduction of an organic compound methyl methane sulfonate (MMS) for the first time in fabrication of polystyrene based proton exchange membrane (PEM) by plasma polymerization process. The membrane is fabricated by co-polymerizing styrene and MMS in capacitively coupled continuous RF plasma. The chemicalmore » composition of the plasma polymerized polymer membrane is investigated using Fourier Transform Infrared Spectroscopy which reveals the formation of composite structure of styrene and MMS. The surface morphology studied using AFM and SEM depicts the effect of higher partial pressure of MMS on surface topography of the membrane. The proton transport property of the membrane studied using electrochemical impedance spectroscopy shows the achievement of maximum proton conductivity of 0.141 S cm{sup −1} which is comparable to Nafion 117 membrane. Fuel cell performance test of the synthesized membrane shows a maximum power density of 500 mW cm{sup −2} and current density of 0.62 A cm{sup −2} at 0.6 V.« less

Methane emissions from a human-dominated lowland coastal river network (Shanghai, China)

NASA Astrophysics Data System (ADS)

Wang, D.; Yu, Z.

2017-12-01

Evasion of methane (CH4) in streams and rivers play a critical role in global carbon (C) cycle, offsetting the C uptake by terrestrial ecosystems. However, little is known about CH4 emissions from lowland coastal rivers profoundly modified by anthropogenic perturbations. Here, we report results from a long-term, large-scale study of CH4 partial pressures (pCH4) and evasion rates in the Shanghai river network. The spatiotemporal variability of pCH4 was examined along a land-use gradient and the annual CH4 evasion were estimated to assess its role in regional C budget. During the study period, the median pCH4 from 87 surveyed rivers was 241 μatm. CH4 was oversaturated throughout the river network, CH4 hotpots were concentrated in the small urban rivers and highly discharge-dependent. The annual median fCH4 for each site ranged from 3.1 mg C•m-2•d-1 to 296.6 mg C•m-2•d-1. The annual CH4 evasion were 105 Gg CO2-eq•yr-1 and 96 Gg CO2-eq•yr-1 for the entire river network and the mainland rivers, respectively. Given the rapid urbanization in global coastal areas, more research is needed to quantify the role of lowland coastal rivers as a major landscape C source in global C budget.

The role of water in gas hydrate dissociation

USGS Publications Warehouse

Circone, S.; Stern, L.A.; Kirby, S.H.

2004-01-01

When raised to temperatures above the ice melting point, gas hydrates release their gas in well-defined, reproducible events that occur within self-maintained temperature ranges slightly below the ice point. This behavior is observed for structure I (carbon dioxide, methane) and structure II gas hydrates (methane-ethane, and propane), including those formed with either H2O- or D2O-host frameworks, and dissociated at either ambient or elevated pressure conditions. We hypothesize that at temperatures above the H2O (or D2O) melting point: (1) hydrate dissociation produces water + gas instead of ice + gas, (2) the endothermic dissociation reaction lowers the temperature of the sample, causing the water product to freeze, (3) this phase transition buffers the sample temperatures within a narrow temperature range just below the ice point until dissociation goes to completion, and (4) the temperature depression below the pure ice melting point correlates with the average rate of dissociation and arises from solution of the hydrate-forming gas, released by dissociation, in the water phase at elevated concentrations. In addition, for hydrate that is partially dissociated to ice + gas at lower temperatures and then heated to temperatures above the ice point, all remaining hydrate dissociates to gas + liquid water as existing barriers to dissociation disappear. The enhanced dissociation rates at warmer temperatures are probably associated with faster gas transport pathways arising from the formation of water product.

METHANE EMISSIONS FROM THE NATURAL GAS INDUSTRY VOLUME 10: METERING AND PRESSURE REGULATING STATIONS IN NATURAL GAS TRANSMISSIONS AND DISTRIBUTION

EPA Science Inventory

The 15-volume report summarizes the results of a comprehensive program to quantify methane (CH4) emissions from the U.S. natural gas industry for the base year. The objective was to determine CH4 emissions from the wellhead and ending downstream at the customer's meter. The accur...

Preservation of methane hydrate at 1 atm

USGS Publications Warehouse

Stern, L.A.; Circone, S.; Kirby, S.H.; Durham, W.B.

2001-01-01

A "pressure-release" method that enables reproducible bulk preservation of pure, porous, methane hydrate at conditions 50 to 75 K above its equilibrium T (193 K) at 1 atm is refined. The amount of hydrate preserved by this method appears to be greatly in excess of that reported in the previous citations, and is likely the result of a mechanism different from ice shielding.

Fundamental Study of Disposition and Release of Methane in a Shale Gas Reservoir

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yifeng; Xiong, Yongliang; Criscenti, Louise J.

The recent boom in shale gas production through hydrofracturing has reshaped the energy production landscape in the United States. Wellbore production rates vary greatly among the wells within a single field and decline rapidly with time, thus bring up a serious concern with the sustainability of shale gas production. Shale gas production starts with creating a fracture network by injecting a pressurized fluid in a wellbore. The induced fractures are then held open by proppant particles. During production, gas releases from the mudstone matrix, migrates to nearby fractures, and ultimately reaches a production wellbore. Given the relatively high permeability ofmore » the induced fractures, gas release and migration in low-permeability shale matrix is likely to be a limiting step for long-term wellbore production. Therefore, a clear understanding of the underlying mechanisms of methane disposition and release in shale matrix is crucial for the development of new technologies to maximize gas production and recovery. Shale is a natural nanocomposite material with distinct characteristics of nanometer-scale pore sizes, extremely low permeability, high clay contents, significant amounts of organic carbon, and large spatial heterogeneities. Our work has shown that nanopore confinement plays an important role in methane disposition and release in shale matrix. Using molecular simulations, we show that methane release in nanoporous kerogen matrix is characterized by fast release of pressurized free gas (accounting for ~ 30 - 47% recovery) followed by slow release of adsorbed gas as the gas pressure decreases. The first stage is driven by the gas pressure gradient while the second stage is controlled by gas desorption and diffusion. The long-term production decline appears controlled by the second stage of gas release. We further show that diffusion of all methane in nanoporous kerogen behaves differently from the bulk phase, with much smaller diffusion coefficients. The MD simulations also indicate that a significant fraction (3 - 35%) of methane deposited in kerogen can potentially become trapped in isolated nanopores and thus not recoverable. We have successfully established experimental capabilities for measuring gas sorption and desorption on shale and model materials under a wide range of physical and chemical conditions. Both low and high pressure measurements show significant sorption of CH 4 and CO 2 onto clays, implying that methane adsorbed on clay minerals could contribute a significant portion of gas-in-place in an unconventional reservoir. We have also studied the potential impact of the interaction of shale with hydrofracking fluid on gas sorption. We have found that the CH 4-CO 2 sorption capacity for the reacted sample is systematically lower (by a factor of ~2) than that for the unreacted (raw) sample. This difference in sorption capacity may result from a mineralogical or surface chemistry change of the shale sample induced by fluid-rock interaction. Our results shed a new light on mechanistic understanding gas release and production decline in unconventional reservoirs.« less

Organic History and Ice-Rock Decoupling on Enceladus

NASA Astrophysics Data System (ADS)

Zolotov, M. Y.

2007-12-01

The Cassini detection of methane, propane and acetylene in the Enceladus plume, and condensed organic compounds (OC) on the south polar region imply an organic-bearing interior of the moon. At least a few wt. % of C is expected in rocks from which Enceladus accreted. By analogy with carbonaceous chondrites, the majority of accreted OC was in a polymer in which polyaromatic groups are linked by O-, N-, and S-bearing aliphatic units. If accreted, cometary-type materials also delivered CO2, CO(?), methanol, ethane, ethene, acetylene, and condensed OC. Subsequent water ice melting and hydrothermal processes driven by decay of short-lived radionuclides led to dissolution of CO, CO2 and methanol in water and transformations of the polymer and cometary OC. CO converted to formic acid, carbonate species, methanol and methane. Hydrous pyrolysis and oxidation of the polymer partially liberated aromatic molecules and led to the formation of O-bearing OC (carboxylic and amino acids, alcohols). Increase in temperature favored oxidation of OC to carbonate species and N2, and led to graphitization of the polymer. Despite net oxidation of OC driven by H2 escape, mineral- catalyzed Fisher-Tropsch like synthesis of hydrocarbons and methane occurred in H2-rich niches. As a result, an array of aromatic, aliphatic, and N-, O-, S-bearing OC, and methane was delivered into a primordial water ocean in hydrothermal fluids. Highly soluble OC (acids, alcohols) made multiple passes through hydrothermal systems causing further oxidation of OC in rocks and solutions. In contrast, hydrocarbons exolved from cold oceanic water and formed an organic layer below the ice shell. Subsequent cooling of ocean-entering fluids and ocean freezing from above led to further separation and accumulation of OC. Some OC was trapped in ice, and methane formed clathrates. After freezing of salt eutectic brines, the light oil (a solution/mixture of ethane, propane, butane, ethene, acetylene, methanol, toluene etc.) remained unfrozen and decoupled the ice shell from underlying salt deposits and rocks. Even after oil solidification, if it occurred, the organic layer had a lower viscosity than salts and ice. An uneven pressure and/or topography at the ice-salt boundary could have led to preferential oil (and salt?) accumulation below the south polar region. Throughout history (and today), the uneven oil-rich layer could have favored tidal motions and heat generation at the bottom of the ice shell.

Microwave Spectrum and Structure of the Methane-Propane Complex

NASA Astrophysics Data System (ADS)

Peterson, Karen I.; Lin, Wei; Arsenault, Eric A.; Choi, Yoon Jeong; Novick, Stewart E.

2017-06-01

Methane is exceptional in its solid-phase orientational disorder that persists down to 24 K. Only below that temperature does the structure become partially ordered, and full crystallinity requires even lower temperatures and high pressures. Not surprisingly, methane appears to freely rotate in most van der Waals complexes, although two notable exceptions are CH_4-HF and CH_4-C_5H_5N. Of interest to us is how alkane interactions affect the methane rotation. Except for CH_4-CH_4, rotationally-resolved spectra of alkane-alkane complexes have not been studied. To fill this void, we present the microwave spectrum of CH_4-C_3H_8 which is the smallest alkane complex with a practical dipole moment. The microwave spectrum of CH_4-C_3H_8 was measured using the Fourier Transform microwave spectrometer at Wesleyan University. In the region between 7100 and 25300 MHz, we observed approximately 70 transitions that could plausibly be attributed to the CH_4-C_3H_8 complex (requiring high power and the proper mixture of gases). Of these, 16 were assigned to the A-state (lowest internal rotor state of methane) and four to the F-state. The A-state transitions were fitted with a Watson Hamiltonian using nine spectroscopic constants of which A = 7553.8144(97) MHz, B = 2483.9183(35) MHz, and C = 2041.8630(21) MHz. The A rotational constant is only 1.5 MHz higher than that of Ar-C_3H_8 and, since the a-axis of the complex passes approximately through the centers of mass of the subunits, this indicates a similar relative orientation. Thus, we find that the CH_4 is located above the plane of the propane. The center-of-mass separation of the subunits in CH_4-C_3H_8 is calculated to be 3.993 Å, 0.16 Å longer than the Ar-C_3H_8 distance of 3.825 Å, a reasonable difference considering the larger van der Waals radius of CH_4. The four F-state lines, which were about twice as strong as the A-state lines, could be fitted to A, B, and C rotational constants, and further analysis is in progress.

Breath Methane Levels Are Increased Among Patients with Diverticulosis.

PubMed

Yazici, Cemal; Arslan, Deniz Cagil; Abraham, Rana; Cushing, Kelly; Keshavarzian, Ali; Mutlu, Ece A

2016-09-01

Diverticulosis and its complications are important healthcare problems in the USA and throughout the Western world. While mechanisms as to how diverticulosis occurs have partially been explored, few studies examined the relationship between colonic gases such as methane and diverticulosis in humans. This study aimed to demonstrate a significant relationship between methanogenic Archaea and development of diverticulosis. Subjects who consecutively underwent hydrogen breath test at Rush University Medical Center between 2003 and 2010 were identified retrospectively through a database. Medical records were reviewed for presence of a colonoscopy report. Two hundred and sixty-four subjects were identified who had both a breath methane level measurement and a colonoscopy result. Additional demographic and clinical data were obtained with chart review. Mean breath methane levels were higher in subjects with diverticulosis compared to those without diverticulosis (7.89 vs. 4.94 ppm, p = 0.04). Methane producers (defined as those with baseline fasting breath methane level >5 ppm) were more frequent among subjects with diverticulosis compared to those without diverticulosis (50.9 vs. 34 %, p = 0.0025). When adjusted for confounders, breath methane levels and age were the two independent predictors of diverticulosis on colonoscopy with logistic regression modeling. Methanogenesis is associated with the presence of diverticulosis. Further studies are needed to confirm our findings and prospectively evaluate a possible etiological role of methanogenesis and methanogenic archaea in diverticulosis.

Hydrogen Profiles and Localization of Methanogenic Activities in the Highly Compartmentalized Hindgut of Soil-Feeding Higher Termites (Cubitermes spp.)

PubMed Central

Schmitt-Wagner, Dirk; Brune, Andreas

1999-01-01

It has been shown that the coexistence of methanogenesis and reductive acetogenesis in the hindgut of the wood-feeding termite Reticulitermes flavipes is based largely on the radial distribution of the respective microbial populations and relatively high hydrogen partial pressures in the gut lumen. Using Clark-type microelectrodes, we showed that the situation in Cubitermes orthognathus and other soil-feeding members of the subfamily Termitinae is different and much more complex. All major compartments of agarose-embedded hindguts were anoxic at the gut center, and high H2 partial pressures (1 to 10 kPa) in the alkaline anterior region rendered the mixed segment and the third proctodeal segment (P3) significant sources of H2. Posterior to the P3 segment, however, H2 concentrations were generally below the detection limit (<100 Pa). All hindgut compartments turned into efficient hydrogen sinks when external H2 was supplied, but methane was formed mainly in the P3/4a and P4b compartments, and in the latter only when H2 or formate was added. Addition of H2 to the gas headspace stimulated CH4 emission of living termites, indicating that endogenous H2 production limits methanogenesis also in vivo. At the low H2 partial pressures in the posterior hindgut, methanogens would most likely outcompete homoacetogens for this electron donor. This might explain the apparent predominance of methanogenesis over reductive acetogenesis in the hindgut of soil-feeding termites, although the presence of homoacetogens in the anterior, highly alkaline region cannot yet be excluded. In addition, the direct contact of anterior and posterior hindgut compartments in situ permits a cross-epithelial transfer of H2 or formate, which would not only fuel methanogenesis in these compartments, but would also create favorable microniches for reductive acetogenesis. In situ rates and spatial distribution of H2-dependent acetogenic activities are addressed in a companion paper (A. Tholen and A. Brune, Appl. Environ. Microbiol. 65:4497–4505, 1999). PMID:10508080

Thin film devices used as oxygen partial pressure sensors

NASA Technical Reports Server (NTRS)

Canady, K. S.; Wortman, J. J.

1970-01-01

Electrical conductivity of zinc oxide films to be used in an oxygen partial pressure sensor is measured as a function of temperature, oxygen partial pressure, and other atmospheric constituents. Time response following partial pressure changes is studied as a function of temperature and environmental changes.

Oceanic methane hydrate: The character of the Blake Ridge hydrate stability zone, and the potential for methane extraction

USGS Publications Warehouse

Max, M.D.; Dillon, William P.

1998-01-01

Oceanic methane hydrates are mineral deposits formed from a crystalline 'ice' of methane and water in sea-floor sediments (buried to less than about 1 km) in water depths greater than about 500 m; economic hydrate deposits are probably restricted to water depths of between 1.5 km and 4 km. Gas hydrates increase a sediment's strength both by 'freezing' the sediment and by filling the pore spaces in a manner similar to water-ice in permafrost. Concentrated hydrate deposits may be underlain by significant volumes of methane gas, and these localities are the most favourable sites for methane gas extraction operations. Seismic reflection records indicate that trapped gas may blow-out naturally, causing large-scale seafloor collapse. In this paper, we consider both the physical properties and the structural integrity of the hydrate stability zone and the associated free gas deposits, with special reference to the Blake Ridge area, SE US offshore, in order to help establish a suitable framework for the safe, efficient, and economic recovery of methane from oceanic gas hydrates. We also consider the potential effects of the extraction of methane from hydrate (such as induced sea-floor faulting, gas venting, and gas-pocket collapse). We assess the ambient pressure effect on the production of methane by hydrate dissociation, and attempt to predict the likelihood of spontaneous gas flow in a production situation.Oceanic methane hydrates are mineral sits formed from a crystalline `ice' of methane and water in sea-floor sediments (buried to less than about 1 km) in water depths greater than about 500 m; economic hydrate deposits are probably restricted to water depths of between 1.5 km and 4 km. Gas hydrates increase a sediment's strength both by `freezing' the sediment and by filling the pore spaces in a manner similar to water-ice in permafrost. Concentrated hydrate deposits may be underlain by significant volumes of methane gas, and these localities are the most favourable sites for methane gas extraction operations. Seismic reflection records indicate that trapped gas may blow-out naturally, causing large-scale seafloor collapse. In this paper, we consider both the physical properties and the structural integrity of the hydrate stability zone and the associated free gas deposits, with special reference to the Blake Ridge area, SE US offshore, in order to help establish a suitable framework for the safe, efficient, and economic recovery of methane from oceanic gas hydrates. We also consider the potential effects of the extraction of methane from hydrate (such as induced sea-floor faulting, gas venting, and gas-pocket collapse). We assess the ambient pressure effect on the production of methane by hydrate dissociation, and attempt to predict the likelihood of spontaneous gas flow in a production situation.

Liquid Methane Testing With a Large-Scale Spray Bar Thermodynamic Vent System

NASA Technical Reports Server (NTRS)

Hastings, L. J.; Bolshinskiy, L. G.; Hedayat, A.; Flachbart, R. H.; Sisco, J. D.; Schnell. A. R.

2014-01-01

NASA's Marshall Space Flight Center conducted liquid methane testing in November 2006 using the multipurpose hydrogen test bed outfitted with a spray bar thermodynamic vent system (TVS). The basic objective was to identify any unusual or unique thermodynamic characteristics associated with densified methane that should be considered in the design of space-based TVSs. Thirteen days of testing were performed with total tank heat loads ranging from 720 to 420 W at a fill level of approximately 90%. It was noted that as the fluid passed through the Joule-Thompson expansion, thermodynamic conditions consistent with the pervasive presence of metastability were indicated. This Technical Publication describes conditions that correspond with metastability and its detrimental effects on TVS performance. The observed conditions were primarily functions of methane densification and helium pressurization; therefore, assurance must be provided that metastable conditions have been circumvented in future applications of thermodynamic venting to in-space methane storage.

Gas hydrate dissociation off Svalbard induced by isostatic rebound rather than global warming.

PubMed

Wallmann, Klaus; Riedel, M; Hong, W L; Patton, H; Hubbard, A; Pape, T; Hsu, C W; Schmidt, C; Johnson, J E; Torres, M E; Andreassen, K; Berndt, C; Bohrmann, G

2018-01-08

Methane seepage from the upper continental slopes of Western Svalbard has previously been attributed to gas hydrate dissociation induced by anthropogenic warming of ambient bottom waters. Here we show that sediment cores drilled off Prins Karls Foreland contain freshwater from dissociating hydrates. However, our modeling indicates that the observed pore water freshening began around 8 ka BP when the rate of isostatic uplift outpaced eustatic sea-level rise. The resultant local shallowing and lowering of hydrostatic pressure forced gas hydrate dissociation and dissolved chloride depletions consistent with our geochemical analysis. Hence, we propose that hydrate dissociation was triggered by postglacial isostatic rebound rather than anthropogenic warming. Furthermore, we show that methane fluxes from dissociating hydrates were considerably smaller than present methane seepage rates implying that gas hydrates were not a major source of methane to the oceans, but rather acted as a dynamic seal, regulating methane release from deep geological reservoirs.

Ductile flow of methane hydrate

USGS Publications Warehouse

Durham, W.B.; Stern, L.A.; Kirby, S.H.

2003-01-01

Compressional creep tests (i.e., constant applied stress) conducted on pure, polycrystalline methane hydrate over the temperature range 260-287 K and confining pressures of 50-100 MPa show this material to be extraordinarily strong compared to other icy compounds. The contrast with hexagonal water ice, sometimes used as a proxy for gas hydrate properties, is impressive: over the thermal range where both are solid, methane hydrate is as much as 40 times stronger than ice at a given strain rate. The specific mechanical response of naturally occurring methane hydrate in sediments to environmental changes is expected to be dependent on the distribution of the hydrate phase within the formation - whether arranged structurally between and (or) cementing sediments grains versus passively in pore space within a sediment framework. If hydrate is in the former mode, the very high strength of methane hydrate implies a significantly greater strain-energy release upon decomposition and subsequent failure of hydrate-cemented formations than previously expected.

LOX/Methane Main Engine Igniter Tests and Modeling

NASA Technical Reports Server (NTRS)

Breisacher, Kevin J.; Ajmani, Kumund

2008-01-01

The LOX/methane propellant combination is being considered for the Lunar Surface Access Module ascent main engine propulsion system. The proposed switch from the hypergolic propellants used in the Apollo lunar ascent engine to LOX/methane propellants requires the development of igniters capable of highly reliable performance in a lunar surface environment. An ignition test program was conducted that used an in-house designed LOX/methane spark torch igniter. The testing occurred in Cell 21 of the Research Combustion Laboratory to utilize its altitude capability to simulate a space vacuum environment. Approximately 750 ignition test were performed to evaluate the effects of methane purity, igniter body temperature, spark energy level and frequency, mixture ratio, flowrate, and igniter geometry on the ability to obtain successful ignitions. Ignitions were obtained down to an igniter body temperature of approximately 260 R with a 10 torr back-pressure. The data obtained is also being used to anchor a CFD based igniter model.

Producing Hydrogen by Plasma Pyrolysis of Methane

NASA Technical Reports Server (NTRS)

Atwater, James; Akse, James; Wheeler, Richard

2010-01-01

Plasma pyrolysis of methane has been investigated for utility as a process for producing hydrogen. This process was conceived as a means of recovering hydrogen from methane produced as a byproduct of operation of a life-support system aboard a spacecraft. On Earth, this process, when fully developed, could be a means of producing hydrogen (for use as a fuel) from methane in natural gas. The most closely related prior competing process - catalytic pyrolysis of methane - has several disadvantages: a) The reactor used in the process is highly susceptible to fouling and deactivation of the catalyst by carbon deposits, necessitating frequent regeneration or replacement of the catalyst. b) The reactor is highly susceptible to plugging by deposition of carbon within fixed beds, with consequent channeling of flow, high pressure drops, and severe limitations on mass transfer, all contributing to reductions in reactor efficiency. c) Reaction rates are intrinsically low. d) The energy demand of the process is high.

Factors associated with blood oxygen partial pressure and carbon dioxide partial pressure regulation during respiratory extracorporeal membrane oxygenation support: data from a swine model.

PubMed

Park, Marcelo; Mendes, Pedro Vitale; Costa, Eduardo Leite Vieira; Barbosa, Edzangela Vasconcelos Santos; Hirota, Adriana Sayuri; Azevedo, Luciano Cesar Pontes

2016-01-01

The aim of this study was to explore the factors associated with blood oxygen partial pressure and carbon dioxide partial pressure. The factors associated with oxygen - and carbon dioxide regulation were investigated in an apneic pig model under veno-venous extracorporeal membrane oxygenation support. A predefined sequence of blood and sweep flows was tested. Oxygenation was mainly associated with extracorporeal membrane oxygenation blood flow (beta coefficient = 0.036mmHg/mL/min), cardiac output (beta coefficient = -11.970mmHg/L/min) and pulmonary shunting (beta coefficient = -0.232mmHg/%). Furthermore, the initial oxygen partial pressure and carbon dioxide partial pressure measurements were also associated with oxygenation, with beta coefficients of 0.160 and 0.442mmHg/mmHg, respectively. Carbon dioxide partial pressure was associated with cardiac output (beta coefficient = 3.578mmHg/L/min), sweep gas flow (beta coefficient = -2.635mmHg/L/min), temperature (beta coefficient = 4.514mmHg/ºC), initial pH (beta coefficient = -66.065mmHg/0.01 unit) and hemoglobin (beta coefficient = 6.635mmHg/g/dL). In conclusion, elevations in blood and sweep gas flows in an apneic veno-venous extracorporeal membrane oxygenation model resulted in an increase in oxygen partial pressure and a reduction in carbon dioxide partial pressure 2, respectively. Furthermore, without the possibility of causal inference, oxygen partial pressure was negatively associated with pulmonary shunting and cardiac output, and carbon dioxide partial pressure was positively associated with cardiac output, core temperature and initial hemoglobin.

Oxygen transport membrane reactor based method and system for generating electric power

DOEpatents

Kelly, Sean M.; Chakravarti, Shrikar; Li, Juan

2017-02-07

A carbon capture enabled system and method for generating electric power and/or fuel from methane containing sources using oxygen transport membranes by first converting the methane containing feed gas into a high pressure synthesis gas. Then, in one configuration the synthesis gas is combusted in oxy-combustion mode in oxygen transport membranes based boiler reactor operating at a pressure at least twice that of ambient pressure and the heat generated heats steam in thermally coupled steam generation tubes within the boiler reactor; the steam is expanded in steam turbine to generate power; and the carbon dioxide rich effluent leaving the boiler reactor is processed to isolate carbon. In another configuration the synthesis gas is further treated in a gas conditioning system configured for carbon capture in a pre-combustion mode using water gas shift reactors and acid gas removal units to produce hydrogen or hydrogen-rich fuel gas that fuels an integrated gas turbine and steam turbine system to generate power. The disclosed method and system can also be adapted to integrate with coal gasification systems to produce power from both coal and methane containing sources with greater than 90% carbon isolation.

Effect of Sodium Dodecyl Sulfate Surfactant on Methane Hydrate Formation: A Molecular Dynamics Study.

PubMed

Choudhary, Nilesh; Hande, Vrushali R; Roy, Sudip; Chakrabarty, Suman; Kumar, Rajnish

2018-06-28

In experimental studies, it has been observed that the presence of sodium dodecyl sulfate (SDS) significantly increases the kinetics of hydrate formation and the final water-to-hydrate conversion ratio. In this study, we intend to understand the molecular mechanism behind the effect of SDS on the formation of methane hydrate through molecular dynamics simulation. Hydrate formation conditions similar to that of laboratory experiments were chosen to study hydrate growth kinetics in 1 wt % SDS solution. We also investigate the effect of interactions with isolated SDS molecules on methane hydrate growth. It was observed that the hydrophobic tail part of the SDS molecule favorably interacts with the growing hydrate surface and may occupy the partial hydrate cages while the head groups remain exposed to water.

Improving methane production from digested manure biofibers by mechanical and thermal alkaline pretreatment.

PubMed

Tsapekos, P; Kougias, Panagiotis G; Frison, A; Raga, R; Angelidaki, I

2016-09-01

Animal manure digestion is associated with limited methane production, due to the high content in fibers, which are hardly degradable lignocellulosic compounds. In this study, different mechanical and thermal alkaline pretreatment methods were applied to partially degradable fibers, separated from the effluent stream of biogas reactors. Batch and continuous experiments were conducted to evaluate the efficiency of these pretreatments. In batch experiments, the mechanical pretreatment improved the degradability up to 45%. Even higher efficiency was shown by applying thermal alkaline pretreatments, enhancing fibers degradability by more than 4-fold. In continuous experiments, the thermal alkaline pretreatment, using 6% NaOH at 55°C was proven to be the most efficient pretreatment method as the methane production was increased by 26%. The findings demonstrated that the methane production of the biogas plants can be increased by further exploiting the fraction of the digested manure fibers which are discarded in the post-storage tank. Copyright © 2016 Elsevier Ltd. All rights reserved.

“Multi-temperature” method for high-pressure sorption measurements on moist shales

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gasparik, Matus; Ghanizadeh, Amin; Gensterblum, Yves

2013-08-15

A simple and effective experimental approach has been developed and tested to study the temperature dependence of high-pressure methane sorption in moist organic-rich shales. This method, denoted as “multi-temperature” (short “multi-T”) method, enables measuring multiple isotherms at varying temperatures in a single run. The measurement of individual sorption isotherms at different temperatures takes place in a closed system ensuring that the moisture content remains constant. The multi-T method was successfully tested for methane sorption on an organic-rich shale sample. Excess sorption isotherms for methane were measured at pressures of up to 25 MPa and at temperatures of 318.1 K, 338.1more » K, and 348.1 K on dry and moisture-equilibrated samples. The measured isotherms were parameterized with a 3-parameter Langmuir-based excess sorption function, from which thermodynamic sorption parameters (enthalpy and entropy of adsorption) were obtained. Using these, we show that by taking explicitly into account water vapor as molecular species in the gas phase with temperature-dependent water vapor pressure during the experiment, more meaningful results are obtained with respect to thermodynamical considerations. The proposed method can be applied to any adsorbent system (coals, shales, industrial adsorbents) and any supercritical gas (e.g., CH{sub 4}, CO{sub 2}) and is particularly suitable for sorption measurements using the manometric (volumetric) method.« less

Cryogenic Propellant Management Device: Conceptual Design Study

NASA Technical Reports Server (NTRS)

Wollen, Mark; Merino, Fred; Schuster, John; Newton, Christopher

2010-01-01

Concepts of Propellant Management Devices (PMDs) were designed for lunar descent stage reaction control system (RCS) and lunar ascent stage (main and RCS propulsion) missions using liquid oxygen (LO2) and liquid methane (LCH4). Study ground rules set a maximum of 19 days from launch to lunar touchdown, and an additional 210 days on the lunar surface before liftoff. Two PMDs were conceptually designed for each of the descent stage RCS propellant tanks, and two designs for each of the ascent stage main propellant tanks. One of the two PMD types is a traditional partial four-screen channel device. The other type is a novel, expanding volume device which uses a stretched, flexing screen. It was found that several unique design features simplified the PMD designs. These features are (1) high propellant tank operating pressures, (2) aluminum tanks for propellant storage, and (3) stringent insulation requirements. Consequently, it was possible to treat LO2 and LCH4 as if they were equivalent to Earth-storable propellants because they would remain substantially subcooled during the lunar mission. In fact, prelaunch procedures are simplified with cryogens, because any trapped vapor will condense once the propellant tanks are pressurized in space.

THE EFFECT OF SULFUR ON METHANE PARTIAL OXIDATION AND REFORMING PROCESSES FOR LEAN NOX TRAP CATALYSIS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parks, II, James E; Ponnusamy, Senthil

2006-01-01

Lean NOx trap catalysis has demonstrated the ability to reduce NOx emissions from lean natural gas reciprocating engines by >90%. The technology operates in a cyclic fashion where NOx is trapped on the catalyst during lean operation and released and reduced to N2 under rich exhaust conditions; the rich cleansing operation of the cycle is referred to as "regeneration" since the catalyst is reactivated for more NOx trapping after NOx purge. Creating the rich exhaust conditions for regeneration can be accomplished by catalytic partial oxidation of methane in the exhaust system. Furthermore, catalytic reforming of partial oxidation exhaust can enablemore » increased quantities of H2 which is an excellent reductant for lean NOx trap regeneration. It is critical to maintain clean and efficient partial oxidation and reforming processes to keep the lean NOx trap functioning properly and to reduce extra fuel consumption from the regeneration process. Although most exhaust constituents do not impede partial oxidation and reforming, some exhaust constituents may negatively affect the catalysts and result in loss of catalytic efficiency. Of particular concern are common catalyst poisons sulfur, zinc, and phosphorous. These poisons form in the exhaust through combustion of fuel and oil, and although they are present at low concentrations, they can accumulate to significant levels over the life of an engine system. In the work presented here, the effects of sulfur on the partial oxidation and reforming catalytic processes were studied to determine any durability limitations on the production of reductants for lean NOx trap catalyst regeneration.« less

Experimental investigations about the effect of trace amount of propane on the formation of mixed hydrates of methane and propane

NASA Astrophysics Data System (ADS)

Cai, W.; Lu, H.; Huang, X.

2016-12-01

In natural gas hydrates, some heavy hydrocarbons are always detected in addition to methane. However, it is still not well understood how the trace amount of heavy gas affect the hydrate properties. Intensive studies have been carried out to study the thermodynamic properties and structure types of mixed gases hydrates, but comparatively few investigations have been carried out on the cage occupancies of guest molecules in mixed gases hydrates. For understanding how trace amount of propane affects the formation of mixed methane-propane hydrates, X-ray diffraction, Raman spectroscopy, and gas chromatography were applied to the synthesized mixed methane-propane hydrate specimens, to get their structural characteristics (structure type, structural parameters, cage occupancy, etc.) and gas compositions. The mixed methane-propane hydrates were prepared by reacting fine ice powders with various gas mixtures of methane and propane. When the propane content was below 0.4%, the hydrates synthesized were found containing both sI methane hydrate and sII methane-propane hydrate; while the hydrates were found always sII when propane was over certain content. Detail studies about the cage occupancies of propane and methane in sII hydrate revealed that: 1) with the increase in propane content of methane-propane mixture, the occupancy of propane in large cage increased as accompanied with the decrease in methane occupancy in large cage, however the occupancy of methane in small cage didn't experience significant change; 2) temperature and pressure seemed no obvious influence on cage occupancy.

The phase transformation of methane caused by pressure change during its rising from seepage, revealed by video　observation　and acoustic reflection data

NASA Astrophysics Data System (ADS)

Aoyama, D.; Aoyama, C.

2014-12-01

The plume comes out to the surface of the water, and methane is released for low water temperature and low temperature in the Arctic Ocean by the atmosphere. Methane released by the atmosphere is combined with oxygen and becomes carbon dioxide and the water, and the greenhouse effect is higher in 20 times than carbon dioxide. If quantity of the　methane　plume is quantified, I may estimate the quantity of existing methane underground and can estimate the scale of methane melting into it in seawater. The　methane　plume solved in seawater is one element of the carbon cycle. It is important that I elucidate this element in thinking about the carbon cycle of the wide sense.　However, there is not the report that I showed quantitatively how much methane melts into it in seawater a year from the methane plume. Therefore, in this article, I identified an aspect of gush methane as it by the sound data with the fishfinder and by a gush picture of the methane plume. With that in mind, I quantified the quantity of the methane plume. As a result, the following things became clear. The methane hydrate grain to gush out from a gush mouth is a solid at the bottom of the sea direct top. In this sea area, methane of 7.7*104m3 per unit area gushes out. In addition, the sea area where 6.3*106m3 gushed out existed.

21 CFR 868.1150 - Indwelling blood carbon dioxide partial pressure (PCO2) analyzer.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Indwelling blood carbon dioxide partial pressure....1150 Indwelling blood carbon dioxide partial pressure (PCO2) analyzer. (a) Identification. An indwelling blood carbon dioxide partial pressure PCO2 analyzer is a device that consists of a catheter-tip...

21 CFR 868.1150 - Indwelling blood carbon dioxide partial pressure (PCO2) analyzer.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Indwelling blood carbon dioxide partial pressure....1150 Indwelling blood carbon dioxide partial pressure (PCO2) analyzer. (a) Identification. An indwelling blood carbon dioxide partial pressure PCO2 analyzer is a device that consists of a catheter-tip...

21 CFR 868.1150 - Indwelling blood carbon dioxide partial pressure (PCO2) analyzer.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Indwelling blood carbon dioxide partial pressure....1150 Indwelling blood carbon dioxide partial pressure (PCO2) analyzer. (a) Identification. An indwelling blood carbon dioxide partial pressure PCO2 analyzer is a device that consists of a catheter-tip...

21 CFR 868.1150 - Indwelling blood carbon dioxide partial pressure (PCO2) analyzer.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Indwelling blood carbon dioxide partial pressure....1150 Indwelling blood carbon dioxide partial pressure (PCO2) analyzer. (a) Identification. An indwelling blood carbon dioxide partial pressure PCO2 analyzer is a device that consists of a catheter-tip...

Process for the preparation of methane and/or ethane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wagstaff, N.

1981-09-22

According to Shell, methane and ethane can be produced from a C/sub 2/-C/sub 4/ paraffin feed stream (such as the by-product of mineral-oil production) by contacting the stream with certain crystalline silicates at temperatures of 800/sup 0/-1200/sup 0/F and 145 psi pressure. The crystalline silicates must be specially prepared to obtain the required characteristics.

Line intensities of methane in the 2700-2862-kayser region

NASA Technical Reports Server (NTRS)

Hunt, R. H.; Brown, L. R.; Toth, R. A.

1978-01-01

Individual strengths and wave numbers of 2080 methane absorption lines have been measured between 2700 and 2862 kaysers at an average resolution of 0.023 kayser using a grating spectrometer. The results include all lines with strengths greater than 0.00003 per sq cm/atm observable at 296 K with a maximum path of 32 m and a pressure of 4 torr.

Factors associated with blood oxygen partial pressure and carbon dioxide partial pressure regulation during respiratory extracorporeal membrane oxygenation support: data from a swine model

PubMed Central

Park, Marcelo; Mendes, Pedro Vitale; Costa, Eduardo Leite Vieira; Barbosa, Edzangela Vasconcelos Santos; Hirota, Adriana Sayuri; Azevedo, Luciano Cesar Pontes

2016-01-01

Objective The aim of this study was to explore the factors associated with blood oxygen partial pressure and carbon dioxide partial pressure. Methods The factors associated with oxygen - and carbon dioxide regulation were investigated in an apneic pig model under veno-venous extracorporeal membrane oxygenation support. A predefined sequence of blood and sweep flows was tested. Results Oxygenation was mainly associated with extracorporeal membrane oxygenation blood flow (beta coefficient = 0.036mmHg/mL/min), cardiac output (beta coefficient = -11.970mmHg/L/min) and pulmonary shunting (beta coefficient = -0.232mmHg/%). Furthermore, the initial oxygen partial pressure and carbon dioxide partial pressure measurements were also associated with oxygenation, with beta coefficients of 0.160 and 0.442mmHg/mmHg, respectively. Carbon dioxide partial pressure was associated with cardiac output (beta coefficient = 3.578mmHg/L/min), sweep gas flow (beta coefficient = -2.635mmHg/L/min), temperature (beta coefficient = 4.514mmHg/ºC), initial pH (beta coefficient = -66.065mmHg/0.01 unit) and hemoglobin (beta coefficient = 6.635mmHg/g/dL). Conclusion In conclusion, elevations in blood and sweep gas flows in an apneic veno-venous extracorporeal membrane oxygenation model resulted in an increase in oxygen partial pressure and a reduction in carbon dioxide partial pressure 2, respectively. Furthermore, without the possibility of causal inference, oxygen partial pressure was negatively associated with pulmonary shunting and cardiac output, and carbon dioxide partial pressure was positively associated with cardiac output, core temperature and initial hemoglobin. PMID:27096671

Phase behaviour of methane clathrate under conditions relevant to Titan's interior

NASA Astrophysics Data System (ADS)

Sclater, G.; Wood, I. G.; Tucker, M. G.; Crawford, I. A.; Fortes, A. D.

2013-09-01

Microporous gas hydrates - known as clathrates - are common on the Earth and are also thought to be abundant in the outer Solar System [1]. The conditions for the existence of clathrates prevail throughout the Solar System and they are considered to be abundant from the Martian permafrost to the surfaces and interiors of many icy satellites [7]. These materials have been extensively studied in the range 0 - 5 GPa at ambient temperatures [2-5]; however, their behaviour in the range close to the dissociation (or melting) point is not well known at all, with some suggesting the occurrence of a facecentred cubic (sII) phase, and others that the clathrate becomes unstable with respect to mixtures of solid methane and ice. The high-pressure behaviour underpins planetary modelling; for example, the behaviour of methane hydrate in the ranges 0-6 GPa and 100-400 K is crucial to accurate modelling of Saturn's largest moon, Titan where clathrates are hypothesised to be the source of CH4 in Titan's atmosphere [6]. In order to address these problems we are carrying out a program of investigation using neutron diffraction to investigate the phase behaviour of methane clathrate close to its dissociation temperature in the 0.6-2.5 GPa region. Our goals were to obtain data to provide the first in-situ diffraction-based evidence for the phase behaviour of methane clathrate near to its high-pressure dissociation temperature (along with a control measurement at room temperature for comparison with other workers), to obtain P-V curves along two isotherms for each of the phases observed, and to complete structure refinements of all three clathrate polymorphs, thereby allowing us to carry out a full audit of the methane concentration in each phase as a function of pressure (including cage occupancies). Thus far we have successfully completed our RT measurements and will make the higher temperature observations in July 2013; we anticipate being able to report our findings from this second experimental run at the EPSC.

Integrating landfill bioreactors, partial nitritation and anammox process for methane recovery and nitrogen removal from leachate

PubMed Central

Sun, Faqian; Su, Xiaomei; Kang, Tingting; Wu, Songwei; Yuan, Mengdong; Zhu, Jing; Zhang, Xiayun; Xu, Fang; Wu, Weixiang

2016-01-01

A new process consisting of a landfill bioreactor, partial-nitritation (PN) and the anammox process has been developed for landfill leachate treatment. In this study, the landfill bioreactor exhibited excellent performance in methane-rich biogas recovery, with a specific biogas yield of 0.47 L gas g−1 COD and methane percentages of 53–76%. PN was achieved in the aerobic reactor by high free ammonia (101 ± 83 mg NH3 L−1) inhibition for nitrite-oxidizing bacteria, and the desired PN effluent composition (effluent nitrite: ammonium ratio of 1.1 ± 0.3) was controlled by adjusting the alkalinity concentration per unit of ammonium oxidized to approximately 14.3 mg CaCO3 mg−1 N in the influent. The startup of anammox process was successfully achieved with a membrane bioreactor in 160 d, and a maximum nitrogen removal rate of 216 mg N L−1 d−1 was attained for real landfill leachate treatment. The quantitative polymerase chain reaction results confirmed that the cell-specific anammox activity was approximately 68–95 fmol N cell−1 d−1, which finally led to the stable operation of the system. PMID:27279481

DNS of turbulent premixed slot flames with mixture inhomogeneity: a study of NOx formation

NASA Astrophysics Data System (ADS)

Luca, Stefano; Attili, Antonio; Bisetti, Fabrizio

2016-11-01

A set of Direct Numerical Simulations of three-dimensional methane/air lean flames in a spatially developing turbulent slot burner are performed. The flames are in the thin-reaction zone regimes and the jet Reynolds number is 5600. This configuration is of interest since it displays turbulent production by mean shear as in real devices. The gas phase hydrodynamics are modeled with the reactive, unsteady Navier-Stokes equations in the low Mach number limit. Combustion is treated with finite-rate chemistry. The jet is characterized by a non-uniform equivalence ratio at the inlet and varying levels of incomplete premixing for the methane/air mixture are considered. The global equivalence ratio is 0.7 and temperature is 800 K. All simulations are performed at 4 atm. The instantaneous profiles of the mass fractions of methane and air at the inlet are sampled from a set of turbulent channel simulations that provide realistic, fully turbulent fields. The data are analyzed to study the influence of partial premixing on the flame structure. Particular focus is devoted to the assessment of heat release rate fluctuations and NOx formation. In particular, the effects of partial premixing on the production rates for the various pathways to NOx formation are investigated.

Methane hydrate - A major reservoir of carbon in the shallow geosphere?

USGS Publications Warehouse

Kvenvolden, K.A.

1988-01-01

Methane hydrates are solids composed of rigid cages of water molecules that enclose methane. Sediment containing methane hydrates is found within specific pressure-temperature conditions that occur in regions of permafrost and beneath the sea in outer continental margins. Because methane hydrates are globally widespread and concentrate methane within the gas-hydrate structure, the potential amount of methane present in the shallow geosphere at subsurface depths of < ???2000 m is very large. However, estimates of the amount are speculative and range over about three orders of magnitude, from 2 ?? 103 to 4 ?? 106 Gt (gigatons = 1015 g) of carbon, depending on the assumptions made. The estimate I favor is ??? 1 ?? 104 Gt of carbon. The estimated amount of organic carbon in the methane-hydrate reservoir greatly exceeds that in many other reservoirs of the global carbon cycle - for example, the atmosphere (3.6 Gt); terrestrial biota (830 Gt); terrestrial soil, detritus and peat (1960 Gt); marine biota (3 Gt); and marine dissolved materials (980 Gt). In fact, the amount of carbon may exceed that in all fossil fuel deposits (5 ?? 103 Gt). Because methane hydrates contain so much methane and occur in the shallow geosphere, they are of interest as a potential resource of natural gas and as a possible source of atmospheric methane released by global warming. As a potential resource, methane hydrates pose both engineering and production problems. As a contributor to a changing global climate, destabilized methane hydrates, particularly those in shallow, nearshore regions of the Arctic Ocean, may have some effect, but this effect will probably be minimal, at least during the next 100 years. ?? 1988.

Laboratory band strengths of methane and their application to the atmospheres of Jupiter, Saturn, Uranus, Neptune, and Titan. II - The red region 6000-7600 A

NASA Technical Reports Server (NTRS)

Lutz, B. L.; Owen, T.; Cess, R. D.

1982-01-01

Lutz et al. (1976) have reported the first quantitative analyses of the strengths of the blue-green bands of methane which dominate the visible spectra of the outer planets. The present investigation represents an extension of the first study to include a number of bands between 6000 and 7500 A. The objective of this extension is to establish the validity of the scaled numerical curve of growth of the first study further into the saturated region and to test the apparent pressure independence of the high-overtone bands over a large pressure range. In addition, it is desired to provide a set of homogeneously determined band strengths and curves of growth over a large spectral region and over a large range of band strengths. This will make it possible to investigate feasible apparent dependences of planetary methane abundances on wavelength and band strength as a probe of the scattering processes in the planetary atmospheres.

Effect of alkaline addition on anaerobic sludge digestion with combined pretreatment of alkaline and high pressure homogenization.

PubMed

Fang, Wei; Zhang, Panyue; Zhang, Guangming; Jin, Shuguang; Li, Dongyi; Zhang, Meixia; Xu, Xiangzhe

2014-09-01

To improve anaerobic digestion efficiency, combination pretreatment of alkaline and high pressure homogenization was applied to pretreat sewage sludge. Effect of alkaline dosage on anaerobic sludge digestion was investigated in detail. SCOD of sludge supernatant significantly increased with the alkaline dosage increase after the combined pretreatment because of sludge disintegration. Organics were significantly degraded after the anaerobic digestion, and the maximal SCOD, TCOD and VS removal was 73.5%, 61.3% and 43.5%, respectively. Cumulative biogas production, methane content in biogas and biogas production rate obviously increased with the alkaline dosage increase. Considering both the biogas production and alkaline dosage, the optimal alkaline dosage was selected as 0.04 mol/L. Relationships between biogas production and sludge disintegration showed that the accumulative biogas was mainly enhanced by the sludge disintegration. The methane yield linearly increased with the DDCOD increase as Methane yield (ml/gVS)=4.66 DDCOD-9.69. Copyright © 2014 Elsevier Ltd. All rights reserved.

Generating Aromatics From CO2 on Mars or Natural Gas on Earth

NASA Technical Reports Server (NTRS)

Muscatello, Anthony C.; Zubrin, Robert; Berggren, Mark

2006-01-01

Methane to aromatics on Mars ( METAMARS ) is the name of a process originally intended as a means of converting Martian atmospheric carbon dioxide to aromatic hydrocarbons and oxygen, which would be used as propellants for spacecraft to return to Earth. The process has been demonstrated on Earth on a laboratory scale. A truncated version of the process could be used on Earth to convert natural gas to aromatic hydrocarbon liquids. The greater (relative to natural gas) density of aromatic hydrocarbon liquids makes it more economically feasible to ship them to distant markets. Hence, this process makes it feasible to exploit some reserves of natural gas that, heretofore, have been considered as being "stranded" too far from markets to be of economic value. In the full version of METAMARS, carbon dioxide is frozen out of the atmosphere and fed to a Sabatier reactor along with hydrogen (which, on Mars, would have been brought from Earth). In the Sabatier reactor, these feedstocks are converted to methane and water. The water is condensed and electrolyzed to oxygen (which is liquefied) and hydrogen (which is recycled to the Sabatier reactor). The methane is sent to an aromatization reactor, wherein, over a molybdenum-on-zeolite catalyst at a temperature 700 C, it is partially converted into aromatic hydrocarbons (specifically, benzene, toluene, and naphthalene) along with hydrogen. The aromatics are collected by freezing, while unreacted methane and hydrogen are separated by a membrane. Most of the hydrogen is recycled to the Sabatier reactor, while the methane and a small portion of the hydrogen are recycled to the aromatization reactor. The partial recycle of hydrogen to the aromatization reactor greatly increases the catalyst lifetime and eases its regeneration by preventing the formation of graphitic carbon, which could damage the catalyst. (Moreover, if graphitic carbon were allowed to form, it would be necessary to use oxygen to remove it.) Because the aromatics contain only one hydrogen atom per carbon atom, METAMARS produces four times as much propellant from a given amount of hydrogen as does a related process that includes the Sabatier reaction and electrolysis but not aromatization. In the terrestrial version of METAMARS, the Sabatier reactor and electrolyzer would be omitted, while the hydrogen/ methane membrane-separating membrane, the aromatization reactor, and the unreacted-gas-recycling subsystem would be retained. Natural gas would be fed directly to the aromatization reactor. Because natural gas consists of higher hydrocarbons in addition to methane, the aromatization subprocess should be more efficient than it is for methane alone.

21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

Comment [on 'Are Proterozoic cap carbonates and isotopic excursions a record of gas hydrate destabilization following Earth’s coldest intervals?, Kennedy et al., Geology 29(5), 442-446

USGS Publications Warehouse

Max, M.D.; Dillon, William P.

2002-01-01

We welcome the evidence noted by Kennedy et al. (2001) for strong methane excursions associated with the cessation of glacial episodes. They identify the carbon in cap carbonates overlying glacial sediments as probably being of biogenic origin and as likely having had a biogenic methane source. These authors suggest that the methane was released from gas hydrate, which we agree is likely. However, we suggest a different mechanism for that release, rather than their suggested warming event. We propose that a dominantly pressure-related mechanism would be more plausible for releasing sufficient methane from the huge gas hydrate reservoir to modify the global greenhouse and drive global warming in a geological instant.

Is the extent of glaciation limited by marine gas-hydrates?

USGS Publications Warehouse

Paull, Charles K.; Ussler, William; Dillon, William P.

1991-01-01

Methane may have been released to the atmosphere during the Quaternary from Arctic shelf gas-hydrates as a result of thermal decomposition caused by climatic warming and rising sea-level; this release of methane (a greenhouse gas) may represent a positive feedback on global warming [Revelle, 1983; Kvenvolden, 1988a; Nisbet, 1990]. We consider the response to sea-level changes by the immense amount of gas-hydrate that exists in continental rise sediments, and suggest that the reverse situation may apply—that release of methane trapped in the deep-sea sediments as gas-hydrates may provide a negative feedback to advancing glaciation. Methane is likely to be released from deep-sea gas-hydrates as sea-level falls because methane gas-hydrates decompose with pressure decrease. Methane would be released to sediment pore space at shallow sub-bottom depths (100's of meters beneath the seafloor, commonly at water depths of 500 to 4,000 m) producing zones of markedly decreased sediment strength, leading to slumping [Carpenter, 1981; Kayen, 1988] and abrupt release of the gas. Methane is likely to be released to the atmosphere in spikes that become larger and more frequent as glaciation progresses. Because addition of methane to the atmosphere warms the planet, this process provides a negative feedback to glaciation, and could trigger deglaciation.

Experimental Simulations of Methane Gas Migration through Water-Saturated Sediment Cores

NASA Astrophysics Data System (ADS)

Choi, J.; Seol, Y.; Rosenbaum, E. J.

2010-12-01

Previous numerical simulations (Jaines and Juanes, 2009) showed that modes of gas migration would mainly be determined by grain size; capillary invasion preferably occurring in coarse-grained sediments vs. fracturing dominantly in fine-grained sediments. This study was intended to experimentally simulate preferential modes of gas migration in various water-saturated sediment cores. The cores compacted in the laboratory include a silica sand core (mean size of 180 μm), a silica silt core (1.7 μm), and a kaolin clay core (1.0 μm). Methane gas was injected into the core placed within an x-ray-transparent pressure vessel, which was under continuous x-ray computed tomography (CT) scanning with controlled radial (σr), axial (σa), and pore pressures (P). The CT image analysis reveals that, under the radial effective stress (σr') of 0.69 MPa and the axial effective stress (σa') of 1.31 MPa, fracturings by methane gas injection occur in both silt and clay cores. Fracturing initiates at the capillary pressure (Pc) of ~ 0.41 MPa and ~ 2.41 MPa for silt and clay cores, respectively. Fracturing appears as irregular fracture-networks consisting of nearly invisibly-fine multiple fractures, longitudinally-oriented round tube-shape conduits, or fine fractures branching off from the large conduits. However, for the sand core, only capillary invasion was observed at or above 0.034 MPa of capillary pressure under the confining pressure condition of σr' = 1.38 MPa and σa' = 2.62 MPa. Compared to the numerical predictions under similar confining pressure conditions, fracturing occurs with relatively larger grain sizes, which may result from lower grain-contact compression and friction caused by loose compaction and flexible lateral boundary employed in the experiment.

Depletion of the vibrational ground state of CH4 in absorption spectroscopy at 3.4 μm in N2 and air in the 1-100 Torr range

NASA Astrophysics Data System (ADS)

Hausmaninger, Thomas; Zhao, Gang; Ma, Weiguang; Axner, Ove

2018-01-01

A model presented in an accompanying work predicts that mid-IR absorption signals from methane in trace concentrations in various buffer gases detected at pressures in the 1-100 Torr range can be reduced and distorted due to depletion of the vibrational ground state if the molecules are exposed to laser powers in the tens of mW range or above. This work provides experimental evidence of such depletion in a resonant cavity under a variety of conditions, e.g. for intracavity laser powers up to 2 W and for buffer gases of N2 or dry air, and verifies the applicability of the model. It was found that the degree of depletion is significantly larger in N2 than dry air, and that it increases with pressure for pressures up to around 10 Torr (attributed to a decreased diffusion rate) but decreases with pressure for pressures above 20 Torr (caused by an increased collisional vibrational decay rate). The maximum degree of depletion (∼80%) was obtained for methane in N2 at around 15 Torr. This implies that absorption spectrometry of methane can experience significant non-linear dependencies on laser power, pressure, as well as buffer gas composition. It is shown that depletion takes place also in 13CH4, which verifies the applicability of the model also for this isotopologue, and that NICE-OHMS signals detected in absorption phase are less affected by depletion than in dispersion. It was concluded that the absorption mode of detection can provide concentration assessments that are virtually free of influence of depletion for intracavity powers below 0.8 W.

Methane Recovery from Gaseous Mixtures Using Carbonaceous Adsorbents

NASA Astrophysics Data System (ADS)

Buczek, Bronisław

2016-06-01

Methane recovery from gaseous mixtures has both economical and ecological aspect. Methane from different waste gases like mine gases, nitrogenated natural gases and biogases can be treated as local source for production electric and heat energy. Also occurs the problem of atmosphere pollution with methane that shows over 20 times more harmful environmental effect in comparison to carbon dioxide. One of the ways utilisation such gases is enrichment of methane in the PSA technique, which requires appropriate adsorbents. Active carbons and carbon molecular sieve produced by industry and obtained in laboratory scale were examined as adsorbent for methane recuperation. Porous structure of adsorbents was investigated using densimetry measurements and adsorption of argon at 77.5K. On the basis of adsorption data, the Dubinin-Radushkevich equation parameters, micropore volume (Wo) and characteristics of energy adsorption (Eo) as well as area micropores (Smi) and BET area (SBET) were determined. The usability of adsorbents in enrichment of the methane was evaluated in the test, which simulate the basic stages of PSA process: a) adsorbent degassing, b) pressure raise in column by feed gas, c) cocurrent desorption with analysis of out flowing gas. The composition of gas phase was accepted as the criterion of the suitability of adsorbent for methane separation from gaseous mixtures. The relationship between methane recovery from gas mixture and texture parameters of adsorbents was found.

Bacterial methane oxidation in sea-floor gas hydrate: Significance to life in extreme environments

NASA Astrophysics Data System (ADS)

Sassen, Roger; MacDonald, Ian R.; Guinasso, Norman L., Jr.; Joye, Samantha; Requejo, Adolfo G.; Sweet, Stephen T.; Alcalá-Herrera, Javier; Defreitas, Debra A.; Schink, David R.

1998-09-01

Samples of thermogenic hydrocarbon gases, from vents and gas hydrate mounds within a sea-floor chemosynthetic community on the Gulf of Mexico continental slope at about 540 m depth, were collected by research submersible. Our study area is characterized by low water temperature (mean =7 °C), high pressure (about 5400 kPa), and abundant structure II gas hydrate. Bacterial oxidation of hydrate-bound methane (CH4) is indicated by three isotopic properties of gas hydrate samples. Relative to the vent gas from which the gas hydrate formed, (1) methane-bound methane is enriched in 13C by as much as 3.8‰ PDB (Peedee belemnite), (2) hydrate-bound methane is enriched in deuterium (D) by as much as 37‰ SMOW (standard mean ocean water), and (3) hydrate-bound carbon dioxide (CO2) is depleted in 13C by as much as 22.4‰ PDB. Hydrate-associated authigenic carbonate rock is also depleted in 13C. Bacterial oxidation of methane is a driving force in chemosynthetic communities, and in the concomitant precipitation of authigenic carbonate rock that modifies sea-floor geology. Bacterial oxidation of hydrate-bound methane expands the potential boundaries of life in extreme environments.

In situ gas analysis for high pressure applications using property measurements

NASA Astrophysics Data System (ADS)

Moeller, J.; Span, R.; Fieback, T.

2013-10-01

As the production, distribution, and storage of renewable energy based fuels usually are performed under high pressures and as there is a lack of in situ high pressure gas analysis instruments on the market, the aim of this work was to develop a method for in situ high pressure gas analysis of biogas and hydrogen containing gas mixtures. The analysis is based on in situ measurements of optical, thermo physical, and electromagnetic properties in gas mixtures with newly developed high pressure sensors. This article depicts the calculation of compositions from the measured properties, which is carried out iteratively by using highly accurate equations of state for gas mixtures. The validation of the method consisted of the generation and measurement of several mixtures, of which three are presented herein: a first mixture of 64.9 mol. % methane, 17.1 mol. % carbon dioxide, 9 mol. % helium, and 9 mol. % ethane at 323 K and 423 K in a pressure range from 2.5 MPa to 17 MPa; a second mixture of 93.0 mol. % methane, 4.0 mol. % propane, 2.0 mol. % carbon dioxide, and 1.0 mol. % nitrogen at 303 K, 313 K, and 323 K in a pressure range from 1.2 MPa to 3 MPa; and a third mixture of 64.9 mol. % methane, 30.1 mol. % carbon dioxide, and 5.0 mol. % nitrogen at 303 K, 313 K, and 323 K in a pressure range from 2.5 MPa to 4 MPa. The analysis of the tested gas mixtures showed that with measured density, velocity of sound, and relative permittivity the composition can be determined with deviations below 1.9 mol. %, in most cases even below 1 mol. %. Comparing the calculated compositions with the generated gas mixture, the deviations were in the range of the combined uncertainty of measurement and property models.

Methane Hydrate Fformation in a Coarse-Grained, Brine-Saturated Sample Through the Induction of a Propagating Gas Front

NASA Astrophysics Data System (ADS)

Meyer, D.

2016-12-01

We generate methane hydrate in a coarse-grained, brine-saturated, vertically-oriented sample through gas injection. From 0 - 80 hours, we estimate a hydrate saturation of 0.56 behind the formation front, using mass balance, indicating that hydrate formation is limited by locally-elevated salinity creating three-phase equilibrium conditions. After 80 hours, the hydrate phase saturation drops to 0.50 and the magnitude of the pressure drop-rebound cycles increases, suggesting temporary reductions in permeability and the development of heterogeneous distributions of free gas in the sample. The sample consists of an industrial, fine sand mixed with a 0.5 wt% fraction of natural, smectitic clay from the Eugene Island region in the Gulf of Mexico (5.08cm diameter, 11.79cm length). The sample is initially saturated with a 7 wt% sodium chloride brine, pressurized to 12.24 MPa, and cooled to 1 degree Celsius, to bring the sample into the hydrate stability zone. Syringe pumps filled with methane gas and brine are connected to the top and bottom of the sample, respectively, to control fluid flow. We withdraw from the base of the sample at a rate of 0.0005 mL/min and inject methane to maintain a constant pressure, initiating hydrate formation. We analyze this experiment, as well as a gas flood experiment executed under the same conditions, using computed-tomography scans and an analytical solution to investigate the formation behavior and thermodynamic state of hydrate in gas-rich, coarse-grained reservoirs.

Long - High Resolution Spectrum of Methane. Towards Titan's Atmosphere

NASA Astrophysics Data System (ADS)

Daumont, Ludovic; Tyuterev, Vladimir; Regalia, Laurence; Thomas, Xavier; von der Heyden, Pierre; Nikitin, Rei; Brown, Linda

2011-06-01

The precise knowledge of the methane absorption in the study of planetary systems, and especially of Titan (Saturn's largest satellite whose atmosphere is mainly composed of nitrogen and methane at temperatures ranging between 70 K and 200 K), is of great importance because it gives access to the determination of the physical properties of these objects. The full interpretation of the Titan data returned by the ground-based and space observations has been hindered by the lack of precise knowledge of the methane absorption which dominates Titan's near infrared spectra. We investigate the methane spectra in the closest conditions to existing Titan's spectra. We used the 50 m long cell from Reims university in front of the Home-made Fourier Transform Spectrometer to study the 12CH_4 spectra with 1603 m absorption path length, 1, 7 and 34 hPa pressures and at room temperature. The spectra was recorded in the all range from 3800 to 8100 Cm-1. The up-to-date measurements and assignments- mainly in the so called methane transparancy windows- will be presented and discussed.

A post-Cassini view of Titan's methane-based hydrologic cycle

NASA Astrophysics Data System (ADS)

Hayes, Alexander G.; Lorenz, Ralph D.; Lunine, Jonathan I.

2018-05-01

The methane-based hydrologic cycle on Saturn's largest moon, Titan, is an extreme analogue to Earth's water cycle. Titan is the only planetary body in the Solar System, other than Earth, that is known to have an active hydrologic cycle. With a surface pressure of 1.5 bar and temperatures of 90 to 95 K, methane and ethane condense out of a nitrogen-based atmosphere and flow as liquids on the moon's surface. Exchange processes between atmospheric, surface and subsurface reservoirs produce methane and ethane cloud systems, as well as erosional and depositional landscapes that have strikingly similar forms to their terrestrial counterparts. Over its 13-year exploration of the Saturn system, the Cassini-Huygens mission revealed that Titan's hydrocarbon-based hydrology is driven by nested methane cycles that operate over a range of timescales, including geologic, orbital (for example, Croll-Milankovitch cycles), seasonal and that of a single convective storm. In this Review Article, we describe the dominant exchange processes that operate over these timescales and present a post-Cassini view of Titan's methane-based hydrologic system.

The interaction of climate change and methane hydrates

USGS Publications Warehouse

Ruppel, Carolyn D.; Kessler, John D.

2017-01-01

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perception that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.

The interaction of climate change and methane hydrates

NASA Astrophysics Data System (ADS)

Ruppel, Carolyn D.; Kessler, John D.

2017-03-01

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perception that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.

The interaction of climate change and methane hydrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruppel, Carolyn D.; Kessler, John D.

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perceptionmore » that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.« less

The interaction of climate change and methane hydrates

DOE PAGES

Ruppel, Carolyn D.; Kessler, John D.

2016-12-14

Gas hydrate, a frozen, naturally-occurring, and highly-concentrated form of methane, sequesters significant carbon in the global system and is stable only over a range of low-temperature and moderate-pressure conditions. Gas hydrate is widespread in the sediments of marine continental margins and permafrost areas, locations where ocean and atmospheric warming may perturb the hydrate stability field and lead to release of the sequestered methane into the overlying sediments and soils. Methane and methane-derived carbon that escape from sediments and soils and reach the atmosphere could exacerbate greenhouse warming. The synergy between warming climate and gas hydrate dissociation feeds a popular perceptionmore » that global warming could drive catastrophic methane releases from the contemporary gas hydrate reservoir. Appropriate evaluation of the two sides of the climate-methane hydrate synergy requires assessing direct and indirect observational data related to gas hydrate dissociation phenomena and numerical models that track the interaction of gas hydrates/methane with the ocean and/or atmosphere. Methane hydrate is likely undergoing dissociation now on global upper continental slopes and on continental shelves that ring the Arctic Ocean. Many factors—the depth of the gas hydrates in sediments, strong sediment and water column sinks, and the inability of bubbles emitted at the seafloor to deliver methane to the sea-air interface in most cases—mitigate the impact of gas hydrate dissociation on atmospheric greenhouse gas concentrations though. There is no conclusive proof that hydrate-derived methane is reaching the atmosphere now, but more observational data and improved numerical models will better characterize the climate-hydrate synergy in the future.« less

Temperature- and pressure-dependent absorption cross sections of gaseous hydrocarbons at 3.39 µm

NASA Astrophysics Data System (ADS)

Klingbeil, A. E.; Jeffries, J. B.; Hanson, R. K.

2006-07-01

The pressure- and temperature-dependent absorption cross sections of several neat hydrocarbons and multi-component fuels are measured using a 3.39 µm helium-neon laser. Absorption cross section measurements are reported for methane, ethylene, propane, n-heptane, iso-octane, n-decane, n-dodecane, JP-10, gasoline and jet-A with an estimated uncertainty of less than 3.5%. The experimental conditions range from 298 to 673 K and from 500 to 2000 Torr with nitrogen as the bath gas. An apparatus is designed to facilitate these measurements, and specific care is taken to ensure the compositional accuracy of the hydrocarbon/N2 mixtures. The absorption cross sections of the smallest hydrocarbons, methane and ethylene, vary with temperature and pressure. The cross sections of larger hydrocarbons show negligible dependence on pressure and only a weak dependence on temperature. The reported data increase the range of conditions and the number of hydrocarbons for which cross section measurements are available at the HeNe laser wavelength.

Combustion Stability Characteristics of the Project Morpheus Liquid Oxygen/Liquid Methane Main Engine

NASA Technical Reports Server (NTRS)

Melcher, J. C.; Morehead, Robert L.

2014-01-01

The Project Morpheus liquid oxygen (LOX) / liquid methane rocket engines demonstrated acousticcoupled combustion instabilities during sea-level ground-based testing at the NASA Johnson Space Center (JSC) and Stennis Space Center (SSC). High-amplitude, 1T, 1R, 1T1R (and higher order) modes appear to be triggered by injector conditions. The instability occurred during the Morpheus-specific engine ignition/start sequence, and did demonstrate the capability to propagate into mainstage. However, the instability was never observed to initiate during mainstage, even at low power levels. The Morpheus main engine is a JSC-designed 5,000 lbf-thrust, 4:1 throttling, pressure-fed cryogenic engine using an impinging element injector design. Two different engine designs, named HD4 and HD5, and two different builds of the HD4 engine all demonstrated similar instability characteristics. Through the analysis of more than 200 hot fire tests on the Morpheus vehicle and SSC test stand, a relationship between ignition stability and injector/chamber pressure was developed. The instability has the distinct characteristic of initiating at high relative injection pressure drop (dP) at low chamber pressure (Pc); i.e., instabilities initiated at high dP/Pc at low Pc during the start sequence. The high dP/Pc during start results during the injector /chamber chill-in, and is enhanced by hydraulic flip in the injector orifice elements. Because of the fixed mixture ratio of the existing engine design (the main valves share a common actuator), it is not currently possible to determine if LOX or methane injector dP/Pc were individual contributors (i.e., LOX and methane dP/Pc typically trend in the same direction within a given test). The instability demonstrated initiation characteristic of starting at or shortly after methane injector chillin. Colder methane (e.g., sub-cooled) at the injector inlet prior to engine start was much more likely to result in an instability. A secondary effect of LOX sub-cooling was also possibly observed; greater LOX sub- cooling improved stability. Some tests demonstrated a low-amplitude 1L-1T instability prior to LOX injector chill-in. The Morpheus main engine also demonstrated chug instabilities during some engine shutdown sequences on the flight vehicle and SSC test stand. The chug instability was also infrequently observed during the startup sequence. The chug instabilities predictably initiated at low dP/Pc at low Pc. The chug instabilities were always self-limiting; startup chug instabilities terminated during throttle-up and shutdown chug instabilities decayed by shutdown termination.

Sensitivity, stability, and precision of quantitative Ns-LIBS-based fuel-air-ratio measurements for methane-air flames at 1-11 bar.

PubMed

Hsu, Paul S; Gragston, Mark; Wu, Yue; Zhang, Zhili; Patnaik, Anil K; Kiefer, Johannes; Roy, Sukesh; Gord, James R

2016-10-01

Nanosecond laser-induced breakdown spectroscopy (ns-LIBS) is employed for quantitative local fuel-air (F/A) ratio (i.e., ratio of actual fuel-to-oxidizer mass over ratio of fuel-to-oxidizer mass at stoichiometry, measurements in well-characterized methane-air flames at pressures of 1-11 bar). We selected nitrogen and hydrogen atomic-emission lines at 568 nm and 656 nm, respectively, to establish a correlation between the line intensities and the F/A ratio. We have investigated the effects of laser-pulse energy, camera gate delay, and pressure on the sensitivity, stability, and precision of the quantitative ns-LIBS F/A ratio measurements. We determined the optimal laser energy and camera gate delay for each pressure condition and found that measurement stability and precision are degraded with an increase in pressure. We have identified primary limitations of the F/A ratio measurement employing ns-LIBS at elevated pressures as instabilities caused by the higher density laser-induced plasma and the presence of the higher level of soot. Potential improvements are suggested.

Autoignition and Burning Speeds of JP-8 Fuel at High Temperatures and Pressures

DTIC Science & Technology

2004-08-25

Editorial Board of the International Journal of Exergy . He is also a member of the Scientific Council of International Center for Applied Thermodynamics...for Schlieren and Shadowgraph Images of Transient Expanding Spherical Thin Flames, ASME International Journal of Engineering for Gas Turbines and...Measurements of Methane-Oxygen-Argon Mixtures and Its Application to Extend the Methane-Air Burning Velocity Measurements”, International Journal of Engine

Changes in pore structure of coal caused by coal-to-gas bioconversion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Rui; Liu, Shimin; Bahadur, Jitendra

Microbial enhanced coalbed methane (ME-CBM) recovery is critically examined as a viable technology for natural gas recovery from coalbed methane (CBM) reservoirs. Since the majority of gas-in-place (GIP) is stored as an adsorbed phase in fine pores of coal matrix, the nano-pore structure directly influences gas storage and transport properties. Only limited studies have quantified the alteration of the nano-pore structure due to ME-CBM treatment. This study examines the evolution of the pore structure using a combination of small angle X-ray scattering (SAXS), low-pressure N 2 and CO 2 adsorption (LPGA) and high-pressure methane adsorption methods. The results show thatmore » the surface fractal dimension decreases for the two bioconverted coals compared to the untreated coal. After bio-treatment, the mesopore surface area and pore volume decrease with the average pore diameter increases, while the micropore surface area increases with pore volume decreases. Both inaccessible meso-/micropore size distributions decrease after bioconversion, while the accessible micropore size distribution increases, making a portion of closed micropore network accessible. In addition, the methane adsorption capacities increase after bio-treatment, which is confirmed by the increase of micropore surface area. A conceptual physical model of methanogenesis is proposed based on the evolution of the pore structure.« less

Changes in pore structure of coal caused by coal-to-gas bioconversion

DOE PAGES

Zhang, Rui; Liu, Shimin; Bahadur, Jitendra; ...

2017-06-19

Microbial enhanced coalbed methane (ME-CBM) recovery is critically examined as a viable technology for natural gas recovery from coalbed methane (CBM) reservoirs. Since the majority of gas-in-place (GIP) is stored as an adsorbed phase in fine pores of coal matrix, the nano-pore structure directly influences gas storage and transport properties. Only limited studies have quantified the alteration of the nano-pore structure due to ME-CBM treatment. This study examines the evolution of the pore structure using a combination of small angle X-ray scattering (SAXS), low-pressure N 2 and CO 2 adsorption (LPGA) and high-pressure methane adsorption methods. The results show thatmore » the surface fractal dimension decreases for the two bioconverted coals compared to the untreated coal. After bio-treatment, the mesopore surface area and pore volume decrease with the average pore diameter increases, while the micropore surface area increases with pore volume decreases. Both inaccessible meso-/micropore size distributions decrease after bioconversion, while the accessible micropore size distribution increases, making a portion of closed micropore network accessible. In addition, the methane adsorption capacities increase after bio-treatment, which is confirmed by the increase of micropore surface area. A conceptual physical model of methanogenesis is proposed based on the evolution of the pore structure.« less

Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking

DOE PAGES

Lustemberg, Pablo G.; Palomino, Robert M.; Gutierrez, Ramon A.; ...

2018-05-28

The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH 4 → CH 3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO 2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy andmore » density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO 2, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. Lastly, these findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels.« less

Direct Conversion of Methane to Methanol on Ni-Ceria Surfaces: Metal-Support Interactions and Water-enabled Catalytic Conversion by Site Blocking

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lustemberg, Pablo G.; Palomino, Robert M.; Gutierrez, Ramon A.

The transformation of methane into methanol or higher alcohols at moderate temperature and pressure conditions is of great environmental interest and remains a challenge despite many efforts. Extended surfaces of metallic nickel are inactive for a direct CH 4 → CH 3OH conversion. This experimental and computational study provides clear evidence that low Ni loadings on a CeO 2(111) support can perform a direct catalytic cycle for the generation of methanol at low temperature using oxygen and water as reactants, with a higher selectivity than ever reported for ceria-based catalysts. On the basis of ambient pressure X-ray photoemission spectroscopy andmore » density functional theory calculations, we demonstrate that water plays a crucial role in blocking catalyst sites where methyl species could fully decompose, an essential factor for diminishing the production of CO and CO 2, and in generating sites on which methoxy species and ultimately methanol can form. In addition to water-site blocking, one needs the effects of metal-support interactions to bind and activate methane and water. Lastly, these findings should be considered when designing metal/oxide catalysts for converting methane to value-added chemicals and fuels.« less

Overcoming sodium toxicity by utilizing grass leaves as co-substrate during the start-up of batch thermophilic anaerobic digestion.

PubMed

Suwannoppadol, Suwat; Ho, Goen; Cord-Ruwisch, Ralf

2012-12-01

Sodium toxicity is a common problem causing inhibition of anaerobic digestion, and digesters treating highly concentrated wastes, such as food and municipal solid waste, and concentrated animal manure, are likely to suffer from partial or complete inhibition of methane-producing consortia, including methanogens. When grass clippings were added at the onset of anaerobic digestion of acetate containing a sodium concentration of 7.8 gNa(+)/L, a total methane production about 8L/L was obtained, whereas no methane was produced in the absence of grass leaves. In an attempt to narrow down which components of grass leaves caused decrease of sodium toxicity, different hypotheses were tested. Results revealed that betaine could be a significant compound in grass leaves causing reduction to sodium inhibition. Copyright © 2012 Elsevier Ltd. All rights reserved.

Method of making compost and spawned compost, mushroom spawn and generating methane gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoller, B.B.

1981-04-28

Newly designed ribbon-type mixers provide an improved method for making composts, aerating composts, growing mushroom spawn, generating methane gas, and filling conveyors in the mushroom-growing industry. The mixers may be the double-ribbon type for purely mixing operations or the single-ribbon type for moving the material from one place to another. Both types can operate under pressure. In preparing compost for mushroom growing, operators can first use the airtight mixers for a preliminary anaerobic fermentation to produce methane, then by changing the atmosphere to an oxidizing one, complete the compost preparation under the necessary aerobic conditions.

Microgravity

NASA Image and Video Library

1997-01-01

Image taken during a ground based investigation of a methane-fueled laminar flame surrounded by co-flowing air. The flame was enclosed in a chamber, and the pressure reduced. As the pressure decreased, the velocity of the flow increased, causing the flame to change from a stabilized condition to near blow-out or extinction.

High performance biological methanation in a thermophilic anaerobic trickle bed reactor.

PubMed

Strübing, Dietmar; Huber, Bettina; Lebuhn, Michael; Drewes, Jörg E; Koch, Konrad

2017-12-01

In order to enhance energy efficiency of biological methanation of CO 2 and H 2 , this study investigated the performance of a thermophilic (55°C) anaerobic trickle bed reactor (ATBR) (58.1L) at ambient pressure. With a methane production rate of up to 15.4m 3 CH4 /(m 3 trickle bed ·d) at methane concentrations above 98%, the ATBR can easily compete with the performance of other mixed culture methanation reactors. Control of pH and nutrient supply turned out to be crucial for stable operation and was affected significantly by dilution due to metabolic water production, especially during demand-orientated operation. Considering practical applications, inoculation with digested sludge, containing a diverse biocenosis, showed high adaptive capacity due to intrinsic biological diversity. However, no macroscopic biofilm formation was observed at thermophilic conditions even after 313days of operation. The applied approach illustrates the high potential of thermophilic ATBRs as a very efficient energy conversion and storage technology. Copyright © 2017 Elsevier Ltd. All rights reserved.

Production of methane-rich syngas from hydrocarbon fuels using multi-functional catalyst/capture agent

DOEpatents

Siefert, Nicholas S; Shekhawat, Dushyant; Berry, David A; Surdoval, Wayne A

2014-12-30

The disclosure provides a gasification process for the production of a methane-rich syngas at temperatures exceeding 700.degree. C. through the use of an alkali hydroxide MOH, using a gasification mixture comprised of at least 0.25 moles and less than 2 moles of water for each mole of carbon, and at least 0.15 moles and less than 2 moles of alkali hydroxide MOH for each mole of carbon. These relative amounts allow the production of a methane-rich syngas at temperatures exceeding 700.degree. C. by enabling a series of reactions which generate H.sub.2 and CH.sub.4, and mitigate the reforming of methane. The process provides a methane-rich syngas comprised of roughly 20% (dry molar percentage) CH.sub.4 at temperatures above 700.degree. C., and may effectively operate within an IGFC cycle at reactor temperatures between 700-900.degree. C. and pressures in excess of 10 atmospheres.

Methane-rich syngas production from hydrocarbon fuels using multi-functional catalyst/capture agent

DOEpatents

Siefert, Nicholas S.; Shekhawat, Dushyant; Berry, David A.; Surdoval, Wayne A.

2017-02-07

The disclosure provides a gasification process for the production of a methane-rich syngas at temperatures exceeding 400.degree. C. through the use of an alkali hydroxide MOH, using a gasification mixture comprised of at least 0.25 moles and less than 2 moles of water for each mole of carbon, and at least 0.15 moles and less than 2 moles of alkali hydroxide MOH for each mole of carbon. These relative amounts allow the production of a methane-rich syngas at temperatures exceeding 400.degree. C. by enabling a series of reactions which generate H.sub.2 and CH.sub.4, and mitigate the reforming of methane. The process provides a methane-rich syngas comprised of roughly 20% (dry molar percentage) CH.sub.4 at temperatures above 400.degree. C., and may effectively operate within an IGFC cycle at reactor temperatures between 400-900.degree. C. and pressures in excess of 10 atmospheres.

Eruption of a deep-sea mud volcano triggers rapid sediment movement.

PubMed

Feseker, Tomas; Boetius, Antje; Wenzhöfer, Frank; Blandin, Jerome; Olu, Karine; Yoerger, Dana R; Camilli, Richard; German, Christopher R; de Beer, Dirk

2014-11-11

Submarine mud volcanoes are important sources of methane to the water column. However, the temporal variability of their mud and methane emissions is unknown. Methane emissions were previously proposed to result from a dynamic equilibrium between upward migration and consumption at the seabed by methane-consuming microbes. Here we show non-steady-state situations of vigorous mud movement that are revealed through variations in fluid flow, seabed temperature and seafloor bathymetry. Time series data for pressure, temperature, pH and seafloor photography were collected over 431 days using a benthic observatory at the active Håkon Mosby Mud Volcano. We documented 25 pulses of hot subsurface fluids, accompanied by eruptions that changed the landscape of the mud volcano. Four major events triggered rapid sediment uplift of more than a metre in height, substantial lateral flow of muds at average velocities of 0.4 m per day, and significant emissions of methane and CO₂ from the seafloor.

Eruption of a deep-sea mud volcano triggers rapid sediment movement

PubMed Central

Feseker, Tomas; Boetius, Antje; Wenzhöfer, Frank; Blandin, Jerome; Olu, Karine; Yoerger, Dana R.; Camilli, Richard; German, Christopher R.; de Beer, Dirk

2014-01-01

Submarine mud volcanoes are important sources of methane to the water column. However, the temporal variability of their mud and methane emissions is unknown. Methane emissions were previously proposed to result from a dynamic equilibrium between upward migration and consumption at the seabed by methane-consuming microbes. Here we show non-steady-state situations of vigorous mud movement that are revealed through variations in fluid flow, seabed temperature and seafloor bathymetry. Time series data for pressure, temperature, pH and seafloor photography were collected over 431 days using a benthic observatory at the active Håkon Mosby Mud Volcano. We documented 25 pulses of hot subsurface fluids, accompanied by eruptions that changed the landscape of the mud volcano. Four major events triggered rapid sediment uplift of more than a metre in height, substantial lateral flow of muds at average velocities of 0.4 m per day, and significant emissions of methane and CO2 from the seafloor. PMID:25384354

Synthesis of ZSM-5 zeolite from coal fly ash and rice husk: characterization and application for partial oxidation of methane to methanol

NASA Astrophysics Data System (ADS)

Krisnandi, Y. K.; Yanti, F. M.; Murti, S. D. S.

2017-04-01

Indonesian fly ash (SiO2/Al2O3 mole ratio = 3.59) was used together with rice husk (SiO2 92%) as raw material for mesoporous ZSM-5 zeolite synthesis. Prior being used, coal fly ash and rice husk were subjected to pre-treatment in order to extract silicate (SiO4 4-) and aluminate (AlO4 5-) and to remove the impurities. Then the ZSM-5 zeolite were synthesized through hydrothermal treatment using two types of templates (TPAOH and PDDA). The as-synthesized ZSM-5 was characterized using FTIR, XRD, SEM-EDX, and BET. The result of FTIR showed peaks at 1250-950 cm-1 (v asymetric T-O), 820-650 cm-1 (v symetric T-O), and at 650-500 cm-1 confirming the presence of the five number ring of the pentasil structure. The result of XRD showed the appearance of certain peaks in the position 2 theta between 7-9° and 22-25° indicative of ZSM-5 structure, but also showed the pattern of low intensity magnetite and hematite. The SEM image showed the rough surface of hexagonal crystals from ZSM-5 structure, indicative of mesoporosity in the structure. EDX result showed Si/Al ratio of 20, while surface area analysis gave SA of 43.16. The ZSM-5 zeolites then was modified with cobalt oxide through impregnation method. The catalytic activity as heterogeneous catalysts in partial oxidation of methane was tested. The result showed that hence the catalytic activity of ZSM-5 and Co/ZSM-5 from fly ash and rice husk were still inferior compared to the pro-analysis sourced-counterpart, they were potential to be used as catalyst in the partial oxidation of methane to methanol.

Turbulent convective heat transfer of methane at supercritical pressure in a helical coiled tube

NASA Astrophysics Data System (ADS)

Wang, Chenggang; Sun, Baokun; Lin, Wei; He, Fan; You, Yingqiang; Yu, Jiuyang

2018-02-01

The heat transfer of methane at supercritical pressure in a helically coiled tube was numerically investigated using the Reynolds Stress Model under constant wall temperature. The effects of mass flux ( G), inlet pressure ( P in) and buoyancy force on the heat transfer behaviors were discussed in detail. Results show that the light fluid with higher temperature appears near the inner wall of the helically coiled tube. When the bulk temperature is less than or approach to the pseudocritical temperature ( T pc ), the combined effects of buoyancy force and centrifugal force make heavy fluid with lower temperature appear near the outer-right of the helically coiled tube. Beyond the T pc , the heavy fluid with lower temperature moves from the outer-right region to the outer region owing to the centrifugal force. The buoyancy force caused by density variation, which can be characterized by Gr/ Re 2 and Gr/ Re 2.7, enhances the heat transfer coefficient ( h) when the bulk temperature is less than or near the T pc , and the h experiences oscillation due to the buoyancy force. The oscillation is reduced progressively with the increase of G. Moreover, h reaches its peak value near the T pc . Higher G could improve the heat transfer performance in the whole temperature range. The peak value of h depends on P in. A new correlation was proposed for methane at supercritical pressure convective heat transfer in the helical tube, which shows a good agreement with the present simulated results.

Attribution of changes in global wetland methane emissions from pre-industrial to present using CLM4.5-BGC

DOE PAGES

Paudel, Rajendra; Mahowald, Natalie M.; Hess, Peter G. M.; ...

2016-03-10

An understanding of potential factors controlling methane emissions from natural wetlands is important to accurately project future atmospheric methane concentrations. Here, we examine the relative contributions of climatic and environmental factors, such as precipitation, temperature, atmospheric CO 2 concentration, nitrogen deposition, wetland inundation extent, and land-use and land-cover change, on changes in wetland methane emissions from preindustrial to present day (i.e., 1850-2005). We apply a mechanistic methane biogeochemical model integrated in the Community Land Model version 4.5 (CLM4.5), the land component of the Community Earth System Model. The methane model explicitly simulates methane production, oxidation, ebullition, transport through aerenchyma ofmore » plants, and aqueous and gaseous diffusion. We conduct a suite of model simulations from 1850 to 2005, with all changes in environmental factors included, and sensitivity studies isolating each factor. Globally, we estimate that preindustrial methane emissions were higher by 10% than present-day emissions from natural wetlands, with emissions changes from preindustrial to the present of +15%, -41%, and -11% for the high latitudes, temperate regions, and tropics, respectively. The most important change is due to the estimated change in wetland extent, due to the conversion of wetland areas to drylands by humans. This effect alone leads to higher preindustrial global methane fluxes by 33% relative to the present, with the largest change in temperate regions (+80%). These increases were partially offset by lower preindustrial emissions due to lower CO 2 levels (10%), shifts in precipitation (7%), lower nitrogen deposition (3%), and changes in land-use and land-cover (2%). Cooler temperatures in the preindustrial regions resulted in our simulations in an increase in global methane emissions of 6% relative to present day. Much of the sensitivity to these perturbations is mediated in the model by changes in methane substrate production and the areal extent of wetlands. The detrended interannual variability of high-latitude methane emissions is explained by the variation in substrate production and wetland inundation extent, whereas the tropical emission variability is explained by both of those variables and precipitation.« less

Gene and transcript abundances of bacterial type III secretion systems from the rumen microbiome are correlated with methane yield in sheep.

PubMed

Kamke, Janine; Soni, Priya; Li, Yang; Ganesh, Siva; Kelly, William J; Leahy, Sinead C; Shi, Weibing; Froula, Jeff; Rubin, Edward M; Attwood, Graeme T

2017-08-08

Ruminants are important contributors to global methane emissions via microbial fermentation in their reticulo-rumens. This study is part of a larger program, characterising the rumen microbiomes of sheep which vary naturally in methane yield (g CH 4 /kg DM/day) and aims to define differences in microbial communities, and in gene and transcript abundances that can explain the animal methane phenotype. Rumen microbiome metagenomic and metatranscriptomic data were analysed by Gene Set Enrichment, sparse partial least squares regression and the Wilcoxon Rank Sum test to estimate correlations between specific KEGG bacterial pathways/genes and high methane yield in sheep. KEGG genes enriched in high methane yield sheep were reassembled from raw reads and existing contigs and analysed by MEGAN to predict their phylogenetic origin. Protein coding sequences from Succinivibrio dextrinosolvens strains were analysed using Effective DB to predict bacterial type III secreted proteins. The effect of S. dextrinosolvens strain H5 growth on methane formation by rumen methanogens was explored using co-cultures. Detailed analysis of the rumen microbiomes of high methane yield sheep shows that gene and transcript abundances of bacterial type III secretion system genes are positively correlated with methane yield in sheep. Most of the bacterial type III secretion system genes could not be assigned to a particular bacterial group, but several genes were affiliated with the genus Succinivibrio, and searches of bacterial genome sequences found that strains of S. dextrinosolvens were part of a small group of rumen bacteria that encode this type of secretion system. In co-culture experiments, S. dextrinosolvens strain H5 showed a growth-enhancing effect on a methanogen belonging to the order Methanomassiliicoccales, and inhibition of a representative of the Methanobrevibacter gottschalkii clade. This is the first report of bacterial type III secretion system genes being associated with high methane emissions in ruminants, and identifies these secretions systems as potential new targets for methane mitigation research. The effects of S. dextrinosolvens on the growth of rumen methanogens in co-cultures indicate that bacteria-methanogen interactions are important modulators of methane production in ruminant animals.

Attribution of changes in global wetland methane emissions from pre-industrial to present using CLM4.5-BGC

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paudel, Rajendra; Mahowald, Natalie M.; Hess, Peter G. M.

An understanding of potential factors controlling methane emissions from natural wetlands is important to accurately project future atmospheric methane concentrations. Here, we examine the relative contributions of climatic and environmental factors, such as precipitation, temperature, atmospheric CO 2 concentration, nitrogen deposition, wetland inundation extent, and land-use and land-cover change, on changes in wetland methane emissions from preindustrial to present day (i.e., 1850-2005). We apply a mechanistic methane biogeochemical model integrated in the Community Land Model version 4.5 (CLM4.5), the land component of the Community Earth System Model. The methane model explicitly simulates methane production, oxidation, ebullition, transport through aerenchyma ofmore » plants, and aqueous and gaseous diffusion. We conduct a suite of model simulations from 1850 to 2005, with all changes in environmental factors included, and sensitivity studies isolating each factor. Globally, we estimate that preindustrial methane emissions were higher by 10% than present-day emissions from natural wetlands, with emissions changes from preindustrial to the present of +15%, -41%, and -11% for the high latitudes, temperate regions, and tropics, respectively. The most important change is due to the estimated change in wetland extent, due to the conversion of wetland areas to drylands by humans. This effect alone leads to higher preindustrial global methane fluxes by 33% relative to the present, with the largest change in temperate regions (+80%). These increases were partially offset by lower preindustrial emissions due to lower CO 2 levels (10%), shifts in precipitation (7%), lower nitrogen deposition (3%), and changes in land-use and land-cover (2%). Cooler temperatures in the preindustrial regions resulted in our simulations in an increase in global methane emissions of 6% relative to present day. Much of the sensitivity to these perturbations is mediated in the model by changes in methane substrate production and the areal extent of wetlands. The detrended interannual variability of high-latitude methane emissions is explained by the variation in substrate production and wetland inundation extent, whereas the tropical emission variability is explained by both of those variables and precipitation.« less

Direct use of methane in coal liquefaction

DOEpatents

Sundaram, Muthu S.; Steinberg, Meyer

1987-01-01

This invention relates to a process for converting solid carbonaceous material, such as coal, to liquid and gaseous hydrocarbons utilizing methane, generally at a residence time of about 20-120 minutes at a temperature of 250.degree.-750.degree. C., preferably 350.degree.-450.degree. C., pressurized up to 6000 psi, and preferably in the 1000-2500 psi range, preferably directly utilizing methane 50-100% by volume in a mix of methane and hydrogen. A hydrogen donor solvent or liquid vehicle such as tetralin, tetrahydroquinoline, piperidine, and pyrolidine may be used in a slurry mix where the solvent feed is 0-100% by weight of the coal or carbonaceous feed. Carbonaceous feed material can either be natural, such as coal, wood, oil shale, petroleum, tar sands, etc., or man-made residual oils, tars, and heavy hydrocarbon residues from other processing systems.

Methane hydrate formation in confined nanospace can surpass nature

DOE PAGES

Casco, Mirian E.; Silvestre-Albero, Joaquín; Ramírez-Cuesta, Anibal J.; ...

2015-03-02

Natural methane hydrates are believed to be the largest source of hydrocarbons on Earth. These structures are formed in specific locations such as deep-sea sediments and the permafrost based on demanding conditions of high pressure and low temperature. We report that, by taking advantage of the confinement effects on nanopore space, synthetic methane hydrates grow under mild conditions (3.5 MPa and 2 degrees C), with faster kinetics (within minutes) than nature, fully reversibly and with a nominal stoichiometry that mimics nature. Furthermore, the formation of the hydrate structures in nanospace and their similarity to natural hydrates is confirmed using inelasticmore » neutron scattering experiments and synchrotron X-ray powder diffraction. Our findings may be a step towards the application of a smart synthesis of methane hydrates in energy-demanding applications (for example, transportation).« less

Background levels of methane in Mars’ atmosphere show strong seasonal variations

NASA Astrophysics Data System (ADS)

Webster, Christopher R.; Mahaffy, Paul R.; Atreya, Sushil K.; Moores, John E.; Flesch, Gregory J.; Malespin, Charles; McKay, Christopher P.; Martinez, German; Smith, Christina L.; Martin-Torres, Javier; Gomez-Elvira, Javier; Zorzano, Maria-Paz; Wong, Michael H.; Trainer, Melissa G.; Steele, Andrew; Archer, Doug; Sutter, Brad; Coll, Patrice J.; Freissinet, Caroline; Meslin, Pierre-Yves; Gough, Raina V.; House, Christopher H.; Pavlov, Alexander; Eigenbrode, Jennifer L.; Glavin, Daniel P.; Pearson, John C.; Keymeulen, Didier; Christensen, Lance E.; Schwenzer, Susanne P.; Navarro-Gonzalez, Rafael; Pla-García, Jorge; Rafkin, Scot C. R.; Vicente-Retortillo, Álvaro; Kahanpää, Henrik; Viudez-Moreiras, Daniel; Smith, Michael D.; Harri, Ari-Matti; Genzer, Maria; Hassler, Donald M.; Lemmon, Mark; Crisp, Joy; Sander, Stanley P.; Zurek, Richard W.; Vasavada, Ashwin R.

2018-06-01

Variable levels of methane in the martian atmosphere have eluded explanation partly because the measurements are not repeatable in time or location. We report in situ measurements at Gale crater made over a 5-year period by the Tunable Laser Spectrometer on the Curiosity rover. The background levels of methane have a mean value 0.41 ± 0.16 parts per billion by volume (ppbv) (95% confidence interval) and exhibit a strong, repeatable seasonal variation (0.24 to 0.65 ppbv). This variation is greater than that predicted from either ultraviolet degradation of impact-delivered organics on the surface or from the annual surface pressure cycle. The large seasonal variation in the background and occurrences of higher temporary spikes (~7 ppbv) are consistent with small localized sources of methane released from martian surface or subsurface reservoirs.

Annual variability and regulation of methane and sulfate fluxes in Baltic Sea estuarine sediments

NASA Astrophysics Data System (ADS)

Sawicka, Joanna E.; Brüchert, Volker

2017-01-01

Marine methane emissions originate largely from near-shore coastal systems, but emission estimates are often not based on temporally well-resolved data or sufficient understanding of the variability of methane consumption and production processes in the underlying sediment. The objectives of our investigation were to explore the effects of seasonal temperature, changes in benthic oxygen concentration, and historical eutrophication on sediment methane concentrations and benthic fluxes at two type localities for open-water coastal versus eutrophic, estuarine sediment in the Baltic Sea. Benthic fluxes of methane and oxygen and sediment pore-water concentrations of dissolved sulfate, methane, and 35S-sulfate reduction rates were obtained over a 12-month period from April 2012 to April 2013. Benthic methane fluxes varied by factors of 5 and 12 at the offshore coastal site and the eutrophic estuarine station, respectively, ranging from 0.1 mmol m-2 d-1 in winter at an open coastal site to 2.6 mmol m-2 d-1 in late summer in the inner eutrophic estuary. Total oxygen uptake (TOU) and 35S-sulfate reduction rates (SRRs) correlated with methane fluxes showing low rates in the winter and high rates in the summer. The highest pore-water methane concentrations also varied by factors of 6 and 10 over the sampling period with the lowest values in the winter and highest values in late summer-early autumn. The highest pore-water methane concentrations were 5.7 mM a few centimeters below the sediment surface, but they never exceeded the in situ saturation concentration. Of the total sulfate reduction, 21-24 % was coupled to anaerobic methane oxidation, lowering methane concentrations below the sediment surface far below the saturation concentration. The data imply that bubble emission likely plays no or only a minor role in methane emissions in these sediments. The changes in pore-water methane concentrations over the observation period were too large to be explained by temporal changes in methane formation and methane oxidation rates due to temperature alone. Additional factors such as regional and local hydrostatic pressure changes and coastal submarine groundwater flow may also affect the vertical and lateral transport of methane.

Gas hydrate dissociation via in situ combustion of methane - lab studies and field tests

NASA Astrophysics Data System (ADS)

Luzi-Helbing, Manja; Schicks, Judith M.; Spangenberg, Erik; Giese, Ronny

2013-04-01

In general, three different methods for gas hydrate production are known: thermal stimulation, pressure reduction, and chemical stimulation. In the framework of the German joint project SUGAR (Submarine Gas Hydrate Reservoirs: exploration, extraction and transport) a countercurrent heat exchange reactor was developed at GFZ which has been designed to decompose gas hydrates in sediments via thermal stimulation. The heat is produced by the catalytic oxidation of methane. The advantage of this method is that the heat is generated in place i.e. within the borehole on the same level like the hydrate-bearing sediments. The system is closed which means that there is no contact between the products or catalyst and the environment. The power output and the temperature of the reactor are regulated via the volume flow of the feed gases air and methane. Therefore, the catalytic reaction runs temperature-controlled, autothermic and safe. So far, a lab-scale prototype of the reactor (outer diameter 40 mm, length 457 mm) was successfully tested in a large reservoir simulator (LARS) which was set up at GFZ. Pt, Pd and Ir on ZrO2 as carrier material turned out to be a robust and reliable catalyst. This work presents results of the latest reactor test for which LARS was filled with sand, and ca. 80 % of the pore space was saturated with methane hydrate. To form hydrates the pore pressure and the confining pressure were kept at 8 MPa and 12 MPa, respectively, and the temperature was set to 278 K. During the start sequence the reactor was ignited at room temperature with hydrogen. By the time the reactor temperature reached ca. 523 K (ca. 15 min after hydrogen ignition) the fuel flow was changed to methane. After 9 hours all temperature sensors which are spatially distributed in LARS showed a temperature above the equilibrium temperature of 282 K at 8 MPa. All in all, the reactor was run for 12 h at 723 K. The data analysis showed that 15 % of the methane gas released from hydrates would have to be used for the catalytic combustion of methane. However, only a part of the hydrate-bound methane gas could be produced during the experiment. The residual gas remained in the pore space. Currently the pilot-scale reactor is developed to a borehole tool with an outer diameter of 90 mm and ca. 5 m length. The first field test is planned for summer 2013 at the continental deep drilling KTB in Windischeschenbach, Germany. In future, we aim for a field test in hydrate-bearing sediments.

Properties of Silurian shales from the Barrandian Basin, Czech Republic

NASA Astrophysics Data System (ADS)

Weishauptová, Zuzana; Přibyl, Oldřich; Sýkorová, Ivana

2017-04-01

Although shale gas-bearing deposits have a markedly lower gas content than coal deposits, great attention has recently been paid to shale gas as a new potential source of fossil energy. Shale gas extraction is considered to be quite economical, despite the lower sorption capacity of shales, which is only about 10% of coal sorption capacities The selection of a suitable locality for extracting shale gas requires the sorption capacity of the shale to be determined. The sorption capacity is determined in the laboratory by measuring the amount of methane absorbed in a shale specimen at a pressure and a temperature corresponding to in situ conditions, using high pressure sorption. According to the principles of reversibility of adsorption/desorption, this amount should be roughly related to the amount of gas released by forced degassing. High pressure methane sorption isotherms were measured on seven representative samples of Silurian shales from the Barrandian Basin, Czech Republic. Excess sorption measurements were performed at a temperature of 45oC and at pressures up to 15 MPa on dry samples, using a manometric method. Experimental methane high-pressure isotherms were fitted to a modified Langmuir equation. The maximum measured excess sorption parameter and the Langmuir sorption capacity parameter were used to study the effect of TOC content, organic maturity, inorganic components and porosity on the methane sorption capacity. The studied shale samples with random reflectance of graptolite 0.56 to 1.76% had a very low TOC content and dominant mineral fractions. Illite was the prevailing clay mineral. The sample porosity ranged from 4.6 to 18.8%. In most samples, the micropore volumes were markedly lower than the meso- and macropore volumes. In the Silurian black shales, the occurrence of fractures parallel with the original sedimentary bending was highly significant. A greater proportion of fragments of carbonaceous particles of graptolites and bitumens in the Barrandian Silurian shales had a smooth surface without pores. No relation has been proven between TOC-normalized excess sorption capacities or the TOC-normalized Langmuir sorption capacities and thermal maturation of the shales. The methane sorption capacities of shale samples show a positive correlation with TOC and a positive correlation with the clay content. The highest sorption capacity was observed in shale samples with the highest percentage of micropores, indicating that the micropore volume in the organic matter and clay minerals is a principal factor affecting the sorption capacity of the shale samples.

Partial Pressures of Te2 and Thermodynamic Properties of Ga-Te System

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Curreri, Peter A. (Technical Monitor)

2001-01-01

The partial pressures of Te2 in equilibrium with Ga(1-x)Te(x) samples were measured by optical absorption technique from 450 to 1100 C for compositions, x, between 0.333 and 0.612. To establish the relationship between the partial pressure of Te, and the measured optical absorbance, the calibration runs of a pure Te sample were also conducted to determine the Beer's Law constants. The partial pressures of Te2 in equilibrium with the GaTe(s) and Ga2Te3(s)compounds, or the so-called three-phase curves, were established. These partial pressure data imply the existence of the Ga3Te4(s) compound. From the partial pressures of Te2 over the Ga-Te melts, partial molar enthalpy and entropy of mixing for Te were derived and they agree reasonable well with the published data. The activities of Te in the Ga-Te melts were also derived from the measured partial pressures of Te2. These data agree well with most of the previous results. The possible reason for the high activity of Te measured for x less than 0.60 is discussed.

Survivability and growth kinetics of methanogenic archaea at various pHs and pressures: Implications for deep subsurface life on Mars

NASA Astrophysics Data System (ADS)

Sinha, Navita; Nepal, Sudip; Kral, Timothy; Kumar, Pradeep

2017-02-01

Life as we know it requires liquid water and sufficient liquid water is highly unlikely on the surface of present-day Mars. However, according to thermal models there is a possibility of liquid water in the deep subsurface of Mars. Thus, the martian subsurface, where the pressure and temperature is higher, could potentially provide a hospitable environment for a biosphere. Also, methane has been detected in the Mars' atmosphere. Analogous to Earth's atmospheric methane, martian methane could also be biological in origin. The carbon and energy sources for methanogenesis in the subsurface of Mars could be available by downwelling of atmospheric CO2 into the regolith and water-rock reactions such as serpentinization, respectively. Corresponding analogs of the martian subsurface on Earth might be the active sites of serpentinization at depths where methanogenic thermophilic archaea are the dominant species. Methanogens residing in Earth's hydrothermal environments are usually exposed to a variety of physiological stresses including a wide range of pressures, temperatures, and pHs. Martian geochemical models imply that the pH of probable groundwater varies from 4.96 to 9.13. In this work, we used the thermophilic methanogen, Methanothermobacter wolfeii, which grows optimally at 55oC. Therefore, a temperature of 55oC was chosen for these experiments, possibly simulating Mars' subsurface temperature. A martian geophysical model suggests depth and pressure corresponding to a temperature of 55 °C would be between 1-30 km and 100-3,000 atm respectively. Here, we have simulated Mars deep subsurface pH, pressure, and temperature conditions and have investigated the survivability, growth rate, and morphology of M. wolfeii after exposure to a wide range of pH 5-9) and pressure (1-1200 atm) at a temperature of 55 °C. Interestingly, in this study we have found that M. wolfeii was able to survive at all the pressures and pHs tested at 55 °C. In order to understand the effect of different pHs and pressures on the metabolic activities of M. wolfeii, we also calculated their growth rate by measuring methane concentration in the headspace gas samples at regular intervals. In acidic conditions, the growth rate (γ) of M. wolfeii increased with the increase in pressure. In neutral and alkaline conditions, the growth rate (γ) of M. wolfeii initially increased with pressure, but decreased upon further increase of pressure. To investigate the effect of combined pH, pressure, and temperature on the morphology of M. wolfeii, we took phase contrast images of the cells. We did not find any obvious significant alteration in the morphology of M. wolfeii cells. Methanogens, chemolithoautotrophic anaerobic microorganisms, are considered as ideal model microorganisms for Mars. In light of research presented here, we suggest that at least one methanogen, M. wolfeii, could survive in the deep subsurface environment of Mars.

[Progress in Raman spectroscopic measurement of methane hydrate].

PubMed

Xu, Feng; Zhu, Li-hua; Wu, Qiang; Xu, Long-jun

2009-09-01

Complex thermodynamics and kinetics problems are involved in the methane hydrate formation and decomposition, and these problems are crucial to understanding the mechanisms of hydrate formation and hydrate decomposition. However, it was difficult to accurately obtain such information due to the difficulty of measurement since methane hydrate is only stable under low temperature and high pressure condition, and until recent years, methane hydrate has been measured in situ using Raman spectroscopy. Raman spectroscopy, a non-destructive and non-invasive technique, is used to study vibrational modes of molecules. Studies of methane hydrate using Raman spectroscopy have been developed over the last decade. The Raman spectra of CH4 in vapor phase and in hydrate phase are presented in this paper. The progress in the research on methane hydrate formation thermodynamics, formation kinetics, decomposition kinetics and decomposition mechanism based on Raman spectroscopic measurements in the laboratory and deep sea are reviewed. Formation thermodynamic studies, including in situ observation of formation condition of methane hydrate, analysis of structure, and determination of hydrate cage occupancy and hydration numbers by using Raman spectroscopy, are emphasized. In the aspect of formation kinetics, research on variation in hydrate cage amount and methane concentration in water during the growth of hydrate using Raman spectroscopy is also introduced. For the methane hydrate decomposition, the investigation associated with decomposition mechanism, the mutative law of cage occupancy ratio and the formulation of decomposition rate in porous media are described. The important aspects for future hydrate research based on Raman spectroscopy are discussed.

Intense methane ebullition from open water area of a shallow peatland lake on the eastern Tibetan Plateau.

PubMed

Zhu, Dan; Wu, Yan; Chen, Huai; He, Yixin; Wu, Ning

2016-01-15

Methane fluxes from a shallow peatland lake (3450 m a.s.l., 1.6 km(2) in area, maximum depth <1m) on eastern Tibetan Plateau were measured with floating chamber method during May to August, 2009. The overall average of methane emission rate during the study period was 34.71±29.15 mg CH4 m(-2) h(-1). The occurrence of ebullition among the overall methane flux from Lake Medo was about 74%. The average rate of ebullition was 32.45±28.31 mg CH4 m(-2) h(-1), which accounted for 93% of the overall average of methane emission. Significant seasonal variation was found for occurrence (P<0.05) and rate (P<0.01) of ebullition, both peaking synchronously in mid-summer. Both the occurrence and rate of ebullition were found positively related to sediment temperature but negatively related to lake water depth. The high methane production in the lake sediment was likely fueled by organic carbon loaded from surrounding peatlands to the lake. The shallowness of the water column could be another important favorable factor for methane-containing bubble formation in the sediment and their transportation to the atmosphere. The methane ebullition must have been enhanced by the low atmospheric pressure (ca. 672 hPa) in the high-altitude environment. For a better understanding on the mechanism of methane emission from alpine lakes, more lakes on the Tibetan Plateau should be studied in the future for their methane ebullition. Copyright © 2015 Elsevier B.V. All rights reserved.

Comparative use of different emission measurement approaches to determine methane emissions from a biogas plant.

PubMed

Reinelt, Torsten; Delre, Antonio; Westerkamp, Tanja; Holmgren, Magnus A; Liebetrau, Jan; Scheutz, Charlotte

2017-10-01

A sustainable anaerobic biowaste treatment has to mitigate methane emissions from the entire biogas production chain, but the exact quantification of these emissions remains a challenge. This study presents a comparative measurement campaign carried out with on-site and ground-based remote sensing measurement approaches conducted by six measuring teams at a Swedish biowaste treatment plant. The measured emissions showed high variations, amongst others caused by different periods of measurement performance in connection with varying operational states of the plant. The overall methane emissions measured by ground-based remote sensing varied from 5 to 25kgh -1 (corresponding to a methane loss of 0.6-3.0% of upgraded methane produced), depending on operating conditions and the measurement method applied. Overall methane emissions measured by the on-site measuring approaches varied between 5 and 17kgh -1 (corresponding to a methane loss of 0.6 and 2.1%) from team to team, depending on the number of measured emission points, operational state during the measurements and the measurement method applied. Taking the operational conditions into account, the deviation between different approaches and teams could be explained, in that the two largest methane-emitting sources, contributing about 90% of the entire site's emissions, were found to be the open digestate storage tank and a pressure release valve on the compressor station. Copyright © 2017. Published by Elsevier Ltd.

The structure of partially-premixed methane/air flames under varying premixing

NASA Astrophysics Data System (ADS)

Kluzek, Celine; Karpetis, Adonios

2008-11-01

The present work examines the spatial and scalar structure of laminar, partially premixed methane/air flames with the objective of developing flamelet mappings that capture the effect of varying premixture strength (air addition in fuel.) Experimental databases containing full thermochemistry measurements within laminar axisymmetric flames were obtained at Sandia National Laboratories, and the measurements of all major species and temperature are compared to opposed-jet one-dimensional flow simulation using Cantera and the full chemical kinetic mechanism of GRI 3.0. Particular emphasis is placed on the scalar structure of the laminar flames, and the formation of flamelet mappings that capture all of the salient features of thermochemistry in a conserved scalar representation. Three different premixture strengths were examined in detail: equivalence ratios of 1.8, 2.2, and 3.17 resulted in clear differences in the flame scalar structure, particularly in the position of the rich premixed flame zone and the attendant levels of major and intermediate species (carbon monoxide and hydrogen).

Formation of hydrocarbons under upper mantle conditions: experimental view

NASA Astrophysics Data System (ADS)

Kolesnikov, Anton; Kutcherov, Vladimir G.

2010-05-01

Main postulates of the theory of abiogenic abyssal origin of petroleum have been developed in the last 50 years in Russia and Ukraine. According to this theory, hydrocarbon compounds were generated in the mantle and migrated through the deep faults into the Earth's crust. There they formed oil and gas deposits in any kinds of rocks and in any kind of their structural positions. Until recently the main obstacle to accept the theory was the lack of reliable and reproducible experimental data confirming the possibility of the synthesis of complex hydrocarbon systems under the mantle conditions. The results received in the last decade by different groups of researchers from Russia, U.S.A. and China have confirmed the possibility of generation of hydrocarbons from inorganic materials, highly distributed in the Earth's mantle, under thermobaric conditions of 70-250 km: 2 - 5 GPa and 1000-1500 K. Experiments made in the CONAC chamber at pressures of 3-5 GPa and temperatures of 1000-1500 K by Kutcherov et al. [1, 2] have demonstrated that the mixtures of hydrocarbons with composition similar to natural hydrocarbon systems have been received as a result of chemical reactions between CaCO3, FeO and H2O. Methane formation from the same compounds was registered after heating up to 600-1500 K at pressures of 4-11 GPa in diamond anvil cells [4, 5, 6]. Influence of oxidation state of carbon donor and cooling rate of the fluid synthesized at high pressure were studied using different types of high pressure equipments. It was shown that composition of the final hydrocarbon mixture depends on these parameters. Experimental investigations of transformation of methane and ethane at 2-5 GPa and 1000-1500 K [3] confirmed thermodynamic stability of heavy hydrocarbons in the upper mantle and showed the possibility of hydrocarbon chain growth even at oxidative environment. For development of the theory of abiogenic abyssal origin of petroleum it is necessary to arrange a set of new experiments to understand the pathways of hydrocarbons formation, influence of pressure, temperature, oxygen fugacity and chemical composition of the environment on the content of the mantle fluid. [1] Kutcherov, V. G., Bendeliani, N. A. Alekseev, V. A. & Kenney, J. F. Synthesis of Hydrocarbons from Minerals at Pressures up to 5 GPa. Doklady Physical Chemistry, 387, 4-6, 328-330 (2002). [2] Kenney, J. F., Kutcherov, V. G., Bendeliani, N. A. & Alekseev, V. A. The Evolution of Multicomponent Systems at High Pressures: VI. The Thermodynamic Stability of the Hydrogen-Carbon System: The Genesis of Hydrocarbons and the Origin of Petroleum. Proc. Natl. Acad. Sci. U.S.A., 99, 10976-10981 (2002). [3] Kolesnikov A., Kutcherov V. G. and Goncharov A. F. Methane-derived hydrocarbons produced under upper-mantle conditions. Nature Geoscience, 2, 566 - 570 (2009). [4] Scott H.P., Hemley R.J, Mao H. et al. Generation of methane in the Earth's mantle: In situ high pressure-temperature measurements of carbonate reduction, Proc. Natl. Acad. Sci. U.S.A., 101 14023-14026 (2004). [5] Chen J.Y., et al. Methane formation from CaCO3 reduction catalyzed by high pressure. Chin. Chem. Lett., 19, 4, 475-478 (2008). [6] Sharma A., Cody G. D., and Hemley R. J. In situ Diamond-anvil cell observations of methanogenesis at high pressures and temperatures. Energy Fuels, 23, 11, 5571-5579 (2009).

Optimization of UA of heat exchangers and BOG compressor exit pressure of LNG boil-off gas reliquefaction system using exergy analysis

NASA Astrophysics Data System (ADS)

Kochunni, Sarun Kumar; Ghosh, Parthasarathi; Chowdhury, Kanchan

2015-12-01

Boil-off gas (BOG) generation and its handling are important issues in Liquefied natural gas (LNG) value chain because of economic, environment and safety reasons. Several variants of reliquefaction systems of BOG have been proposed by researchers. Thermodynamic analyses help to configure them and size their components for improving performance. In this paper, exergy analysis of reliquefaction system based on nitrogen-driven reverse Brayton cycle is carried out through simulation using Aspen Hysys 8.6®, a process simulator and the effects of heat exchanger size with and without related pressure drop and BOG compressor exit pressure are evaluated. Nondimensionalization of parameters with respect to the BOG load allows one to scale up or down the design. The process heat exchanger (PHX) requires much higher surface area than that of BOG condenser and it helps to reduce the quantity of methane vented out to atmosphere. As pressure drop destroys exergy, optimum UA of PHX decreases for highest system performance if pressure drop is taken into account. Again, for fixed sizes of heat exchangers, as there is a range of discharge pressures of BOG compressor at which the loss of methane in vent minimizes, the designer should consider choosing the pressure at lower value.

Determination of Water Vapor Pressure Over Corrosive Chemicals Versus Temperature Using Raman Spectroscopy as Exemplified with 85.5% Phosphoric Acid.

PubMed

Rodier, Marion; Li, Qingfeng; Berg, Rolf Willestofte; Bjerrum, Niels Janniksen

2016-07-01

A method to determine the water vapor pressure over a corrosive substance was developed and tested with 85.5 ± 0.4% phosphoric acid. The water vapor pressure was obtained at a range of temperatures from ∼25 ℃ to ∼200 ℃ using Raman spectrometry. The acid was placed in an ampoule and sealed with a reference gas (either hydrogen or methane) at a known pressure (typically ∼0.5 bar). By comparing the Raman signals from the water vapor and the references, the water pressure was determined as a function of temperature. A considerable amount of data on the vapor pressure of phosphoric acid are available in the literature, to which our results could successfully be compared. A record value of the vapor pressure, 3.40 bar, was determined at 210 ℃. The method required a determination of the precise Raman scattering ratios between the substance, water, and the used reference gas, hydrogen or methane. In our case the scattering ratios between water and reference ν1 Q-branches were found to be 1.20 ± 0.03 and 0.40 ± 0.02 for H2 and CH4, respectively. © The Author(s) 2016.

Determination of the combustion behavior for pure components and mixtures using a 20-liter sphere

NASA Astrophysics Data System (ADS)

Mashuga, Chad Victor

1999-11-01

The safest method to prevent fires and explosions of flammable vapors is to prevent the existence of flammable mixtures in the first place. This methodology requires detailed knowledge of the flammability region as a function of the fuel, oxygen, and nitrogen concentrations. A triangular flammability diagram is the most useful tool to display the flammability region, and to determine if a flammable mixture is present during plant operations. An automated apparatus for assessing the flammability region and for determining the potential effect of confined fuel-air explosions is described. Data derived from the apparatus included the limits of combustion, maximum combustion pressure, and the deflagration index, or KG. Accurate measurement of these parameters can be influenced by numerous experimental conditions, including igniter energy, humidity and gas composition. Gas humidity had a substantial effect on the deflagration index, but had little effect on the maximum combustion pressure. Small changes in gas compositions had a greater effect on the deflagration index than the maximum combustion pressure. Both the deflagration indices and the maximum combustion pressure proved insensitive to the range of igniter energies examined. Estimation of flammability limits using a calculated adiabatic flame temperature (CAFT) method is demonstrated. The CAFT model is compared with the extensive experimental data from this work for methane, ethylene and a 50/50 mixture of methane and ethylene. The CAFT model compares well to methane and ethylene throughout the flammability zone when using a 1200K threshold temperature. Deviations between the method and the experimental data occurs in the fuel rich region. For the 50/50 fuel mixture the CAFT deviates only in the fuel rich region---the inclusion of carbonaceous soot as one of the equilibrium products improved the fit. Determination of burning velocities from a spherical flame model utilizing the extensive pressure---time data was also completed. The burning velocities determined compare well to other investigators using this method. The data collected for the methane/ethylene mixture was used to evaluate mixing rules for the flammability limits, maximum combustion pressure, deflagration index, and burning velocity. These rules attempt to predict the behavior of fuel mixtures from pure component data. Le Chatelier's law and averaging both work well for predicting the flammability boundary in the fuel lean region and for mixtures of inerted fuel and air. Both methods underestimate the flammability boundary in the fuel rich region. For a mixture of methane and ethylene, we were unable to identify mixing rules for estimating the maximum combustion pressure and the burning velocity from pure component data. Averaging the deflagration indices for fuel air mixtures did provide a adequate estimation of the mixture behavior. Le Chatelier's method overestimated the maximum deflagration index in air but provided a satisfactory estimation in the extreme fuel lean and rich regions.

Natural gas hydrate occurrence and issues

USGS Publications Warehouse

Kvenvolden, K.A.

1994-01-01

Naturally occurring gas hydrate is found in sediment of two regions: (1) continental, including continental shelves, at high latitudes where surface temperatures are very cold, and (2) submarine outer continental margins where pressures are very high and bottom-water temperatures are near 0??C. Continental gas hydrate is found in association with onshore and offshore permafrost. Submarine gas hydrate is found in sediment of continental slopes and rises. The amount of methane present in gas hydrate is thought to be very large, but the estimates that have been made are more speculative than real. Nevertheless, at the present time there has been a convergence of ideas regarding the amount of methane in gas hydrate deposits worldwide at about 2 x 1016 m3 or 7 x 1017 ft3 = 7 x 105 Tcf [Tcf = trillion (1012) ft3]. The potentially large amount of methane in gas hydrate and the shallow depth of gas hydrate deposits are two of the principal factors driving research concerning this substance. Such a large amount of methane, if it could be commercially produced, provides a potential energy resource for the future. Because gas hydrate is metastable, changes of surface pressure and temperature affect its stability. Destabilized gas hydrate beneath the sea floor leads to geologic hazards such as submarine mass movements. Examples of submarine slope failures attributed to gas hydrate are found worldwide. The metastability of gas hydrate may also have an effect on climate. The release of methane, a 'greenhouse' gas, from destabilized gas hydrate may contribute to global warming and be a factor in global climate change.

Nitrogen oxides and methane treatment by non-thermal plasma

NASA Astrophysics Data System (ADS)

Alva, E.; Pacheco, M.; Colín, A.; Sánchez, V.; Pacheco, J.; Valdivia, R.; Soria, G.

2015-03-01

Non thermal plasma was used to treat nitrogen oxides (NOx) and methane (CH4), since they are important constituents of hydrocarbon combustion emissions processes and, both gases, play a key role in the formation of tropospheric ozone. These gases are involved in environmental problems like acid rain and some diseases such as bronchitis and pneumonia. In the case of methane is widely known its importance in the global climate change, and currently accounts for 30% of global warming. There is a growing concern for methane leaks, associated with a rapid expansion of unconventional oil and gas extraction techniques as well as a large-scale methane release from Arctic because of ice melting and the subsequent methane production of decaying organic matter. Therefore, methane mitigation is a key to avoid dangerous levels of global warming. The research, here reported, deals about the generation of non-thermal plasma with a double dielectric barrier (2DBD) at atmospheric pressure with alternating current (AC) for NOx and CH4 treatment. The degradation efficiencies and their respective power consumption for different reactor configurations (cylindrical and planar) are also reported. Qualitative and quantitative analysis of gases degradation are reported before and after treatment with cold plasma. Experimental and theoretical results are compared obtaining good removal efficiencies, superior to 90% and to 20% respectively for NOx and CH4.

Oxygen Partial Pressure and Oxygen Concentration Flammability: Can They Be Correlated?

NASA Technical Reports Server (NTRS)

Harper, Susana A.; Juarez, Alfredo; Perez, Horacio, III; Hirsch, David B.; Beeson, Harold D.

2016-01-01

NASA possesses a large quantity of flammability data performed in ISS airlock (30% Oxygen 526mmHg) and ISS cabin (24.1% Oxygen 760 mmHg) conditions. As new programs develop, other oxygen and pressure conditions emerge. In an effort to apply existing data, the question arises: Do equivalent oxygen partial pressures perform similarly with respect to flammability? This paper evaluates how material flammability performance is impacted from both the Maximum Oxygen Concentration (MOC) and Maximum Total Pressures (MTP) perspectives. From these studies, oxygen partial pressures can be compared for both the MOC and MTP methods to determine the role of partial pressure in material flammability. This evaluation also assesses the influence of other variables on flammability performance. The findings presented in this paper suggest flammability is more dependent on oxygen concentration than equivalent partial pressure.

Effects of Mars Regolith Analogs, UVC radiation, Temperature, Pressure, and pH on the Growth and Survivability of Methanogenic Archaea and Stable Carbon Isotope Fractionation: Implications for Surface and Subsurface Life on Mars

NASA Astrophysics Data System (ADS)

Sinha, Navita

Mars is one of the suitable bodies in our solar system that can accommodate extraterrestrial life. The detection of plumes of methane in the Martian atmosphere, geochemical evidence, indication of flow of intermittent liquid water on the Martian surface, and geomorphologies of Mars have bolstered the plausibility of finding extant or evidence of extinct life on its surface and/or subsurface. However, contemporary Mars has been considered as an inhospitable planet for several reasons, such as low atmospheric surface pressure, low surface temperature, and intense DNA damaging radiation. Despite the hostile conditions of Mars, a few strains of methanogenic archaea have shown survivability in limited surface and subsurface conditions of Mars. Methanogens, which are chemolithoautotrophic non-photosynthetic anaerobic archaea, have been considered ideal models for possible Martian life forms for a long time. The search for biosignatures in the Martian atmosphere and possibility of life on the Martian surface under UVC radiation and deep subsurface under high pressure, temperature, and various pHs are the motivations of this research. Analogous to Earth, Martian atmospheric methane could be biological in origin. Chapter 1 provides relevant information about Mars' habitability, methane on Mars, and different strains of methanogens used in this study. Chapter 2 describes the interpretation of the carbon isotopic data of biogenic methane produced by methanogens grown on various Mars analogs and the results provide clues to determine ambiguous sources of methane on Mars. Chapter 3 illustrates the sensitivity of hydrated and desiccated cultures of halophilic and non-halophilic methanogens to DNA-damaging ultraviolet radiations, and the results imply that UVC radiation may not be an enormous constraint for methanogenic life forms on the surface of Mars. Chapters 4, 5, and 6 discuss the data for the survivability, growth, and morphology of methanogens in presumed deep subsurface physicochemical conditions such as temperature, pressure, hydrogen concentration, and pH of Mars. Finally, chapter 7 provides conclusions, limitations of the experiments, and future perspective of the work. Overall, the quantitative measurements obtained in the various sections of this novel work provide insights to atmospheric biosignatures and survivability of methanogenic organisms on the surface and subsurface of Mars.

Impact of gas backing pressure and geometry of conical nozzle on the formation of methane clusters in supersonic jets.

PubMed

Lu, Haiyang; Chen, Guanglong; Ni, Guoquan; Li, Ruxin; Xu, Zhizhan

2010-01-14

We present an experimental investigation of the dependence of the production of large methane clusters on the cluster source conditions. The clusters were produced at room temperature through supersonic expansion of methane gas at the backing pressures P(0) ranging from 10 to 84 bar using five conical nozzles of different geometries. The cluster size was characterized by Rayleigh scattering measurements and calibrated with Coulomb explosion of the clusters at P(0) = 44 bar subjected to an ultraintense laser pulse. A quantitative evaluation of the performance of the conical nozzles against the nozzle geometry and the backing pressure was made by introducing a parameter delta. Differ from the idealized case where the performance of the conical nozzle can be described by the equivalent sonic nozzle of diameter d(eq), in the present work, the "effective equivalent sonic-nozzle diameter" of the conical nozzle defined by d(eq)* = deltad(eq) is introduced. delta represents the deviation of the performance in cluster formation of the conical nozzles from that predicted on the basis of the concept of the equivalent diameter d(eq) = d/tan alpha, with d being the throat diameter, and alpha the half-opening angle of the conical nozzle. Experimental results show that the cluster growth process will be restricted when the gas backing pressure P(0) is higher and/or d/tan alpha of the conical nozzle becomes larger, resulting in smaller delta. From the experimental data, delta can be expressed by an empirical relation delta = A/[P(0)(B)(d/tan alpha)(1.36)], where A = 8.4 and B = 0.26 for 24 bar

40 CFR Table W - 7 of Subpart W of Part 98-Default Methane Emission Factors for Natural Gas Distribution

Code of Federal Regulations, 2014 CFR

2014-07-01

... Connector 1.69 Block Valve 0.557 Control Valve 9.34 Pressure Relief Valve 0.27 Orifice Meter 0.212 Regulator 0.772 Open-ended Line 26.131 Population Emission Factors—Below Grade Metering-Regulating station 1..., Inlet Pressure 100 to 300 psig 0.20 Below Grade M&R Station, Inlet Pressure Population...

40 CFR Table W - 7 of Subpart W of Part 98-Default Methane Emission Factors for Natural Gas Distribution

Code of Federal Regulations, 2013 CFR

2013-07-01

... Connector 1.69 Block Valve 0.557 Control Valve 9.34 Pressure Relief Valve 0.27 Orifice Meter 0.212 Regulator 0.772 Open-ended Line 26.131 Population Emission Factors—Below Grade Metering-Regulating station 1..., Inlet Pressure 100 to 300 psig 0.20 Below Grade M&R Station, Inlet Pressure Population...

Laboratory measurements and methane photochemistry modeling

NASA Technical Reports Server (NTRS)

Romani, P. N.

1990-01-01

Methane is photolyzed by the solar UV in the stratosphere of Saturn. Subsequent photochemistry leads to the production of acetylene (C2H2) and diacetylene (C4H2). These species are produced where it is relatively warm (T is greater than or equal to 140 K), but the tropopause temperature of Saturn (approximately 80 K) is low enough that these two species may freeze out to their respective ices. Numerical models which include both photochemistry and condensation loss make predictions about the mixing ratios of these species and haze production rates. These models are dependent upon knowing reaction pathways and their associated kinetic reaction rate constants and vapor pressures. How uncertainties in the chemistry and improvements in the vapor pressures affect model predictions for Saturn are discussed.

Thermal regulation of methane hydrate dissociation: Implications for gas production models

USGS Publications Warehouse

Circone, S.; Kirby, S.H.; Stern, L.A.

2005-01-01

Thermal self-regulation of methane hydrate dissociation at pressure, temperature conditions along phase boundaries, illustrated by experiment in this report, is a significant effect with potential relevance to gas production from gas hydrate. In surroundings maintained at temperatures above the ice melting point, the temperature in the vicinity of dissociating methane hydrate will decrease because heat flow is insufficient to balance the heat absorbed by the endothermic reaction: CH4??nH2O (s) = CH4 (g) + nH2O (l). Temperature decreases until either all of the hydrate dissociates or a phase boundary is reached. At pressures above the quadruple point, the temperature-limiting phase boundary is that of the dissociation reaction itself. At lower pressures, the minimum temperature is limited by the H2O solid/liquid boundary. This change in the temperature-limiting phase boundary constrains the pressure, temperature conditions of the quadruple point for the CH4-H2O system to 2.55 ?? 0.02 MPa and 272.85 ?? 0.03 K. At pressures below the quadruple point, hydrate dissociation proceeds as the liquid H2O produced by dissociation freezes. In the laboratory experiments, dissociation is not impeded by the formation of ice byproduct per se; instead rates are proportional to the heat flow from the surroundings. This is in contrast to the extremely slow dissociation rates observed when surrounding temperatures are below the H2O solid/liquid boundary, where no liquid water is present. This "anomalous" or "self" preservation behavior, most pronounced near 268 K, cannot be accessed when surrounding temperatures are above the H2O solid/liquid boundary. ?? 2005 American Chemical Society.

Thermal properties of methane gas hydrates

USGS Publications Warehouse

Waite, William F.

2007-01-01

Gas hydrates are crystalline solids in which molecules of a “guest” species occupy and stabilize cages formed by water molecules. Similar to ice in appearance (fig. 1), gas hydrates are stable at high pressures and temperatures above freezing (0°C). Methane is the most common naturally occurring hydrate guest species. Methane hydrates, also called simply “gas hydrates,” are extremely concentrated stores of methane and are found in shallow permafrost and continental margin sediments worldwide. Brought to sea-level conditions, methane hydrate breaks down and releases up to 160 times its own volume in methane gas. The methane stored in gas hydrates is of interest and concern to policy makers as a potential alternative energy resource and as a potent greenhouse gas that could be released from sediments to the atmosphere and ocean during global warming. In continental margin settings, methane release from gas hydrates also is a potential geohazard and could cause submarine landslides that endanger offshore infrastructure. Gas hydrate stability is sensitive to temperature changes. To understand methane release from gas hydrate, the U.S. Geological Survey (USGS) conducted a laboratory investigation of pure methane hydrate thermal properties at conditions relevant to accumulations of naturally occurring methane hydrate. Prior to this work, thermal properties for gas hydrates generally were measured on analog systems such as ice and non-methane hydrates or at temperatures below freezing; these conditions limit direct comparisons to methane hydrates in marine and permafrost sediment. Three thermal properties, defined succinctly by Briaud and Chaouch (1997), are estimated from the experiments described here: - Thermal conductivity, λ: if λ is high, heat travels easily through the material. - Thermal diffusivity, κ: if κ is high, it takes little time for the temperature to rise in the material. - Specific heat, cp: if cp is high, it takes a great deal of heat to raise the temperature of the material.

Partial oxidation of methane (POM) assisted solid oxide co-electrolysis

DOEpatents

Chen, Fanglin; Wang, Yao

2017-02-21

Methods for simultaneous syngas generation by opposite sides of a solid oxide co-electrolysis cell are provided. The method can comprise exposing a cathode side of the solid oxide co-electrolysis cell to a cathode-side feed stream; supplying electricity to the solid oxide co-electrolysis cell such that the cathode side produces a product stream comprising hydrogen gas and carbon monoxide gas while supplying oxygen ions to an anode side of the solid oxide co-electrolysis cell; and exposing the anode side of the solid oxide co-electrolysis cell to an anode-side feed stream. The cathode-side feed stream comprises water and carbon dioxide, and the anode-side feed stream comprises methane gas such that the methane gas reacts with the oxygen ions to produce hydrogen and carbon monoxide. The cathode-side feed stream can further comprise nitrogen, hydrogen, or a mixture thereof.

Theoretical insights into the selective oxidation of methane to methanol in copper-exchanged mordenite

DOE PAGES

Zhao, Zhi -Jian; Kulkarni, Ambarish; Vilella, Laia; ...

2016-05-02

Selective oxidation of methane to methanol is one of the most difficult chemical processes to perform. A potential group of catalysts to achieve CH 4 partial oxidation are Cu-exchanged zeolites mimicking the active structure of the enzyme methane monooxygenase. However, the details of this conversion, including the structure of the active site, are still under debate. In this contribution, periodic density functional theory (DFT) methods were employed to explore the molecular features of the selective oxidation of methane to methanol catalyzed by Cu-exchanged mordenite (Cu-MOR). We focused on two types of previously suggested active species, CuOCu and CuOOCu. Our calculationsmore » indicate that the formation of CuOCu is more feasible than that of CuOOCu. In addition, a much lower C–H dissociation barrier is located on the former active site, indicating that C–H bond activation is easily achieved with CuOCu. We calculated the energy barriers of all elementary steps for the entire process, including catalyst activation, CH 4 activation, and CH 3OH desorption. Finally, our calculations are in agreement with experimental observations and present the first theoretical study examining the entire process of selective oxidation of methane to methanol.« less

Diffusional limits to the consumption of atmospheric methane by soils

USGS Publications Warehouse

Striegl, Robert G.

1993-01-01

Net transport of atmospheric gases into and out of soil systems is primarily controlled by diffusion along gas partial pressure gradients. Gas fluxes between soil and the atmosphere can therefore be estimated by a generalization of the equation for ordinary gaseous diffusion in porous unsaturated media. Consumption of CH4 by methylotrophic bacteria in the top several centimeters of soil causes the uptake of atmospheric CH4 by aerated soils. The capacity of the methylotrophs to consume CH4 commonly exceeds the potential of CH4 to diffuse from the atmosphere to the consumers. The maximum rate of uptake of atmospheric CH4 by soil is, therefore, limited by diffusion and can be calculated from soil physical properties and the CH4 concentration gradient. The CH4 concentration versus depth profile is theoretically described by the equation for gaseous diffusion with homogeneous chemical reaction in porous unsaturated media. This allows for calculation of the in situ rate of CH4 consumption within specified depth intervals.

Engineering Development of Ceramic Membrane Reactor System for Converting Natural Gas to Hydrogen and Synthesis Gas for Liquid Transportation Fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Air Products and Chemicals

2008-09-30

An Air Products-led team successfully developed ITM Syngas technology from the concept stage to a stage where a small-scale engineering prototype was about to be built. This technology produces syngas, a gas containing carbon monoxide and hydrogen, by reacting feed gas, primarily methane and steam, with oxygen that is supplied through an ion transport membrane. An ion transport membrane operates at high temperature and oxygen ions are transported through the dense membrane's crystal lattice when an oxygen partial pressure driving force is applied. This development effort solved many significant technical challenges and successfully scaled-up key aspects of the technology tomore » prototype scale. Throughout the project life, the technology showed significant economic benefits over conventional technologies. While there are still on-going technical challenges to overcome, the progress made under the DOE-funded development project proved that the technology was viable and continued development post the DOE agreement would be warranted.« less

Synthesis of molybdenum carbide superconducting compounds by microwave-plasma chemical vapor deposition

NASA Astrophysics Data System (ADS)

Zhao, Hongyang; Cai, Kang; Ma, Zhibin; Cheng, Zhenxiang; Jia, Tingting; Kimura, Hideo; Fu, Qiuming; Tao, Hong; Xiong, Liwei

2018-02-01

A method to synthesize molybdenum carbides has been developed based on microwave plasma treatment with methane and hydrogen mixed gases, using a microwave-plasma chemical vapor deposition device. The device framework and its mechanism are described in detail. Two-dimensional α-Mo2C has been directly synthesized by a plate-to-plate substrate holder structure with a microwave power of 920 W and a partial pressure of 20 kPa. In-situ optical emission spectroscopy was used to measure the radical types in the plasma ball during glow discharge. The as-grown α-Mo2C samples were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy to determine their phases, purity and chemical groups. The superconducting transition temperature was measured, and the transition temperatures of the relevant phases are discussed in detail. The results confirmed that this method is an efficient way to obtain molybdenum carbides and inspire new research interest in transition metal carbides, which have many intrinsic local properties and applications.

Surface analysis of mixed-conducting ferrite membranes by the conversion-electron Mössbauer spectroscopy

NASA Astrophysics Data System (ADS)

Waerenborgh, J. C.; Tsipis, E. V.; Yaremchenko, A. A.; Kharton, V. V.

2011-09-01

Conversion-electron Mössbauer spectroscopy analysis of iron surface states in the dense ceramic membranes made of 57Fe-enriched SrFe 0.7Al 0.3O 3- δ perovskite, shows no traces of reductive decomposition or carbide formation in the interfacial layers after operation under air/CH 4 gradient at 1173 K, within the limits of experimental uncertainty. The predominant trivalent state of iron cations at the membrane permeate-side surface exposed to flowing dry methane provides evidence of the kinetic stabilization mechanism, which is only possible due to slow oxygen-exchange kinetics and enables long-term operation of the ferrite-based ceramic reactors for natural gas conversion. At the membrane feed-side surface exposed to air, the fractions of Fe 4+ and Fe 3+ are close to those in the powder equilibrated at atmospheric oxygen pressure, suggesting that the exchange limitations to oxygen transport are essentially localized at the partially reduced surface.

Pressure (Or No Royal Road)

ERIC Educational Resources Information Center

Bradley, J.

1973-01-01

Discusses how difficult the various problems of pressure, partial pressure, gas laws, and vapor pressure are for students. Outlines the evolution of the concept of pressure, the gas equation for a perfect gas, partial pressures, saturated vapor pressure, Avogadro's hypothesis, Raoult's law, and the vapor pressure of ideal solutions. (JR)

Reduced Equations for Calculating the Combustion Rates of Jet-A and Methane Fuel

NASA Technical Reports Server (NTRS)

Molnar, Melissa; Marek, C. John

2003-01-01

Simplified kinetic schemes for Jet-A and methane fuels were developed to be used in numerical combustion codes, such as the National Combustor Code (NCC) that is being developed at Glenn. These kinetic schemes presented here result in a correlation that gives the chemical kinetic time as a function of initial overall cell fuel/air ratio, pressure, and temperature. The correlations would then be used with the turbulent mixing times to determine the limiting properties and progress of the reaction. A similar correlation was also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium concentration of carbon monoxide as a function of fuel air ratio, pressure, and temperature. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates and the values obtained from the equilibrium correlations were then used to calculate the necessary chemical kinetic times. Chemical kinetic time equations for fuel, carbon monoxide, and NOx were obtained for both Jet-A fuel and methane.

Explosion characteristics of synthesised biogas at various temperatures.

PubMed

Dupont, L; Accorsi, A

2006-08-25

Biogas is considered as a valuable source of renewable energy. Indeed, it can be turned into useful energy (heat, electricity, fuel) and can contribute to reduce greenhouse gas emissions. Knowledge of its safety characteristics is a very important practical issue. Experimental investigation of synthesised biogas explosion characteristics was conducted in a 20-L sphere at various temperatures (30-70 degrees C) and at atmospheric pressure. The studied biogas was made of 50% methane (CH(4)) and 50% carbon dioxide (CO(2)). It was also saturated with humidity: this composition is frequently met in digesters during waste methanisation. There are two inert gases in biogas: water vapour and carbon dioxide. Its vapour water content rises along with temperature. The presence of these inert gases modifies considerably biogas characteristics compared to the ones of pure methane: explosion limits are lowered and beyond 70 degrees C, water vapour content is sufficient to inert the mixture. Furthermore, explosion violence (estimated with the maximum rate of pressure rise values, (dp/dt)(max)) is three times lower for biogas than for pure methane at ambient temperature.

Thermodynamic Analysis on of Skid-Mounted Coal-bed Methane Liquefaction Device using Cryogenic Turbo-Expander

NASA Astrophysics Data System (ADS)

Chen, Shuangtao; Niu, Lu; Zeng, Qiang; Li, Xiaojiang; Lou, Fang; Chen, Liang; Hou, Yu

2017-12-01

Coal-bed methane (CBM) reserves are rich in Sinkiang of China, and liquefaction is a critical step for the CBM exploration and utilization. Different from other CBM gas fields in China, CBM distribution in Sinkiang is widespread but scattered, and the pressure, flow-rate and nitrogen content of CBM feed vary significantly. The skid-mounted liquefaction device is suggested as an efficient and economical way to recover methane. Turbo-expander is one of the most important parts which generates the cooling capacity for the cryogenic liquefaction system. Using turbo-expander, more cooling capacity and higher liquefied fraction can be achieved. In this study, skid-mounted CBM liquefaction processes based on Claude cycle are established. Cryogenic turbo-expander with high expansion ratio is employed to improve the efficiency of CBM liquefaction process. The unit power consumption per liquefaction mole flow-rate for CBM feed gas is used as the object function for process optimization, compressor discharge pressure, flow ratio of feed gas to turbo-expander and nitrogen friction are analyzed, and optimum operation range of the liquefaction processes are obtained.

Direct use of methane in coal liquefaction

DOEpatents

Sundaram, M.S.; Steinberg, M.

1985-06-19

This invention relates to a process for converting solid carbonaceous material, such as coal, to liquid and gaseous hydrocarbons utilizing methane, generally at a residence time of about 20 to 120 minutes at a temperature of 250 to 750/sup 0/C, preferably 350 to 450/sup 0/C, pressurized up to 6000 psi, and preferably in the 1000 to 2500 psi range, preferably directly utilizing methane 50 to 100% by volume in a mix of methane and hydrogen. A hydrogen donor solvent or liquid vehicle such as tetralin, tetrahydroquinoline, piperidine, and pyrolidine may be used in a slurry mix where the solvent feed is 0 to 100% by weight of the coal or carbonaceous feed. Carbonaceous feed material can either be natural, such as coal, wood, oil shale, petroleum, tar sands, etc., or man-made residual oils, tars, and heavy hydrocarbon residues from other processing systems. 1 fig.

Uranus - Disk structure within the 7300-A methane band

NASA Technical Reports Server (NTRS)

Price, M. J.; Franz, O. G.

1979-01-01

Orthogonal narrow-band (100 A) photoelectric slit scan photometry of Uranus has been used to infer the basic two-dimensional structure of the disk within the 7300-A methane band. Numerical image reconstruction and restoration techniques have been applied to quantitatively estimate the degrees of polar and limb brightening on the planet. Through partial removal of atmospheric smearing, an effective spatial resolution of approximately 0.9 arcsec has been achieved. Peak polar, limb, and central intensities on the disk are in the respective proportions 3:2:1. In addition, the bright polar feature is displaced from the geometric pole towards the equator of the planet.

Transport of dissolved gases through unsaturated porous media

NASA Astrophysics Data System (ADS)

Maryshev, B. S.

2017-06-01

The natural porous media (e.g. soil, sand, peat etc.) usually are partially saturated by groundwater. The saturation of soil depends on hydrostatic pressure which is linearly increased with depth. Often some gases (e.g. nitrogen, oxygen, carbon dioxide, methane etc.) are dissolved into the groundwater. The solubility of gases is very small because of that two assumptions is applied: I. The concentration of gas is equal to solubility, II. Solubility depends only on pressure (for isothermal systems). In this way some part of dissolved gas transfers from the solution to the bubble phase. The gas bubbles are immovably trapped in a porous matrix by surface-tension forces and the dominant mechanism of transport of gas mass becomes the diffusion of gas molecules through the liquid. If the value of water content is small then the transport of gas becomes slow and gas accumulates into bubble phase. The presence of bubble phase additionally decreases the water content and slows down the transport. As result the significant mass of gas should be accumulated into the massif of porous media. We derive the transport equations and find the solution which is demonstrated the accumulation of gases. The influence of saturation, porosity and filtration velocity to accumulation process is investigated and discussed.

Ground based mobile isotopic methane measurements in the Front Range, Colorado

NASA Astrophysics Data System (ADS)

Vaughn, B. H.; Rella, C.; Petron, G.; Sherwood, O.; Mielke-Maday, I.; Schwietzke, S.

2014-12-01

Increased development of unconventional oil and gas resources in North America has given rise to attempts to monitor and quantify fugitive emissions of methane from the industry. Emission estimates of methane from oil and gas basins can vary significantly from one study to another as well as from EPA or State estimates. New efforts are aimed at reconciling bottom-up, or inventory-based, emission estimates of methane with top-down estimates based on atmospheric measurements from aircraft, towers, mobile ground-based vehicles, and atmospheric models. Attributing airborne measurements of regional methane fluxes to specific sources is informed by ground-based measurements of methane. Stable isotopic measurements (δ13C) of methane help distinguish between emissions from the O&G industry, Confined Animal Feed Operations (CAFO), and landfills, but analytical challenges typically limit meaningful isotopic measurements to individual point sampling. We are developing a toolbox to use δ13CH4 measurements to assess the partitioning of methane emissions for regions with multiple methane sources. The method was applied to the Denver-Julesberg Basin. Here we present data from continuous isotopic measurements obtained over a wide geographic area by using MegaCore, a 1500 ft. tube that is constantly filled with sample air while driving, then subsequently analyzed at slower rates using cavity ring down spectroscopy (CRDS). Pressure, flow and calibration are tightly controlled allowing precise attribution of methane enhancements to their point of collection. Comparisons with point measurements are needed to confirm regional values and further constrain flux estimates and models. This effort was made in conjunction with several major field campaigns in the Colorado Front Range in July-August 2014, including FRAPPÉ (Front Range Air Pollution and Photochemistry Experiment), DISCOVER-AQ, and the Air Water Gas NSF Sustainability Research Network at the University of Colorado.

Implications of New Methane Absorption Coefficients on Uranus Vertical Structure Derived from Near-IR Spectra

NASA Astrophysics Data System (ADS)

Fry, Patrick M.; Sromovsky, L. A.

2009-09-01

Using new methane absorption coefficients from Karkoschka and Tomasko (2009, submitted to Icarus, "Methane Absorption Coefficients for the Jovian Planets from Laboratory, Huygens, and HST Data"), we fit Uranus near-IR spectra previously analyzed in Sromovsky et al. (2006, Icarus 182, 577-593, Fink and Larson, 1979 J- and H-band), Sromovsky and Fry (2008, Icarus 193, 252-266, 2006 NIRC2 J- and H-band, 2006 SpeX) using Irwin et al. (2006, Icarus 181, 309-319) methane absorption coefficients. Because the new absorption coefficients usually result in higher opacities at the low temperatures seen in Uranus' upper troposphere, our previously derived cloud altitudes are expected to generally rise to higher altitudes. For example, using Lindal et al. (1987, JGR 92, 14987-15001) model D temperature and methane abundance profiles, we are better able to fit the J-band 43-deg. south bright band with the new coefficients (chi-square=205, vs. 315 for Irwin), with the pressure of the upper tropospheric cloud decreasing to 1.6 bars (from 2.4 bars using Irwin coefficients). Improvements in fitting H-band spectra from the same latitude are not as readily obtained. Derived upper tropospheric cloud pressures are very similar using the two absorption datasets (1.6-1.7 bars), but the character of the fits differs. New Karkoschka and Tomasko coefficients better fit some details in the 1.5-1.58 micron region, but Irwin fits the broad absorption band wing at 1.61-1.62 microns better, and the fit chi-square values are similar (K&T: 243, Irwin: 220). Results for a higher methane concentration (Lindal et al. model F) were similar. Whether the new coefficients will simply raise derived altitudes across the planet or will result in fundamental changes in structure is as yet unclear. This work was suported by NASA planetary astronomy and planetary atmospheres programs.

Effect of well construction on the mechanical state of unconsolidated methane hydrate-bearing sediment

NASA Astrophysics Data System (ADS)

Sasaki, T.; Soga, K.; Yamamoto, K.

2016-12-01

World's first offshore production of gas from methane hydrate-bearing sediment was accomplished in Nankai Trough off the coast of Japan. The achievement signals the beginning of exploitation of methane hydrate as a new source of energy, as an estimated amount of the new gas resource significantly exceeds that of the existing conventional oil and gas resources. Conventional gas reservoirs exist in consolidated sediment (i.e. rocks) thousands of metres below seafloor, and such sediment is hard enough to resist deformation. Methane hydrate reservoirs, on the other hand, lies only a couple of hundreds of metres down the seafloor, which means the sediment is unconsolidated (i.e. soils) and is readily deformed. In addition, the hydrate melts away in the pore space when it releases gas, giving rise to a significant rearrangement of stresses in the sediment. Well construction in methane hydrate reservoir might affect the mechanical state of the sediment to the point where the interpretation of the fracture pressure test becomes difficult and sand production could be enhanced. Existing numerical simulations tend to overlook soil mechanics, which is more appropriate than rock mechanics to model unconsolidated sediment, and the effect of methane hydrate on soil's mechanical behaviour is missed. In the present research, the construction of well in unconsolidated hydrate-bearing sediment was modelled with finite element analysis incorporating the critical state soil mechanics. Results showed that cement shrinkage in the well annulus would have a significant effect on the principal stresses and directions of the sediment even if the magnitude of the shrinkage was 0.1%. Cement shrinkage would also promote the generation of plastic strains, potentially enhancing sand production. Results also showed that the direction of fracture inferred from a fracture pressure test at Nankai Trough might have been vertical, indicating it was developed at the cement-sediment interface.

Factors controlling the concentration of methane and other volatiles in groundwater and soil-gas around a waste site

NASA Astrophysics Data System (ADS)

Barber, C.; Davis, G. B.; Briegel, D.; Ward, J. K.

1990-01-01

The concentration of methane in groundwater and soil-gas in the vicinity of a waste landfill on an unconfined sand aquifer has been investigated in detail. These data have been used to evaluate techniques which use volatile organic compounds in soil-gas as indicators of groundwater contamination. Simple one-dimensional models of gas advection and diffusion have been adapted for use in the study. Lateral advection of gas in the unsaturated sand was found to be seasonal and was most noticeable in winter when the profile was wet; a mean velocity of 1 m d - was measured from breakthrough of a helium tracer in an injection test. The effects of advection on trace concentrations of methane in soil-gas were limited to within 150-200m from the waste site and resulted from pressure gradients brought about by positive gas pressures in the landfill, and also as a result of ebullition (gas bubbling) from contaminated groundwater. The distribution of methane in soil-gas at shallow (2m) depth gave a general indication of the direction of movement of contaminants with groundwater in close proximity to the landfill. Outside this zone, diffusional transport of methane from groundwater to soil-gas occurred and methane in soil-gas sampled close to the water table was found to be a useful indicator of contaminated groundwater. Modelling the exchange of volatiles between aqueous and gas phases indicates that a wide range of organic compounds, particularly those with Henry's Law constants greater than 2.5 × 10 t-2 kPam 3mol -1, would have potential for use as indicators of pollution, if these were present in groundwater and they behaved relatively conservatively. In general, the principal factors controlling the concentration of these volatiles in soil-gas were the concentration gradient at the water table and capillary fringe and the ratio of diffusion coefficients in the saturated and unsaturated zones.

Heat of adsorption, adsorption stress, and optimal storage of methane in slit and cylindrical carbon pores predicted by classical density functional theory.

PubMed

Hlushak, Stepan

2018-01-03

Temperature, pressure and pore-size dependences of the heat of adsorption, adsorption stress, and adsorption capacity of methane in simple models of slit and cylindrical carbon pores are studied using classical density functional theory (CDFT) and grand-canonical Monte-Carlo (MC) simulation. Studied properties depend nontrivially on the bulk pressure and the size of the pores. Heat of adsorption increases with loading, but only for sufficiently narrow pores. While the increase is advantageous for gas storage applications, it is less significant for cylindrical pores than for slits. Adsorption stress and the average adsorbed fluid density show oscillatory dependence on the pore size and increase with bulk pressure. Slit pores exhibit larger amplitude of oscillations of the normal adsorption stress with pore size increase than cylindrical pores. However, the increase of the magnitude of the adsorption stress with bulk pressure increase is more significant for cylindrical than for slit pores. Adsorption stress appears to be negative for a wide range of pore sizes and external conditions. The pore size dependence of the average delivered density of the gas is analyzed and the optimal pore sizes for storage applications are estimated. The optimal width of slit pore appears to be almost independent of storage pressure at room temperature and pressures above 10 bar. Similarly to the case of slit pores, the optimal radius of cylindrical pores does not exhibit much dependence on the storage pressure above 15 bar. Both optimal width and optimal radii of slit and cylindrical pores increase as the temperature decreases. A comparison of the results of CDFT theory and MC simulations reveals subtle but important differences in the underlying fluid models employed by the approaches. The differences in the high-pressure behaviour between the hard-sphere 2-Yukawa and Lennard-Jones models of methane, employed by the CDFT and MC approaches, respectively, result in an overestimation of the heat of adsorption by the CDFT theory at higher loadings. However, both adsorption stress and adsorption capacity appear to be much less sensitive to the differences between the models and demonstrate excellent agreement between the theory and the computer experiment.

Pressures of Partial Crystallization of Magmas Along Transforms: Implications for Crustal Accretion

NASA Astrophysics Data System (ADS)

Scott, J. L.; Zerda, C.; Brown, D.; Ciaramitaro, S. C.; Barton, M.

2016-12-01

Plate spreading at mid-ocean ridges is responsible for the creation of most of the crust on earth. The ridge system is very complex and many questions remain unresolved. Among these is the nature of magma plumbing systems beneath transform faults. Pervious workers have suggested that increased conductive cooling along transforms promotes higher pressures of partial crystallization, and that this explains the higher partial pressures of crystallization inferred for magmas erupted along slow spreading ridges compared to magmas erupted along faster spreading ridges. To test this hypothesis, we undertook a detailed analysis of pressures of partial crystallization for magmas erupted at 3 transforms along the fast to intermediate spreading East Pacific Rise(Blanco, Clipperton, and Siqueiros) and 3 transforms along the slow spreading Mid Atlantic Ridge(Famous Transform B, Kane, and 15°20'N). Pressures of partial crystallization were calculated from the compositions of glasses (quenched liquids) lying along the P (and T) dependent olivine, plagioclase, and augite cotectic using the method described by Kelley and Barton (2008). Published analyses of mid-ocean ridge basalt glasses sampled from these transforms and surrounding ridge segments were used as input data. Samples with anomalous chemical compositions and samples that yielded pressures associated with unrealistically large uncertainties were filtered out of the database. The pressures of partial crystallization for the remaining 916 samples ranged from 0 to 520 MPa with the great majority ( 95%) of sample returning pressures of less than 300 MPa. Pressures of < 300 MPa are within error of the pressure range associated with partial crystallization within oceanic crust with a thickness of 7 km. Higher (sub-crustal) pressures (>300 MPa) are associated with a small number of samples from the Pacific segments. Except for the Blanco, pressures of partial crystallization do not increase as transforms are approached. These observations contrast with those of previous workers, who reported anomalously high pressures (up to 1000 MPa) for a large number of samples erupted near both Atlantic and Pacific Transforms. We conclude that higher rates of cooling along transform does not have a major effect on the onset of partial crystallization along the mid-ocean ridges

Relationship between Maceral of Coal and Coal-bed Methane adsorption ability in Sihe Coalmine of Qinshui Basin, China

NASA Astrophysics Data System (ADS)

Wang, M. S.; Zou, G. G.; Zhu, R. B.

2018-05-01

Maceral components and its content of coal were divided based on the microscopic characteristics of coal. The Langmuir volume and the Langmuir pressure were tested, and the Langmuir volume represents the adsorption capacity of coal. The formation of coal bed methane is affected by the partition of the maceral components in coal. Therefore, the relationship between maceral composition and coal bed methane adsorption capacity of coal was analyzed. The results show that the maceral components of coal are dominated by vitrinite and inertinite in the study area, and the content of inertinite is below 32%. The vitrinite group has a negative linear correlation with the Langmuir volume, and the inertia composition has a positive linear correlation with it. The cellular structures in the inertinite are the main site of coal bed methane enrichment. The microstructure of coal affects the coalbed methane content and the stage of hydrocarbon generation in coal. This indicates that the microstructure of coal is one of the important factors influencing the adsorption capacity of coal seam.

A Simulation Model of Carbon Cycling and Methane Emissions in Amazon Wetlands

NASA Technical Reports Server (NTRS)

Potter, Christopher; Melack, John; Hess, Laura; Forsberg, Bruce; Novo, Evlyn Moraes; Klooster, Steven

2004-01-01

An integrative carbon study is investigating the hypothesis that measured fluxes of methane from wetlands in the Amazon region can be predicted accurately using a combination of process modeling of ecosystem carbon cycles and remote sensing of regional floodplain dynamics. A new simulation model has been build using the NASA- CASA concept for predicting methane production and emission fluxes in Amazon river and floodplain ecosystems. Numerous innovations area being made to model Amazon wetland ecosystems, including: (1) prediction of wetland net primary production (NPP) as the source for plant litter decomposition and accumulation of sediment organic matter in two major vegetation classes - flooded forests (varzea or igapo) and floating macrophytes, (2) representation of controls on carbon processing and methane evasion at the diffusive boundary layer, through the lake water column, and in wetland sediments as a function of changes in floodplain water level, (3) inclusion of surface emissions controls on wetland methane fluxes, including variations in daily surface temperature and of hydrostatic pressure linked to water level fluctuations. A model design overview and early simulation results are presented.

Biocatalytic methanation of hydrogen and carbon dioxide in an anaerobic three-phase system.

PubMed

Burkhardt, M; Koschack, T; Busch, G

2015-02-01

A new type of anaerobic trickle-bed reactor was used for biocatalytic methanation of hydrogen and carbon dioxide under mesophilic temperatures and ambient pressure in a continuous process. The conversion of gaseous substrates through immobilized hydrogenotrophic methanogenic archaea in a biofilm is a unique feature of this type of reactor. Due to the formation of a three-phase system on the carrier surface and operation as a plug flow reactor without gas recirculation, a complete reaction could be observed. With a methane concentration higher than c(CH4) = 98%, the product gas exhibits a very high quality. A specific methane production of P(CH4) = 1.49 Nm(3)/(m(3)(SV) d) was achieved at a hydraulic loading rate of LR(H2) = 6.0 Nm(3)/(m(3)(SV) d). The relation between trickle flow through the reactor and productivity could be shown. An application for methane enrichment in combination with biogas facilities as a source of carbon dioxide has also been positively proven. Copyright © 2014 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan Zhang; Jin-hu Wu; Dong-ke Zhang

The cracking of oil refinery off-gas, simulated with a gas mixture containing methane (51%), ethylene (21.4%), ethane (21.1%), and propane (6.5%), over a coal char, petroleum coke, and quartz, respectively, has been studied in a fixed bed reactor. The experiments were performed at temperatures between 850 and 1000{sup o}C and at atmospheric pressure. The results show that the conversions of all species considered increased with increasing temperature. Ethane and propane completely decomposed over all three bed materials in the temperature range investigated. However, the higher initial conversion rates of methane and ethylene cracking at all temperatures were observed only overmore » the coal char and not on the petroleum coke and quartz, indicating a significant catalytic effect of the coal char on methane and ethylene cracking. Methane and ethylene conversions decreased with reaction time due to deactivation of the coal char by carbon deposition on the char surface and, in the later stage of a cracking experiment, became negative, suggesting that methane and ethylene had been formed during the cracking of ethane and propane. 16 refs., 13 figs., 2 tabs.« less

High-temperature measurements of methane and acetylene using quantum cascade laser absorption near 8 μm

NASA Astrophysics Data System (ADS)

Sajid, M. B.; Javed, T.; Farooq, A.

2015-04-01

The mid-infrared wavelength region near 8 μm contains absorption bands of several molecules such as water vapor, hydrogen peroxide, nitrous oxide, methane and acetylene. A new laser absorption sensor based on the ν4 band of methane and the ν4+ν5 band of acetylene is reported for interference-free, time-resolved measurements under combustion-relevant conditions. A detailed line-selection procedure was used to identify optimum transitions. Methane and acetylene were measured at the line centers of Q12 (1303.5 cm-1) and P23 (1275.5 cm-1) transitions, respectively. High-temperature absorption cross sections of methane and acetylene were measured at peaks (on-line) and valleys (off-line) of the selected absorption transitions. The differential absorption strategy was employed to eliminate interference absorption from large hydrocarbons. Experiments were performed behind reflected shock waves over a temperature range of 1200-2200 K, between pressures of 1-4 atm. The diagnostics were then applied to measure the respective species time-history profiles during the shock-heated pyrolysis of n-pentane.

Ammonia clathrate hydrates as new solid phases for Titan, Enceladus, and other planetary systems.

PubMed

Shin, Kyuchul; Kumar, Rajnish; Udachin, Konstantin A; Alavi, Saman; Ripmeester, John A

2012-09-11

There is interest in the role of ammonia on Saturn's moons Titan and Enceladus as the presence of water, methane, and ammonia under temperature and pressure conditions of the surface and interior make these moons rich environments for the study of phases formed by these materials. Ammonia is known to form solid hemi-, mono-, and dihydrate crystal phases under conditions consistent with the surface of Titan and Enceladus, but has also been assigned a role as water-ice antifreeze and methane hydrate inhibitor which is thought to contribute to the outgassing of methane clathrate hydrates into these moons' atmospheres. Here we show, through direct synthesis from solution and vapor deposition experiments under conditions consistent with extraterrestrial planetary atmospheres, that ammonia forms clathrate hydrates and participates synergistically in clathrate hydrate formation in the presence of methane gas at low temperatures. The binary structure II tetrahydrofuran + ammonia, structure I ammonia, and binary structure I ammonia + methane clathrate hydrate phases synthesized have been characterized by X-ray diffraction, molecular dynamics simulation, and Raman spectroscopy methods.

Vehicle-based Methane Mapping Helps Find Natural Gas Leaks and Prioritize Leak Repairs

NASA Astrophysics Data System (ADS)

von Fischer, J. C.; Weller, Z.; Roscioli, J. R.; Lamb, B. K.; Ferrara, T.

2017-12-01

Recently, mobile methane sensing platforms have been developed to detect and locate natural gas (NG) leaks in urban distribution systems and to estimate their size. Although this technology has already been used in targeted deployment for prioritization of NG pipeline infrastructure repair and replacement, one open question regarding this technology is how effective the resulting data are for prioritizing infrastructure repair and replacement. To answer this question we explore the accuracy and precision of the natural gas leak location and emission estimates provided by methane sensors placed on Google Street View (GSV) vehicles. We find that the vast majority (75%) of methane emitting sources detected by these mobile platforms are NG leaks and that the location estimates are effective at identifying the general location of leaks. We also show that the emission rate estimates from mobile detection platforms are able to effectively rank NG leaks for prioritizing leak repair. Our findings establish that mobile sensing platforms are an efficient and effective tool for improving the safety and reducing the environmental impacts of low-pressure NG distribution systems by reducing atmospheric methane emissions.

Perchlorate bioreduction linked to methane oxidation in a membrane biofilm reactor: Performance and microbial community structure.

PubMed

Xie, Ting; Yang, Qi; Winkler, Mari K H; Wang, Dongbo; Zhong, Yu; An, Hongxue; Chen, Fei; Yao, Fubin; Wang, Xiaolin; Wu, Jiawei; Li, Xiaoming

2018-06-05

Perchlorate bioreduction coupled to methane oxidation was successfully achieved without the addition of nitrate or nitrite in a membrane biofilm reactor (MBfR) inoculated with a mixture of freshwater sediments and anaerobic digester sludge as well as return activated sludge. The reactor was operated at different methane pressures (60, 40 and 20 Kpa) and influent perchlorate concentrations (1, 5 and 10 mg/L) to evaluate the biochemical process of perchlorate bioreduction coupled to methane oxidation. Perchlorate was completely reduced with a higher removal flux of 92.75 mg/m 2 ·d using methane as the sole carbon source and electron donor, other than hydrogen or other limiting organics. Quantitative real-time PCR showed that bacteria prevailed over archaea and the abundances of mcrA, pMMO, pcrA, and nirS genes were correlated with the influent perchlorate flux. High-throughput sequencing of 16S rRNA genes demonstrated that the functional community consisted of methanotrophs, methylotrophs, perchlorate-reducing bacteria, as well as various denitrifiers. Copyright © 2018 Elsevier B.V. All rights reserved.

Ammonia clathrate hydrates as new solid phases for Titan, Enceladus, and other planetary systems

PubMed Central

Shin, Kyuchul; Kumar, Rajnish; Udachin, Konstantin A.; Alavi, Saman; Ripmeester, John A.

2012-01-01

There is interest in the role of ammonia on Saturn’s moons Titan and Enceladus as the presence of water, methane, and ammonia under temperature and pressure conditions of the surface and interior make these moons rich environments for the study of phases formed by these materials. Ammonia is known to form solid hemi-, mono-, and dihydrate crystal phases under conditions consistent with the surface of Titan and Enceladus, but has also been assigned a role as water-ice antifreeze and methane hydrate inhibitor which is thought to contribute to the outgassing of methane clathrate hydrates into these moons’ atmospheres. Here we show, through direct synthesis from solution and vapor deposition experiments under conditions consistent with extraterrestrial planetary atmospheres, that ammonia forms clathrate hydrates and participates synergistically in clathrate hydrate formation in the presence of methane gas at low temperatures. The binary structure II tetrahydrofuran + ammonia, structure I ammonia, and binary structure I ammonia + methane clathrate hydrate phases synthesized have been characterized by X-ray diffraction, molecular dynamics simulation, and Raman spectroscopy methods. PMID:22908239

Molecular dynamics study of methane hydrate formation at a water/methane interface.

PubMed

Zhang, Junfang; Hawtin, R W; Yang, Ye; Nakagava, Edson; Rivero, M; Choi, S K; Rodger, P M

2008-08-28

We present molecular dynamics simulation results of a liquid water/methane interface, with and without an oligomer of poly(methylaminoethylmethacrylate), PMAEMA. PMAEMA is an active component of a commercial low dosage hydrate inhibitor (LDHI). Simulations were performed in the constant NPT ensemble at temperatures of 220, 235, 240, 245, and 250 K and a pressure of 300 bar. The simulations show the onset of methane hydrate growth within 30 ns for temperatures below 245 K in the methane/water systems; at 240 K there is an induction period of ca. 20 ns, but at lower temperatures growth commences immediately. The simulations were analyzed to calculate hydrate content, the propensity for hydrogen bond formation, and how these were affected by both temperature and the presence of the LDHI. As expected, both the hydrogen bond number and hydrate content decreased with increasing temperature, though little difference was observed between the lowest two temperatures considered. In the presence of PMAEMA, the temperature below which sustained hydrate growth occurred was observed to decrease. Some of the implications for the role of PMAEMA in LDHIs are discussed.

Thermodynamic equilibrium calculations of hydrogen production from the combined processes of dimethyl ether steam reforming and partial oxidation

NASA Astrophysics Data System (ADS)

Semelsberger, Troy A.; Borup, Rodney L.

Thermodynamic analyses of producing a hydrogen-rich fuel-cell feed from the combined processes of dimethyl ether (DME) partial oxidation and steam reforming were investigated as a function of oxygen-to-carbon ratio (0.00-2.80), steam-to-carbon ratio (0.00-4.00), temperature (100 °C-600 °C), pressure (1-5 atm) and product species. Thermodynamically, dimethyl ether processed with air and steam generates hydrogen-rich fuel-cell feeds; however, the hydrogen concentration is less than that for pure DME steam reforming. Results of the thermodynamic processing of dimethyl ether indicate the complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide for temperatures greater than 200 °C, oxygen-to-carbon ratios greater than 0.00 and steam-to-carbon ratios greater than 1.25 at atmospheric pressure (P = 1 atm). Increasing the operating pressure has negligible effects on the hydrogen content. Thermodynamically, dimethyl ether can produce concentrations of hydrogen and carbon monoxide of 52% and 2.2%, respectively, at a temperature of 300 °C, and oxygen-to-carbon ratio of 0.40, a pressure of 1 atm and a steam-to-carbon ratio of 1.50. The order of thermodynamically stable products (excluding H 2, CO, CO 2, DME, NH 3 and H 2O) in decreasing mole fraction is methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol and methyl-ethyl ether; trace amounts of formaldehyde, formic acid and methanol are observed. Ammonia and hydrogen cyanide are also thermodynamically favored products. Ammonia is favored at low temperatures in the range of oxygen-to-carbon ratios of 0.40-2.50 regardless of the steam-to-carbon ratio employed. The maximum ammonia content (i.e., 40%) occurs at an oxygen-to-carbon ratio of 0.40, a steam-to-carbon ratio of 1.00 and a temperature of 100 °C. Hydrogen cyanide is favored at high temperatures and low oxygen-to-carbon ratios with a maximum of 3.18% occurring at an oxygen-to-carbon ratio of 0.40 and a steam-to-carbon ratio of 0.00 in the temperature range of 400 °C-500 °C. Increasing the system pressure shifts the equilibrium toward ammonia and hydrogen cyanide.

Factors affecting the process of CO2 replacement of CH4 from methane hydrate in sediments - Constrained from experimental results

NASA Astrophysics Data System (ADS)

Lu, H.; Hu, G.; Vanderveen, J.; Liu, C.; Ratcliffe, C.; Ripmeester, J.

2011-12-01

CO2 replacement of CH4 from methane hydrate has been proposed as a method to produce gas from natural gas hydrate by taking advantage of both the production of natural gas and the sequestration of CO2. To examine the validity of this method DOE/Conoco-Philips is considering having a field test in Alaska. The reaction of CO2 replacing CH4 from methane hydrate has been confirmed to be thermodynamically feasible, but concern is always raised about the reaction kinetics. Some kinetic studies in the system of methane hydrate and liquid or gaseous CO2 have found that the reaction proceeds at a very low rate. Natural gas hydrate occurs in sediments with multi-components and complex structure, so matters will be even more complicated. Up to now, few investigations have been carried out concerning the factors affecting the reaction process of CO2 replacing CH4 from methane hydrate. Experiments were implemented with sands, which were recovered from Mallik 5L-38 well, Mackenzie Delta, Northwest Territory, Canada, sediment that previously contained hydrate although it had been dried completely before our experiments. The water-saturated sands were tightly charged into a plastic bottle (90 mm deep and 60 mm wide), and then this test specimen was sealed in a pressure cell. After methane hydrate was synthesized in the test specimen for 108 days under a pressure of 11 to 8 MPa and a temperature of 3 degrees Celsius, liquid CO2 was introduced into the pressure cell. The conditions under which CO2 was reacted with methane hydrate were ~5.3 MPa and 5 degrees Celsius. After reacting for 15 days, the test specimen was recovered. The test specimen was cut into ~10 mm thick discs, and sub-samples were further taken from each of the discs. In addition to the determination of hydrate saturation and the gas composition, Raman spectroscopic studies were carried out for the sub-samples obtained. The results revealed: 1) less CO2 replacement in the bottom disc of the test specimen as compared with that in the top disc, implying that diffusion was a factor that controlled the movement of CO2 in the sediments, 2) an inhomogeneous replacement reaction even within the same disc, indicating that the contact area between methane hydrate and CO2 was a factor that determined the degree of replacement of CH4 from methane hydrate 3) the separate appearance of CO2 Raman intensities and CH4 Raman intensities in some portions of the test specimen, suggesting that CO2 was present in the form of CO2 hydrate in addition to being together with CH4 in other parts of the hydrate. Further analysis found that both CO2 diffusion and the contact area for reaction were associated with the pore structure of the sediments, which were heterogeneous both in pore size and in pore shape as observed with high resolution X-ray CT.

Influence of N2 partial pressure on structural and microhardness properties of TiN/ZrN multilayers deposited by Ar/N2 vacuum arc discharge

NASA Astrophysics Data System (ADS)

Naddaf, M.; Abdallah, B.; Ahmad, M.; A-Kharroub, M.

2016-08-01

The influence of N2 partial pressure on structural, mechanical and wetting properties of multilayered TiN/ZrN thin films deposited on silicon substrates by vacuum arc discharge of (N2 + Ar) gas mixtures is investigated. X-ray diffraction (XRD) results show that the average texturing coefficient of (1 1 1) orientation and the grain size of both TiN and ZrN individual layers increase with increasing the N2 partial pressure. The Rutherford back scattering (RBS) measurements and analysis reveal that incorporation of the nitrogen in the film increases with increasing the N2 partial pressure and both TiN and ZrN individual layers have a nitrogen over-stoichiometry for N2 partial pressure ⩾50%. The change in the film micro-hardness is correlated to the changes in crystallographic texture, grain size, stoichiometry and the residual stress in the film as a function of the N2 partial pressure. In particular, stoichiometry of ZrN and TiN individual is found to play the vital role in determining the multilayer hardness. The multilayer film deposited at N2 partial pressure of 25% has the best stoichiometric ratio of both TiN and ZrN layers and the highest micro-hardness of about 32 GPa. In addition, water contact angle (WCA) measurements and analysis show a decrease in the work of adhesion on increasing the N2 partial pressure.

On the state of methane and nitrogen ice on Pluto and Triton: Implications of the binary phase diagram

NASA Astrophysics Data System (ADS)

Trafton, Laurence M.

2015-01-01

Compositional analyses of Pluto's surface ice in the literature typically include large areas on the body where CH4 and other volatiles are segregated in the pure form from the solid solution N2:CH4 in which CH4 is diluted. However, the existence of continent-size areas of pure CH4 are in conflict with both of the alternative models that successfully explain the enhancement of CH4 in Pluto's atmosphere, the Detailed Balancing thermal equilibrium model and the Hot Methane Patch model. Pluto's spectrum includes an apparently unshifted CH4 component while Triton's does not, and 93% of the concentration range of the binary phase diagram at 38 K shows that these species exist as a mixture of two saturated solid solution phases. Recognizing this, we propose that both of these saturated phases are present on Pluto and the CH4-rich phase of the mixture, CH4:N2, is the source of the relatively unshifted CH4 spectrum attributed to pure CH4. We also propose that CH4 is less abundant in Triton's ice to the point where either the ice is not saturated or the saturated CH4:N2 phase has not been detected. In this scenario, the partial vapor pressures do not change when the relative proportions of these saturated phases are varied in the mixture. Thus, the partial vapor pressures are independent of N2-CH4 concentrations if both saturated phases are present. Accordingly, the longitudinal and seasonal variations of CH4 and N2 features in Pluto's spectrum would be attributed to spatial variations in the relative proportions of these species. This may occur during volatile transport in the sublimation wind through extensive influences. The lower, unsaturated, values of the mole fraction of CH4 in the ice reported by Owen et al. (Owen et al. [1993]. Science 261, 745-748) and Cruikshank et al. (Cruikshank, D.P., Rush, T.L., Owen, T.C., Quirico, E., de Bergh, C. [1998]. The surface compositions of Triton, Pluto, and Charon. In: Solar System Ices. Astrophysics and Space Science Library Series, vol. 227. Kluwer Academic Publishers, Dordrecht), and by Doute et al. (Doute, S., Schmitt, B., Quirico, E., Owen, T.C., Cruikshank, D.P., de Bergh, C., Geballe, T.R., Roush, T.L. [1999]. Icarus 142, 421-444) based on a compositional analysis of Pluto's surface, were not obtained using optical constants for components consistent with the constraints of the phase diagram.

Methane hydrates in nature - Current knowledge and challenges

USGS Publications Warehouse

Collett, Timothy S.

2014-01-01

Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate research in recent years has mostly focused on: (1) documenting the geologic parameters that control the occurrence and stability of methane hydrates in nature, (2) assessing the volume of natural gas stored within various methane hydrate accumulations, (3) analyzing the production response and characteristics of methane hydrates, (4) identifying and predicting natural and induced environmental and climate impacts of natural methane hydrates, (5) analyzing the methane hydrate role as a geohazard, (6) establishing the means to detect and characterize methane hydrate accumulations using geologic and geophysical data, and (7) establishing the thermodynamic phase equilibrium properties of methane hydrates as a function of temperature, pressure, and gas composition. The U.S. Department of Energy (DOE) and the Consortium for Ocean Leadership (COL) combined their efforts in 2012 to assess the contributions that scientific drilling has made and could continue to make to advance our understanding of methane hydrates in nature. COL assembled a Methane Hydrate Project Science Team with members from academia, industry, and government. This Science Team worked with COL and DOE to develop and host the Methane Hydrate Community Workshop, which surveyed a substantial cross section of the methane hydrate research community for input on the most important research developments in our understanding of methane hydrates in nature and their potential role as an energy resource, a geohazard, and/or as an agent of global climate change. Our understanding of how methane hydrates occur in nature is still growing and evolving, and it is known with certainty that field, laboratory, and modeling studies have contributed greatly to our understanding of hydrates in nature and will continue to be a critical source of the information needed to advance our understanding of methane hydrates.

Methane Recycling During Burial of Methane Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

You, K.; Flemings, P. B.

2017-12-01

We quantitatively investigate the integral processes of methane hydrate formation from local microbial methane generation, burial of methane hydrate with sedimentation, and methane recycling at the base of the hydrate stability zone (BHSZ) with a multiphase multicomponent numerical model. Methane recycling happens in cycles, and there is not a steady state. Each cycle starts with free gas accumulation from hydrate dissociation below the BHSZ. This free gas flows upward under buoyancy, elevates the hydrate saturation and capillary entry pressure at the BHSZ, and this prevents more free gas flowing in. Later as this layer with elevated hydrate saturation is buried and dissociated, the large amount of free gas newly released and accumulated below rapidly intrudes into the hydrate stability zone, drives rapid hydrate formation and creates three-phase (gas, liquid and hydrate) equilibrium above the BHSZ. The gas front retreats to below the BHSZ until all the free gas is depleted. The shallowest depth that the free gas reaches in one cycle moves toward seafloor as more and more methane is accumulated to the BHSZ with time. More methane is stored above the BHSZ in the form of concentrated hydrate in sediments with relatively uniform pore throat, and/or with greater compressibility. It is more difficult to initiate methane recycling in passive continental margins where the sedimentation rate is low, and in sediments with low organic matter content and/or methanogenesis reaction rate. The presence of a permeable layer can store methane for significant periods of time without recycling. In a 2D system where the seafloor dips rapidly, the updip gas flow along the BHSZ transports more methane toward topographic highs where methane gas and elevated hydrate saturation intrude deeper into the hydrate stability zone within one cycle. This could lead to intermittent gas venting at seafloor at the topographic highs. This study provides insights on many phenomenon associated with methane recycling, such as the formation of free gas zone, concentrated hydrate zone, bottom simulating reflector, and overpressured zone around the BHSZ, and gas venting at seafloor.

Pore Scale Mechanistic Study of the Preferential Mode of Hydrate Formation in Sediments: Fluid Flow Aspects

NASA Astrophysics Data System (ADS)

Behseresht, J.; Prodanović, M.; Bryant, S. L.

2007-12-01

A spectrum of behavior is encountered in ocean sediments bearing methane hydrates, ranging from essentially static accumulations where hydrate and brine co-exist, to active cold seeps where hydrate and a methane gas phase co-exist in the hydrate stability zone (HSZ). In this and a companion paper (Jain and Juanes) we describe methods to test the following hypothesis: the coupling between drainage and fracturing, both induced by pore pressure, determines whether methane gas entering the HSZ is converted completely to hydrate. Here we describe a novel implementation of the level set method (LSM) to determine the capillarity-controlled displacement of brine by gas from sediment and from fractures within the sediment. Predictions of fluid configurations in infinite-acting model sediments indicate that the brine in drained sediment (after invasion by methane gas) is better connected than previously believed. This increases the availability of water and the rate of counter-diffusion of salinity ions, thus relaxing the limit on hydrate build-up within gas- invaded grain matrix. Simulated drainage of a fracture in sediment shows that points of contact between fracture faces are crucial. They allow residual water saturation to remain within an otherwise gas-filled fracture. Simulations of imbibition, which can occur for example after drainage into surrounding sediment reduces gas phase pressure in the fracture, indicate that the gas/water interfaces at contact points significantly shifts the threshold pressures for withdrawal of gas. During both drainage and imbibition, the contact points greatly increase water availability for hydrate formation within the fracture. We discuss coupling this capillarity-controlled displacement model with a discrete element model for grain-scale mechanics. The coupled model provides a basis for evaluating the macroscopic conditions (thickness of gas accumulation below the hydrate stability zone; average sediment grain size; principal earth stresses) favoring co- existence of methane gas and hydrate in the HSZ. Explaining the range of behavior is useful in assessing resource volumes and evaluating pore-to-core scale flow paths in production strategies.

Energy storage using high pressure electrolysis and methods for reconversion. [in automobile fuel synthesis

NASA Technical Reports Server (NTRS)

Hughes, W. L.

1973-01-01

Theoretical and experimental studies on high pressure electrolysis producing hydrogen and oxygen for energy storage and reconversion are reported. Moderate temperature, high pressure hydrogen/oxygen fuel cells with nickel electrodes are investigated for effects of pressure, temperature, and membrane porosity. Test results from an aphodid burner turbine generator combination obtained 40 percent kilowatt hours out of the fuel cell divided by kilowatt hours into the electrolyzer. It is concluded that high pressure hydrogenation of organic materials can be used to synthesize hydrozenes and methanes for making synthetic vehicular fuels.

Effect of pressure on structure and NO sub X formation in CO-air diffusion flames

NASA Technical Reports Server (NTRS)

Maahs, H. G.; Miller, I. M.

1979-01-01

A study was made of nitric oxide formation in a laminar CO-air diffusion flame over a pressure range from 1 to 50 atm. The carbon monoxide (CO) issued from a 3.06 mm diameter port coaxially into a coflowing stream of air confined within a 20.5 mm diameter chimney. Nitric oxide concentrations from the flame were measured at two carbon monoxide (fuel) flow rates: 73 standard cubic/min and 146 sccm. Comparison of the present data with data in the literature for a methane-air diffusion flame shows that for flames of comparable flame height (8 to 10 mm) and pseudoequivalence ratio (0.162), the molar emission index of a CO-air flame is significantly greater than that of a methane-air flame.

Rapid gas hydrate formation processes: Will they work?

DOE PAGES

Brown, Thomas D.; Taylor, Charles E.; Bernardo, Mark P.

2010-06-07

Researchers at DOE’s National Energy Technology Laboratory (NETL) have been investigating the formation of synthetic gas hydrates, with an emphasis on rapid and continuous hydrate formation techniques. The investigations focused on unconventional methods to reduce dissolution, induction, nucleation and crystallization times associated with natural and synthetic hydrates studies conducted in the laboratory. Numerous experiments were conducted with various high-pressure cells equipped with instrumentation to study rapid and continuous hydrate formation. The cells ranged in size from 100 mL for screening studies to proof-of-concept studies with NETL’s 15-Liter Hydrate Cell. The results from this work demonstrate that the rapid and continuousmore » formation of methane hydrate is possible at predetermined temperatures and pressures within the stability zone of a Methane Hydrate Stability Curve.« less

Experimental study on a comparison of typical premixed combustible gas-air flame propagation in a horizontal rectangular closed duct.

PubMed

Jin, Kaiqiang; Duan, Qiangling; Liew, K M; Peng, Zhongjing; Gong, Liang; Sun, Jinhua

2017-04-05

Research surrounding premixed flame propagation in ducts has a history of more than one hundred years. Most previous studies focus on the tulip flame formation and flame acceleration in pure gas fuel-air flame. However, the premixed natural gas-air flame may show different behaviors and pressure dynamics due to its unique composition. Natural gas, methane and acetylene are chosen here to conduct a comparison study on different flame behaviors and pressure dynamics, and to explore the influence of different compositions on premixed flame dynamics. The characteristics of flame front and pressure dynamics are recorded using high-speed schlieren photography and a pressure transducer, respectively. The results indicate that the compositions of the gas mixture greatly influence flame behaviors and pressure. Acetylene has the fastest flame tip speed and the highest pressure, while natural gas has a faster flame tip speed and higher pressure than methane. The Bychkov theory for predicting the flame skirt motion is verified, and the results indicate that the experimental data coincide well with theory in the case of equivalence ratios close to 1.00. Moreover, the Bychkov theory is able to predict flame skirt motion for acetylene, even outside of the best suitable expansion ratio range of 6

The 1992-1993 advanced design program. Part 1: The Mars methane engine project. Part 2: The Mars oxygen processor new furnace

NASA Astrophysics Data System (ADS)

Lauer, Stephen; Hoover, Scott; Lawrence, Lori; Paparistodemou, Christos; Taylor, Doug

1993-04-01

Three constituents of the Martian atmosphere, methane, carbon dioxide, and oxygen, can be used for internal combustion in engines utilized for future space exploration on Mars. These three gases, considered as the test case in this research, will be examined to determine required flow rates needed for combustion and optimization of engine performance. Results of the test case are examined in relation to a base case of methane and air for comparative purposes. Testing of exhaust temperatures, cylinder pressure, and exhaust gas analysis were performed for the base case and test case. Also described is a study utilizing a zirconia cell to convert carbon dioxide into usable oxygen to help support future Mars missions.

The 1992-1993 advanced design program. Part 1: The Mars methane engine project. Part 2: The Mars oxygen processor new furnace

NASA Technical Reports Server (NTRS)

Lauer, Stephen; Hoover, Scott; Lawrence, Lori; Paparistodemou, Christos; Taylor, Doug

1993-01-01

Three constituents of the Martian atmosphere, methane, carbon dioxide, and oxygen, can be used for internal combustion in engines utilized for future space exploration on Mars. These three gases, considered as the test case in this research, will be examined to determine required flow rates needed for combustion and optimization of engine performance. Results of the test case are examined in relation to a base case of methane and air for comparative purposes. Testing of exhaust temperatures, cylinder pressure, and exhaust gas analysis were performed for the base case and test case. Also described is a study utilizing a zirconia cell to convert carbon dioxide into usable oxygen to help support future Mars missions.

The Abundances of Methane and Ortho/Para Hydrogen in Uranus and Neptune: Implications of New Laboratory 4-0 H(sub 2) Quadrapole Line Parameters

NASA Technical Reports Server (NTRS)

Baines, K.; Mickelson, M.; Larson, L.; Ferguson, D.

1994-01-01

The tropospheric methane molar fraction (f(sub ch4,t)) and the ortho/para hydrogen ratio are derived for Uranus and Neptune based on new determinations of spectroscopic parameters for key hydrogen features as reported by Ferguson et al. (1993, J. Mol. Spec 160, 315-325). For each planet, the relatively weak laboratory linestrengths (approximately 30% and 15% less than the theoretical 4-0 S(0) and S(1) linestrengths, respectively) results, when compared to analyses adopting theoretical values, in a 30% decrease in the tropospheric methane ratio and a comparable increase in the pressure level of the optically-thick cloudtop marking the bottom of the visible atmosphere (P(sub cld)).

Methane Emissions from Permafrost Regions using Low-Power Eddy Covariance Stations

NASA Astrophysics Data System (ADS)

Burba, G.; Sturtevant, C.; Schreiber, P.; Peltola, O.; Zulueta, R.; Mammarella, I.; Haapanala, S.; Rinne, J.; Vesala, T.; McDermitt, D.; Oechel, W.

2012-04-01

Methane is an important greenhouse gas with a warming potential 23 times that of carbon dioxide over a 100-year cycle. The permafrost regions of the world store significant amounts of organic materials under anaerobic conditions, leading to large methane production and accumulation in the upper layers of bedrock, soil and ice. These regions are currently undergoing dramatic change in response to warming trends, and may become a significant potential source of global methane release under a warming climate over the coming decades and centuries. Presently, most measurements of methane fluxes in permafrost regions have been made with static chamber techniques, and very few were done with the eddy covariance approach using closed-path analyzers. Although chambers and closed-path analyzers have advantages, both techniques have significant limitations, especially for permafrost research. Static chamber measurements are discrete in time and space, and particularly difficult to use over polygonal tundra with highly non-uniform micro-topography and active water layer. They also may not capture the dynamics of methane fluxes on varying time scales (hours to annual estimates). In addition, placement of the chamber may disturb the surface integrity causing a significant over-estimation of the measured flux. Closed-path gas analyzers for measuring methane eddy fluxes employ advanced technologies such as TDLS (Tunable Diode Laser Spectroscopy), ICOS (Integrated Cavity Output Spectroscopy), WS-CRDS (wavelength scanned cavity ring-down spectroscopy), but require high flow rates at significantly reduced optical cell pressures to provide adequate response time and sharpen absorption features. Such methods, when used with the eddy covariance technique, require a vacuum pump and a total of 400-1500 Watts of grid power for the pump and analyzer system. The weight of such systems often exceeds 100-200 lbs, restricting practical applicability for remote or portable field studies. As a result, spatial coverage of eddy covariance methane flux measurements remains limited. Remote permafrost wetlands of Arctic tundra, northern boreal peatlands of Canada and Siberia, and other highly methanogenic ecosystems have few eddy covariance methane measurement stations. Those existing are often located near grid power sources and roads rather than in the middle of the methane-producing ecosystem, while those that are placed appropriately may require extraordinary efforts to build and maintain them, with large investments into man-power and infrastructure. Alternatively, open-path approach allows methane flux measurements at ambient pressure without the need for a pump. As a result, the measurements can be done with very low-power (e.g. 5-10 Watts), light (5 .2 kg) instruments permitting solar- and wind- powered remote deployments in hard-to-reach sites from permanent, portable or mobile stations, and cost-effective additions of a methane measurement to the present array of CO2 and H2O measurements. The low-power operation and light weight of open-path eddy covariance stations is important for a number of ecosystems (rice fields, landfills, wetlands, cattle yards), but it is especially important for permafrost regions where grid power and access roads are generally not available, and the logistics of running the experiments are particularly expensive. Emerging research on methane flux measurements using low-power stations equipped with LI-7700 open-path methane analyzer (LI-COR Biosciences) are presented from several permafrost ecosystems with contrasting setups, and weather conditions. Principles of operation, station characteristics and requirements are also discussed.

40 CFR Table W - 7 of Subpart W-Default Methane Emission Factors for Natural Gas Distribution

Code of Federal Regulations, 2012 CFR

2012-07-01

... Valve 0.557 Control Valve 9.34 Pressure Relief Valve 0.27 Orifice Meter 0.212 Regulator 0.772 Open-ended Line 26.131 Population Emission Factors—Below Grade Metering-Regulating station 1 Components, Gas... 100 to 300 psig 0.20 Below Grade M&R Station, Inlet Pressure Population Emission...

Liquid Hydrocarbons on Titan's Surface? How Cassini ISS Observations Fit into the Story (So Far)

NASA Technical Reports Server (NTRS)

Turtle, E. P.; Dawson, D. D.; Fussner, S.; Hardegree-Ullman, E.; Ewen, A. S.; Perry, J.; Porco, C. C.; West, R. A.

2005-01-01

Titan is the only satellite in our Solar System with a substantial atmosphere, the origins and evolution of which are still not well understood. Its primary (greater than 90%) component is nitrogen, with a few percent methane and lesser amounts of other species. Methane and ethane are stable in the liquid state under the temperature and pressure conditions in Titan s lower atmosphere and at the surface; indeed, clouds, likely composed of methane, have been detected. Photochemical processes acting in the atmosphere convert methane into more complex hydrocarbons, creating Titan s haze and destroying methane over relatively short timescales. Therefore, it has been hypothesized that Titan s surface has reservoirs of liquid methane which serve to resupply the atmosphere. Early observations of Titan s surface revealed albedo patterns which have been interpreted as dark hydrocarbon liquids occupying topographically low regions between higher-standing exposures of bright, water-ice bedrock, although this is far from being the only explanation for the observed albedo contrast. Observations made by the Imaging Science Subsystem during Cassini's approach to Saturn and its first encounters with Titan show the bright and dark regions in greater detail but have yet to resolve the question of whether there are liquids on the surface.

Alternative technologies to steam-methane reforming

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tindall, B.M.; Crews, M.A.

1995-11-01

Steam-methane reforming (SMR) has been the conventional route for hydrogen and carbon monoxide production from natural gas feedstocks. However, several alternative technologies are currently finding favor for an increasing number of applications. The competing technologies include: steam-methane reforming combined with oxygen secondary reforming (SMR/O2R); autothermal reforming (ATR); thermal partial oxidation (POX). Each of these alternative technologies uses oxygen as a feedstock. Accordingly, if low-cost oxygen is available, they can be an attractive alternate to SMR with natural gas feedstocks. These technologies are composed technically and economically. The following conclusions can be drawn: (1) the SMR/O2R, ATR and POX technologies canmore » be attractive if low-cost oxygen is available; (2) for competing technologies, the H{sub 2}/CO product ratio is typically the most important process parameter; (3) for low methane slip, the SMR/O2R, ATR and POX technologies are favored; (4) for full CO{sub 2} recycle, POX is usually better than ATR; (5) relative to POX, the ATR is a nonlicensed technology that avoids third-party involvement; (6) economics of each technology are dependent on the conditions and requirements for each project and must be evaluated on a case-by-case basis.« less

Effects of Chamber Pressure and Partial Pressure of Water Vapor on Secondary Drying in Lyophilization.

PubMed

Searles, James A; Aravapalli, Sridhar; Hodge, Cody

2017-10-01

Secondary drying is the final step of lyophilization before stoppering, during which water is desorbed from the product to yield the final moisture content. We studied how chamber pressure and partial pressure of water vapor during this step affected the time course of water content of aqueous solutions of polyvinylpyrrolidone (PVP) in glass vials. The total chamber pressure had no effect when the partial pressure of water vapor was very low. However, when the vapor phase contained a substantial fraction of water vapor, the PVP moisture content was much higher. We carried out dynamic vapor sorption experiments (DVS) to demonstrate that the higher PVP moisture content was a straightforward result of the higher water vapor content in the lyophilizer. The results highlight that the partial pressure of water vapor is extremely important during secondary drying in lyophilization, and that lower chamber pressure set points for secondary drying may sometimes be justified as a strategy for ensuring low partial pressure of water vapor, especially for lyophilizers that do not inject dry gas to control pressure. These findings have direct application for process transfers/scale ups from freeze-dryers that do not inject dry gas for pressure control to those that do, and vice versa.

Effect of organic-matter type and thermal maturity on methane adsorption in shale-gas systems

USGS Publications Warehouse

Zhang, Tongwei; Ellis, Geoffrey S.; Ruppel, Stephen C.; Milliken, Kitty; Yang, Rongsheng

2012-01-01

A series of methane (CH4) adsorption experiments on bulk organic rich shales and their isolated kerogens were conducted at 35 °C, 50 °C and 65 °C and CH4 pressure of up to 15 MPa under dry conditions. Samples from the Eocene Green River Formation, Devonian–Mississippian Woodford Shale and Upper Cretaceous Cameo coal were studied to examine how differences in organic matter type affect natural gas adsorption. Vitrinite reflectance values of these samples ranged from 0.56–0.58 %Ro. In addition, thermal maturity effects were determined on three Mississippian Barnett Shale samples with measured vitrinite reflectance values of 0.58, 0.81 and 2.01 %Ro. For all bulk and isolated kerogen samples, the total amount of methane adsorbed was directly proportional to the total organic carbon (TOC) content of the sample and the average maximum amount of gas sorption was 1.36 mmol of methane per gram of TOC. These results indicate that sorption on organic matter plays a critical role in shale-gas storage. Under the experimental conditions, differences in thermal maturity showed no significant effect on the total amount of gas sorbed. Experimental sorption isotherms could be fitted with good accuracy by the Langmuir function by adjusting the Langmuir pressure (PL) and maximum sorption capacity (Γmax). The lowest maturity sample (%Ro = 0.56) displayed a Langmuir pressure (PL) of 5.15 MPa, significantly larger than the 2.33 MPa observed for the highest maturity (%Ro > 2.01) sample at 50 °C. The value of the Langmuir pressure (PL) changes with kerogen type in the following sequence: type I > type II > type III. The thermodynamic parameters of CH4 adsorption on organic rich shales were determined based on the experimental CH4 isotherms. For the adsorption of CH4 on organic rich shales and their isolated kerogen, the heat of adsorption (q) and the standard entropy (Δs0) range from 7.3–28.0 kJ/mol and from −36.2 to −92.2 J/mol/K, respectively.

Applying Chemical Potential and Partial Pressure Concepts to Understand the Spontaneous Mixing of Helium and Air in a Helium-Inflated Balloon

ERIC Educational Resources Information Center

Jee-Yon Lee; Hee-Soo Yoo; Jong Sook Park; Kwang-Jin Hwang; Jin Seog Kim

2005-01-01

The spontaneous mixing of helium and air in a helium-inflated balloon is described in an experiment in which the partial pressure of the gases in the balloon are determined from the mole factions and the total pressure measured in the balloon. The results described provide a model for teaching concepts of partial pressure, chemical potential, and…

Transport processes in intertidal sand flats

NASA Astrophysics Data System (ADS)

Wu, Christy

2010-05-01

Methane rich sulfate depleted seeps are observed along the low water line of the intertidal sand flat Janssand in the Wadden Sea. It is unclear where in the flat the methane is formed, and how it is transported to the edge of the sand flat where the sulfidic water seeps out. Methane and sulfate distributions in pore water were determined along transects from low water line toward the central area of the sand flat. The resulting profiles showed a zone of methane-rich and sulfate-depleted pore water below 2 m sediment depth. Methane production and sulfate reduction are monitored over time for surface sediments collected from the upper flat and seeping area. Both activities were at 22 C twice as high as at 15 C. The rates in sediments from the central area were higher than in sediments from the methane seeps. Methanogenesis occurred in the presence of sulfate, and was not significantly accelerated when sulfate was depleted. The observations show a rapid anaerobic degradation of organic matter in the Janssand. The methane rich pore water is obviously transported with a unidirectional flow from the central area of the intertidal sand flat toward the low water line. This pore water flow is driven by the pressure head caused by elevation of the pore water relative to the sea surface at low tide (Billerbeck et al. 2006a). The high methane concentration at the low water line accumulates due to a continuous outflow of pore water at the seepage site that prevents penetration of electron acceptors such as oxygen and sulfate to reoxidize the reduced products of anaerobic degradation (de Beer et al. 2006). It is, however, not clear why no methane accumulates or sulfate is depleted in the upper 2 m of the flats.