Showing papers on "Methane published in 2005"

Different Adsorption Behaviors of Methane and Carbon Dioxide in the Isotypic Nanoporous Metal Terephthalates MIL-53 and MIL-47

Abstract: A distinct step in the isotherm occurs during the adsorption of CO2 on MIL-53 at 304 K. Such behavior is neither observed during the adsorption of CH4 on MIL-53 nor during the adsorption on the isostructural MIL-47. This phenomenon seems to be due to a different mechanism than that of previous adsorption steps on MOF samples. It is suggested that a breathing behavior is induced in MIL-53 during CO2 adsorption.

Biogeochemistry of Methane Exchange between Natural Wetlands and the Atmosphere

Abstract: This review examines the interactions among physical, chemical, and biological factors responsible for methane (CH4) emission from natural wetlands. Methane is a chemically and radiatively important atmospheric trace gas. Emission from wetlands is a significant component of the atmospheric CH4 budget, releasing 145 Tg CH4 annually to the atmosphere, or about 25% of total emissions from all anthropogenic and natural sources. Wetlands are characterized by a subsurface, anaerobic zone of CH4 production by methanogenic bacteria and an surficial, aerobic zone of CH4 oxidation by methanotrophic bacteria. Wetlands transfer CH4 to the atmosphere by diffusion, ebullition, and by transport through arenchymous vascular plants. However, about 20 to 40% of the CH4 produced in anaerobic wetland soils is oxidized in the rhizosphere and in surficial oxic layers during diffusive transport to the soil surface. Rates of CH4 emission in wetlands are commonly 100 mg m-2 day-1, and represent the net effect of production and co...

Volumetric strain associated with methane desorption and its impact on coalbed gas production from deep coal seams

Abstract: The permeability of deep (1000 m; 3300 ft) coal seams is commonly low. For deep coal seams, significant reservoir pressure drawdown is required to promote gas desorption because of the Langmuir-type isotherm that typifies coals. Hence, a large permeability decline may occur because of pressure drawdown and the resulting increase in effective stress, depending on coal properties and the stress field during production. However, the permeability decline can potentially be offset by the permeability enhancement caused by the matrix shrinkage associated with methane desorption. The predictability of varying permeability is critical for coalbed gas exploration and production-well management. We have investigated quantitatively the effects of reservoir pressure and sorption-induced volumetric strain on coal-seam permeability with constraints from the adsorption isotherm and associated volumetric strain measured on a Cretaceous Mesaverde Group coal (Piceance basin) and derived a stress-dependent permeability model. Our results suggest that the favorable coal properties that can result in less permeability reduction during earlier production and an earlier strong permeability rebound (increase in permeability caused by coal shrinkage) with methane desorption include (1) large bulk or Young's modulus; (2) large adsorption or Langmuir volume; (3) high Langmuir pressure; (4) high initial permeability and dense cleat spacing; and (5) low initial reservoir pressure and high in-situ gas content. Permeability variation with gas production is further dependent on the orientation of the coal seam, the reservoir stress field, and the cleat structure. Well completion with injection of N2 and displacement of CH4 only results in short-term enhancement of permeability and does not promote the overall gas production for the coal studied.

Crystal structure of a membrane-bound metalloenzyme that catalyses the biological oxidation of methane.

Abstract: Particulate methane monooxygenase (pMMO) is an integral membrane metalloenzyme that catalyses the conversion of methane to methanol. Knowledge of how pMMO performs this extremely challenging chemistry may have an impact on the use of methane as an alternative energy source by facilitating the development of new synthetic catalysts. We have determined the structure of pMMO from the methanotroph Methylococcus capsulatus (Bath) to a resolution of 2.8 A. The enzyme is a trimer with an α3β3γ3 polypeptide arrangement. Two metal centres, modelled as mononuclear copper and dinuclear copper, are located in soluble regions of each pmoB subunit, which resembles cytochrome c oxidase subunit II. A third metal centre, occupied by zinc in the crystal, is located within the membrane. The structure provides new insight into the molecular details of biological methane oxidation. Methane is the main component of natural gas, so there is keen interest in methods of converting it into liquids such as methanol for use as alternatives to petroleum. But it is also the most inert hydrocarbon, and no practical catalysts have been developed to crack the problem. Methane-eating bacteria have cracked it, however, most of them with the enzyme methane monooxygenase. The structure of this enzyme has now been determined to 2.8 A resolution, revealing that the protein contains three monomers and three metal centres. Future work to establish which of the metal centres is catalytic and how the electrons needed to oxidize methane are delivered may facilitate development of synthetic catalysts to convert methane into methanol.

High-Pressure Adsorption Equilibria of Methane and Carbon Dioxide on Several Activated Carbons

Abstract: High-pressure excess adsorption equilibria of methane and carbon dioxide on five microporous activated carbons were measured. Adsorption isotherms were obtained at temperatures ranging from (273 to 333) K and at pressures ranging from (0.5 to 6000) kPa using a static volumetric apparatus. The experimental data were analyzed using the Toth model and the Dubinin−Astakhov model. The isosteric enthalpies of adsorption and the limiting heat of adsorption for both adsorbates on all activated carbons were calculated using the Clausius−Clapeyron equations and the van't Hoff equations, respectively.

Rain, winds and haze during the Huygens probe's descent to Titan's surface

Abstract: The irreversible conversion of methane into higher hydrocarbons in Titan's stratosphere implies a surface or subsurface methane reservoir. Recent measurements from the cameras aboard the Cassini orbiter fail to see a global reservoir, but the methane and smog in Titan's atmosphere impedes the search for hydrocarbons on the surface. Here we report spectra and high-resolution images obtained by the Huygens Probe Descent Imager/Spectral Radiometer instrument in Titan's atmosphere. Although these images do not show liquid hydrocarbon pools on the surface, they do reveal the traces of once flowing liquid. Surprisingly like Earth, the brighter highland regions show complex systems draining into flat, dark lowlands. Images taken after landing are of a dry riverbed. The infrared reflectance spectrum measured for the surface is unlike any other in the Solar System; there is a red slope in the optical range that is consistent with an organic material such as tholins, and absorption from water ice is seen. However, a blue slope in the near-infrared suggests another, unknown constituent. The number density of haze particles increases by a factor of just a few from an altitude of 150 km to the surface, with no clear space below the tropopause. The methane relative humidity near the surface is 50 per cent.

Global Distribution of Methane Hydrate in Ocean Sediment

Abstract: In this paper, we present an equilibrium thermodynamic model to accurately predict the maximum depth of hydrate stability in the seafloor, including the effects of water salinity, hydrate confinement in pores, and the distribution of pore sizes in natural sediments. This model uses sediment type, geothermal gradient, and seafloor depth as input to predict the thickness of the hydrate zone. Using this hydrate model and a mass-transfer description for hydrate formation, we have also developed a predictive method for the occurrence of methane hydrates in the ocean. Based on this information, a prediction for the distribution of methane hydrate in ocean sediment is presented on a 1° latitude by 1° longitude (1° × 1°) global grid. From this detailed prediction, we estimate that there is a total volume of 1.2 × 1017 m3 of methane gas (expanded to atmospheric conditions), or, equivalently, 74 400 Gt of CH4 in ocean hydrates, which is 3 orders of magnitude larger than worldwide conventional natural gas reserves. ...

Changes in carbon dioxide during an oceanic anoxic event linked to intrusion into Gondwana coals

Abstract: The marine sedimentary record exhibits evidence for episodes of enhanced organic carbon burial known as 'oceanic anoxic events' (OAEs). They are characterized by carbon-isotope excursions in marine and terrestrial reservoirs and mass extinction of marine faunas. Causal mechanisms for the enhancement of organic carbon burial during OAEs are still debated, but it is thought that such events should draw down significant quantities of atmospheric carbon dioxide. In the case of the Toarcian OAE (approximately 183 million years ago), a short-lived negative carbon-isotope excursion in oceanic and terrestrial reservoirs has been interpreted to indicate raised atmospheric carbon dioxide caused by oxidation of methane catastrophically released from either marine gas hydrates or magma-intruded organic-rich rocks. Here we test these two leading hypotheses for a negative carbon isotopic excursion marking the initiation of the Toarcian OAE using a high-resolution atmospheric carbon dioxide record obtained from fossil leaf stomatal frequency. We find that coincident with the negative carbon-isotope excursion carbon dioxide is first drawn down by 350 +/- 100 p.p.m.v. and then abruptly elevated by 1,200 +/- 400 p.p.m.v, and infer a global cooling and greenhouse warming of 2.5 +/- 0.1 degrees C and 6.5 +/- 1 degrees C, respectively. The pattern and magnitude of carbon dioxide change are difficult to reconcile with catastrophic input of isotopically light methane from hydrates as the cause of the negative isotopic signal. Our carbon dioxide record better supports a magma-intrusion hypothesis, and suggests that injection of isotopically light carbon from the release of thermogenic methane occurred owing to the intrusion of Gondwana coals by Toarcian-aged Karoo-Ferrar dolerites.

Assessing Methane Emissions from Global Space-Borne Observations

Abstract: In the past two centuries, atmospheric methane has more than doubled and now constitutes 20% of the anthropogenic climate forcing by greenhouse gases. Yet its sources are not well quantified, introducing uncertainties in its global budget. We retrieved the global methane distribution by using spaceborne near-infrared absorption spectroscopy. In addition to the expected latitudinal gradient, we detected large-scale patterns of anthropogenic and natural methane emissions. Furthermore, we observed unexpectedly high methane concentrations over tropical rainforests, revealing that emission inventories considerably underestimated methane sources in these regions during the time period of investigation (August through November 2003).

Methanotrophic symbionts provide carbon for photosynthesis in peat bogs

Abstract: Wetlands are the largest natural source of atmospheric methane, the second most important greenhouse gas. Methane flux to the atmosphere depends strongly on the climate; however, by far the largest part of the methane formed in wetland ecosystems is recycled and does not reach the atmosphere. The biogeochemical controls on the efficient oxidation of methane are still poorly understood. Here we show that submerged Sphagnum mosses, the dominant plants in some of these habitats, consume methane through symbiosis with partly endophytic methanotrophic bacteria, leading to highly effective in situ methane recycling. Molecular probes revealed the presence of the bacteria in the hyaline cells of the plant and on stem leaves. Incubationwith 13C-methane showed rapid in situ oxidation by these bacteria to carbon dioxide, which was subsequently fixed by Sphagnum, as shown by incorporation of 13C-methane into plant sterols. In this way, methane acts as a significant (10–15%) carbon source for Sphagnum. The symbiosis explains both the efficient recycling of methane and the high organic carbon burial in these wetland ecosystems.

Characterization of the effects of pressure and hydrogen concentration on laminar burning velocities of methane–hydrogen–air mixtures

Abstract: The aim of the present work was to characterize both the effects of pressure and of hydrogen addition on methane/air premixed laminar flames. The experimental setup consists of a spherical combustion chamber coupled to a classical shadowgraphy system. Flame pictures are recorded by a high speed camera. Global equivalence ratios were varied from 0.7 to 1.2 for the initial pressure range from 0.1 to 0.5 MPa. The mole fraction of hydrogen in the methane + hydrogen mixture was varied from 0 to 0.2. Experimental results were compared to calculations using a detailed chemical kinetic scheme (GRIMECH 3.0). First, the results for atmospheric laminar CH4/air flames were compared to the literature. Very good agreements were obtained both for laminar burning velocities and for burned gas Markstein length. Then, increasing the hydrogen content in the mixture was found to be responsible for an increase in the laminar burning velocity and for a reduction of the flame dependence on stretch. Transport effects, through the reduction of the fuel Lewis number, play a role in reducing the sensitivity of the fundamental flame velocity to the stretch. Finally, when the pressure was increased, the laminar burning velocity decreased for all mixtures. The pressure domain was limited to 0.5 MPa due to the onset of instabilities at pressures above this value.

Episodic outgassing as the origin of atmospheric methane on Titan

Abstract: The 5% methane present in the nitrogen-rich atmosphere of Titan, Saturn's largest moon, would disappear in tens of millions of years in the absence of a methane source to replenish it. Until the arrival of the Cassini-Huygens mission at Saturn the favoured candidate source had been liquid hydrocarbon seas hundreds of metres thick, but no trace of such seas was found. Now numerical modelling suggests that episodic outgassing of methane stored as clathrate hydrates, associated with an ammonia-rich water ocean is the most likely source, which ties in with a Cassini fly-by image showing a possible cryovolcano. Saturn's largest satellite, Titan, has a massive nitrogen atmosphere containing up to 5 per cent methane near its surface. Photochemistry in the stratosphere would remove the present-day atmospheric methane in a few tens of millions of years1. Before the Cassini-Huygens mission arrived at Saturn, widespread liquid methane or mixed hydrocarbon seas hundreds of metres in thickness were proposed as reservoirs from which methane could be resupplied to the atmosphere over geologic time2. Titan fly-by observations3,4,5 and ground-based observations6 rule out the presence of extensive bodies of liquid hydrocarbons at present, which means that methane must be derived from another source over Titan's history. Here we show that episodic outgassing of methane stored as clathrate hydrates within an icy shell above an ammonia-enriched water ocean is the most likely explanation for Titan's atmospheric methane. The other possible explanations all fail because they cannot explain the absence of surface liquid reservoirs and/or the low dissipative state of the interior. On the basis of our models, we predict that future fly-bys should reveal the existence of both a subsurface water ocean and a rocky core, and should detect more cryovolcanic edifices.

Methane reforming kinetics within a Ni–YSZ SOFC anode support

Abstract: This paper reports experimental and modeling investigations of thermal methane reforming chemistry within porous Ni–YSZ anode materials. Because the reforming chemistry is difficult to observe directly in an operating fuel cell, a specially designed experiment is developed. In the experiment a 0.75 mm-thick anode is sandwiched between two small co-flowing gas channels. One channel represents the fuel channel of a solid-oxide fuel cell (SOFC). The composition in the other channel carries the species that would be produced in an operating fuel cell by the electrochemical charge-transfer reactions in the thin three-phase regions near the interface between the anode and the dense electrolyte membrane (i.e., H2O and CO2). Because the anode structure is porous (and there is no dense electrolyte or cathode applied), there is convective and diffusive species flux between the two flow channels. The entire assembly is maintained at approximately 800 ° C in a furnace. The results of heterogeneous reforming kinetics are determined by using mass spectrometry to measure the species composition at the outlet of both channels. Experimental results are interpreted using a computational model that incorporates channel gas flow, porous-media transport, and elementary heterogeneous chemical kinetics. The overall objective is to develop quantitative models of non-electrochemical heterogeneous reforming chemistry within a Ni–YSZ anode.

Catalytic dry reforming of methane over high surface area ceria

Abstract: High surface area ceria (CeO 2 (HSA)), synthesized by a surfactant-assisted approach, was found to have useful dry reforming activity for H 2 and CO production under solid oxide fuel cells (SOFCs) conditions. The catalyst provides significantly higher reforming reactivity and excellent resistance toward carbon deposition compared to Ni/Al 2 O 3 and conventional low surface area ceria (CeO 2 (LSA)) under dry reforming conditions. These enhancements are due to the high redox property of CeO 2 (HSA). During the dry reforming process, the redox reactions between the gaseous components in the system and the lattice oxygen (O x ) take place on ceria surface. Among these reactions, the rapid redox reactions of carbon compounds such as CH 4 , and CO with lattice oxygen (CH 4 + O x → CO + H 2 + O x −1 and CO + O x = CO 2 + O x −1 ) can prevent the formation of carbon species from the methane decomposition and Boudard reactions even at low inlet carbon dioxide concentration. In particular, the dry reforming rate over CeO 2 (HSA) is proportional to the methane partial pressure and the operating temperature. Carbon dioxide presents weak positive impact on the methane conversion, whereas both carbon monoxide and hydrogen inhibit the reforming rate. The activation energies and reforming rates under the same methane concentration for CeO 2 toward the dry reforming are almost equal to the steam reforming as previously reported [1–4] . This result suggests the similar reaction mechanisms for both the steam reforming and the dry reforming over CeO 2 ; i.e., the dry reforming rate is governed by the slow reaction of adsorbed methane, or surface hydrocarbon species, with oxygen in CeO 2 , and a rapid gas–solid reaction between CO 2 and CeO 2 to replenish the oxygen.

Have olivine, will gas: Serpentinization and the abiogenic production of methane on Mars

Abstract: [1] Spatial variability of methane (CH4) on Mars suggests the presence of localized subsurface sources. Here, we show that olivine hydration in the Martian regolith and crust may be a major CH4 source, which contributed significantly to the warming of early Mars. Methane production is kinetically and thermodynamically favored during low-T aqueous alteration of olivine-rich rocks. Sustained release of CH4 on present-day Mars may come through the breakdown of ancient CH4 hydrates and from springs driven by geothermal heat.

Efficient recovery of CO2 from flue gas by clathrate hydrate formation in porous silica gels.

Abstract: Thermodynamic measurements and NMR spectroscopic analysis were used to show that it is possible to recover CO2 from flue gas by forming a mixed hydrate that removes CO2 preferentially from CO2/N2 gas mixtures using water dispersed in the pores of silica gel. Kinetic studies with 1H NMR microimaging showed that the dispersed water in the silica gel pore system reacts readily with the gas, thus obviating the need for a stirred reactor and excess water. Hydrate phase equilibria for the ternary CO2−N2−water system in silica gel pores were measured, which show that the three-phase hydrate−water-rich liquid−vapor equilibrium curves were shifted to higher pressures at a specific temperature when the concentration of CO2 in the vapor phase decreased. 13C cross-polarization NMR spectral analysis and direct measurement of the CO2 content in the hydrate phase suggested that the mixed hydrate is structure I at gas compositions of more than 10 mol % CO2, and that the CO2 molecules occupy mainly the more abundant 51262...

Coke Formation over a Nickel Catalyst under Methane Dry Reforming Conditions: Thermodynamic and Kinetic Models

Abstract: The CO2 reforming of methane is studied over a 20 wt % Ni/USY-zeolite, and more specifically, a thermodynamic analysis of the formation of coke is used as a basis for the kinetic modeling of coke phenomena that exist under dry reforming conditions. Two thermodynamic parameters, α and β, are compared to the equilibrium constants for the CH4 decomposition and the CO disproportionation reactions and defined to determine whether coke formation is favored. This thermodynamic analysis elucidates the significance of the CO disproportionation reaction on the amount of coke deposited over the catalyst under consideration. A kinetic model with negative overall order of one, with respect to the partial pressure of carbon monoxide, is found as the most accurate prediction of the rate of coke formation. This type of kinetics strongly suggests the requirement of three adjacent free catalyst sites for the coking reaction to proceed under allowable thermodynamic conditions.

An overview of the descent and landing of the Huygens probe on Titan

Abstract: Titan, Saturn's largest moon, is the only Solar System planetary body other than Earth with a thick nitrogen atmosphere. The Voyager spacecraft confirmed that methane was the second-most abundant atmospheric constituent in Titan's atmosphere, and revealed a rich organic chemistry, but its cameras could not see through the thick organic haze. After a seven-year interplanetary journey on board the Cassini orbiter, the Huygens probe was released on 25 December 2004. It reached the upper layer of Titan's atmosphere on 14 January and landed softly after a parachute descent of almost 2.5 hours. Here we report an overview of the Huygens mission, which enabled studies of the atmosphere and surface, including in situ sampling of the organic chemistry, and revealed an Earth-like landscape. The probe descended over the boundary between a bright icy terrain eroded by fluvial activity--probably due to methane-and a darker area that looked like a river- or lake-bed. Post-landing images showed centimetre-sized surface details.