Showing papers on "Methane published in 2013"

Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation

Abstract: A series of porous crystalline materials known as metal–organic materials are prepared, and a full sorption study shows that controlled pore size (rather than large surface area) coupled with appropriate chemistry lead to materials exhibiting fast and highly selective CO2 sorption. Metal organic frameworks are porous crystalline materials widely studied as potential gas separation and storage materials for clean energy applications. A general trend in this field has been the development of materials with the largest possible surface area with the aim of maximizing uptake of gases. In this paper the authors generate a series of metal organic frameworks and carry out sorption experiments that suggest that surface area may not be as important as was thought. Rather, pore size, coupled with appropriate chemistry, are the keys to fast CO2 uptake and strong CO2 sorption. Materials designed on these principles attain high selectivity for CO2 over nitrogen, oxygen, methane and hydrogen even in the presence of moisture. The energy costs associated with the separation and purification of industrial commodities, such as gases, fine chemicals and fresh water, currently represent around 15 per cent of global energy production, and the demand for such commodities is projected to triple by 2050 (ref. 1). The challenge of developing effective separation and purification technologies that have much smaller energy footprints is greater for carbon dioxide (CO2) than for other gases; in addition to its involvement in climate change, CO2 is an impurity in natural gas, biogas (natural gas produced from biomass), syngas (CO/H2, the main source of hydrogen in refineries) and many other gas streams. In the context of porous crystalline materials that can exploit both equilibrium and kinetic selectivity, size selectivity and targeted molecular recognition are attractive characteristics for CO2 separation and capture, as exemplified by zeolites 5A and 13X (ref. 2), as well as metal–organic materials (MOMs)3,4,5,6,7,8,9. Here we report that a crystal engineering7 or reticular chemistry5,9 strategy that controls pore functionality and size in a series of MOMs with coordinately saturated metal centres and periodically arrayed hexafluorosilicate (SiF62−) anions enables a ‘sweet spot’ of kinetics and thermodynamics that offers high volumetric uptake at low CO2 partial pressure (less than 0.15 bar). Most importantly, such MOMs offer an unprecedented CO2 sorption selectivity over N2, H2 and CH4, even in the presence of moisture. These MOMs are therefore relevant to CO2 separation in the context of post-combustion (flue gas, CO2/N2), pre-combustion (shifted synthesis gas stream, CO2/H2) and natural gas upgrading (natural gas clean-up, CO2/CH4).

Three decades of global methane sources and sinks

Abstract: Methane is an important greenhouse gas, responsible for about 20% of the warming induced by long-lived greenhouse gases since pre-industrial times. By reacting with hydroxyl radicals, methane reduces the oxidizing capacity of the atmosphere and generates ozone in the troposphere. Although most sources and sinks of methane have been identified, their relative contributions to atmospheric methane levels are highly uncertain. As such, the factors responsible for the observed stabilization of atmospheric methane levels in the early 2000s, and the renewed rise after 2006, remain unclear. Here, we construct decadal budgets for methane sources and sinks between 1980 and 2010, using a combination of atmospheric measurements and results from chemical transport models, ecosystem models, climate chemistry models and inventories of anthropogenic emissions. The resultant budgets suggest that data-driven approaches and ecosystem models overestimate total natural emissions. We build three contrasting emission scenarios-which differ in fossil fuel and microbial emissions-to explain the decadal variability in atmospheric methane levels detected, here and in previous studies, since 1985. Although uncertainties in emission trends do not allow definitive conclusions to be drawn, we show that the observed stabilization of methane levels between 1999 and 2006 can potentially be explained by decreasing-to-stable fossil fuel emissions, combined with stable-to-increasing microbial emissions. We show that a rise in natural wetland emissions and fossil fuel emissions probably accounts for the renewed increase in global methane levels after 2006, although the relative contribution of these two sources remains uncertain. © 2013 Macmillan Publishers Limited.

A Hierarchical and Comparative Kinetic Modeling Study of C1 − C2 Hydrocarbon and Oxygenated Fuels

Abstract: A detailed chemical kinetic mechanism has been developed to describe the oxidation of small hydrocarbon and oxygenated hydrocarbon species. The reactivity of these small fuels and intermediates is of critical importance in understanding and accurately describing the combustion characteristics, such as ignition delay time, flame speed, and emissions of practical fuels. The chosen rate expressions have been assembled through critical evaluation of the literature, with minimum optimization performed. The mechanism has been validated over a wide range of initial conditions and experimental devices, including flow reactor, shock tube, jet-stirred reactor, and flame studies. The current mechanism contains accurate kinetic descriptions for saturated and unsaturated hydrocarbons, namely methane, ethane, ethylene, and acetylene, and oxygenated species; formaldehyde, methanol, acetaldehyde, and ethanol.

Selectivity of CO2 reduction on copper electrodes: The role of the kinetics of elementary steps

Abstract: On the right path: Based on DFT calculations (incorporating the role of water solvation) of the activation barriers of elementary steps, a new path that leads to methane and ethylene for CO(2) electroreduction on Cu(111) was identified. Methane formation proceeds through reduction of CO to COH (path II, see picture), which leads to CH(x) species that can produce both methane and ethylene, as observed experimentally.

Increased stray gas abundance in a subset of drinking water wells near Marcellus shale gas extraction

Abstract: Horizontal drilling and hydraulic fracturing are transforming energy production, but their potential environmental effects remain controversial. We analyzed 141 drinking water wells across the Appalachian Plateaus physiographic province of northeastern Pennsylvania, examining natural gas concentrations and isotopic signatures with proximity to shale gas wells. Methane was detected in 82% of drinking water samples, with average concentrations six times higher for homes <1 km from natural gas wells (P = 0.0006). Ethane was 23 times higher in homes <1 km from gas wells (P = 0.0013); propane was detected in 10 water wells, all within approximately 1 km distance (P = 0.01). Of three factors previously proposed to influence gas concentrations in shallow groundwater (distances to gas wells, valley bottoms, and the Appalachian Structural Front, a proxy for tectonic deformation), distance to gas wells was highly significant for methane concentrations (P = 0.007; multiple regression), whereas distances to valley bottoms and the Appalachian Structural Front were not significant (P = 0.27 and P = 0.11, respectively). Distance to gas wells was also the most significant factor for Pearson and Spearman correlation analyses (P < 0.01). For ethane concentrations, distance to gas wells was the only statistically significant factor (P < 0.005). Isotopic signatures (δ13C-CH4, δ13C-C2H6, and δ2H-CH4), hydrocarbon ratios (methane to ethane and propane), and the ratio of the noble gas 4He to CH4 in groundwater were characteristic of a thermally postmature Marcellus-like source in some cases. Overall, our data suggest that some homeowners living <1 km from gas wells have drinking water contaminated with stray gases.

Anthropogenic emissions of methane in the United States

Abstract: sions nationally by a factor of ∼1.5 and ∼1.7, respectively. Our study indicates that emissions due to ruminants and manure are up to twice the magnitude of existing inventories. In addition, the discrepancy in methane source estimates is particularly pronounced in the south-central United States, where we find total emissions are ∼2.7 times greater than in most inventories and account for 24 ± 3% of national emissions. The spatial patterns of our emission fluxes and observed methane–propane correlations indicate that fossil fuel extraction and refining are major contributors (45 ± 13%) in the south-central United States. This result suggests that regional methane emissions due to fossil fuel extraction and processing could be 4.9 ± 2.6 times larger than in EDGAR, the most comprehensive global methane inventory. These results cast doubt on the US EPA’s recent decision to downscale its estimate of national natural gas emissions by 25–30%. Overall, we conclude that methane emissions associated with both the animal husbandry and fossil fuel industries have larger greenhouse gas impacts than indicated by existing inventories.

Methane emissions estimate from airborne measurements over a western United States natural gas field

Abstract: [1] Methane (CH4) emissions from natural gas production are not well quantified and have the potential to offset the climate benefits of natural gas over other fossil fuels. We use atmospheric measurements in a mass balance approach to estimate CH4 emissions of 55 ± 15 × 103 kg h−1 from a natural gas and oil production field in Uintah County, Utah, on 1 day: 3 February 2012. This emission rate corresponds to 6.2%–11.7% (1σ) of average hourly natural gas production in Uintah County in the month of February. This study demonstrates the mass balance technique as a valuable tool for estimating emissions from oil and gas production regions and illustrates the need for further atmospheric measurements to determine the representativeness of our single-day estimate and to better assess inventories of CH4 emissions.

Progress in solid oxide fuel cells with nickel-based anodes operating on methane and related fuels.

Abstract: Operating on Methane and Related Fuels Wei Wang,† Chao Su,‡ Yuzhou Wu, Ran Ran,† and Zongping Shao*,† †State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry & Chemical Engineering, Nanjing University of Technology, No. 5 Xin Mofan Road, Nanjing 210009, People’s Republic of China ‡Department of Chemical Engineering, Curtin University, Perth, WA 6845, Australia Department of Chemical Engineering, Monash University, Clayton, VIC 3800, Australia

Methane Adsorption on Shale under Simulated Geological Temperature and Pressure Conditions

Abstract: Shale gas is becoming an increasingly important energy resource. In this study, the adsorption of methane on a dry, organic-rich Alum shale sample was studied at pressures up to ∼14 MPa and temperatures in the range 300–473 K, which are relevant to gas storage under geological conditions. Maximum methane excess uptake was 0.176–0.042 mmol g–1 (125–30 scf t–1) for the temperature range of 300–473 K. The decrease in maximum methane surface excess with increasing temperature can be described with a linear model. An isosteric enthalpy of adsorption 19.2 ± 0.1 kJ mol–1 was determined at 0.025 mmol g–1 using the van’t Hoff equation. Supercritical adsorption was modeled using the modified Dubinin–Radushkevich and the Langmuir equations. The results are compared with absolute isotherms calculated from surface excess and the pore volumes obtained from subcritical gas adsorption (nitrogen (78 K), carbon dioxide (273 and 195 K), and CH4 (112 K)). The subcritical adsorption and the surface excess results allow an upp...

The Global Occurrence of Natural Gas Hydrate

Abstract: Natural gas hydrate occurs worldwide in oceanic sediment of continental and insular slopes and rises of active and passive margins, in deep-water sediment of inland lakes and seas, and in polar sediment on both continents and continental shelves. In aquatic sediment, where water depths exceed about 300 m and bottom water temperatures approach 0° C, gas hydrate is found at the seafloor to sediment depths of about 1,100 m. In polar continental regions, gas hydrate can be present in sediment at depths between about 150 and 2000 m. Thus, natural gas hydrate is restricted to the shallow geosphere where its presence affects the physical and chemical properties of near-surface sediment. An updated global inventory reports on natural gas hydrate recovered from 19 places worldwide and includes 77 places where the presence of gas hydrate has been inferred from geophysical, geochemical, and geological evidence. The potential amount of methane in natural gas hydrate is enormous, with current estimates converging around about 10 teratonnes (10 19 g) of methane carbon.

Highly efficient methane biocatalysis revealed in a methanotrophic bacterium

Abstract: Methane is a promising renewable carbon source for chemical synthesis, yet methane bio-gas is currently underutilised as a feedstock. Here the authors examine the metabolic processes of methanotrophic bacteria to assess their use for conversion of methane to value-added chemical products.

Preindustrial to present-day changes in tropospheric hydroxyl radical and methane lifetime from the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP)

Abstract: . We have analysed time-slice simulations from 17 global models, participating in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), to explore changes in present-day (2000) hydroxyl radical (OH) concentration and methane (CH4) lifetime relative to preindustrial times (1850) and to 1980. A comparison of modeled and observation-derived methane and methyl chloroform lifetimes suggests that the present-day global multi-model mean OH concentration is overestimated by 5 to 10% but is within the range of uncertainties. The models consistently simulate higher OH concentrations in the Northern Hemisphere (NH) compared with the Southern Hemisphere (SH) for the present-day (2000; inter-hemispheric ratios of 1.13 to 1.42), in contrast to observation-based approaches which generally indicate higher OH in the SH although uncertainties are large. Evaluation of simulated carbon monoxide (CO) concentrations, the primary sink for OH, against ground-based and satellite observations suggests low biases in the NH that may contribute to the high north–south OH asymmetry in the models. The models vary widely in their regional distribution of present-day OH concentrations (up to 34%). Despite large regional changes, the multi-model global mean (mass-weighted) OH concentration changes little over the past 150 yr, due to concurrent increases in factors that enhance OH (humidity, tropospheric ozone, nitrogen oxide (NOx) emissions, and UV radiation due to decreases in stratospheric ozone), compensated by increases in OH sinks (methane abundance, carbon monoxide and non-methane volatile organic carbon (NMVOC) emissions). The large inter-model diversity in the sign and magnitude of preindustrial to present-day OH changes (ranging from a decrease of 12.7% to an increase of 14.6%) indicate that uncertainty remains in our understanding of the long-term trends in OH and methane lifetime. We show that this diversity is largely explained by the different ratio of the change in global mean tropospheric CO and NOx burdens (ΔCO/ΔNOx, approximately represents changes in OH sinks versus changes in OH sources) in the models, pointing to a need for better constraints on natural precursor emissions and on the chemical mechanisms in the current generation of chemistry-climate models. For the 1980 to 2000 period, we find that climate warming and a slight increase in mean OH (3.5 ± 2.2%) leads to a 4.3 ± 1.9% decrease in the methane lifetime. Analysing sensitivity simulations performed by 10 models, we find that preindustrial to present-day climate change decreased the methane lifetime by about four months, representing a negative feedback on the climate system. Further, we analysed attribution experiments performed by a subset of models relative to 2000 conditions with only one precursor at a time set to 1860 levels. We find that global mean OH increased by 46.4 ± 12.2% in response to preindustrial to present-day anthropogenic NOx emission increases, and decreased by 17.3 ± 2.3%, 7.6 ± 1.5%, and 3.1 ± 3.0% due to methane burden, and anthropogenic CO, and NMVOC emissions increases, respectively.

Methane, microbes and models: fundamental understanding of the soil methane cycle for future predictions

Abstract: Methane is an important greenhouse gas and microbes in the environment play major roles in both global methane emissions and terrestrial sinks However, a full mechanistic understanding of the response of the methane cycle to global change is lacking Recent studies suggest that a number of biological and environmental processes can influence the net flux of methane from soils to the atmosphere but the magnitude and direction of their impact are still debated Here, we synthesize recent knowledge on soil microbial and biogeochemical process and the impacts of climate change factors on the soil methane cycle We focus on (i) identification of the source and magnitude of methane flux and the global factors that may change the flux rate and magnitude in the future, (ii) the microbial communities responsible for methane production and terrestrial sinks, and (iii) how they will respond to future climatic scenarios and the consequences for feedback responses at a global scale We also identify the research gaps in each of the topics identified above, provide evidence which can be used to demonstrate microbial regulation of methane cycle and suggest that incorporation of microbial data from emerging -omic technologies could be harnessed to increase the predictive power of simulation models

Evaluation of Methane Sources in Groundwater in Northeastern Pennsylvania

Abstract: Testing of 1701 water wells in northeastern Pennsylvania shows that methane is ubiquitous in groundwater, with higher concentrations observed in valleys vs. upland areas and in association with calcium-sodiumbicarbonate, sodium-bicarbonate, and sodium-chloride rich waters—indicating that, on a regional scale, methane concentrations are best correlated to topographic and hydrogeologic features, rather than shale-gas extraction. In addition, our assessment of isotopic and molecular analyses of hydrocarbon gases in the Dimock Township suggest that gases present in local water wells are most consistent with Middle and Upper Devonian gases sampled in the annular spaces of local gas wells, as opposed to Marcellus Production gas. Combined, these findings suggest that the methane concentrations in Susquehanna County water wells can be explained without the migration of Marcellus shale gas through fractures, an observation that has important implications for understanding the nature of risks associated with shale-gas extraction.

Bi-reforming of methane from any source with steam and carbon dioxide exclusively to metgas (CO-2H2) for methanol and hydrocarbon synthesis.

Abstract: A catalyst based on nickel oxide on magnesium oxide (NiO/MgO) thermally activated under hydrogen is effective for the bi-reforming with steam and CO2 (combined steam and dry reforming) of methane as well as natural gas in a tubular flow reactor at elevated pressures (5–30 atm) and temperatures (800–950 °C). By adjusting the CO2-to-steam ratio in the gas feed, the H2/CO ratio in the produced syn-gas could be easily adjusted in a single step to the desired value of 2 for methanol and hydrocarbon synthesis.

Methane as raw material in synthetic chemistry: the final frontier

Abstract: In spite of its large availability in natural or shale gas deposits, the use of methane in the chemical industry as feedstock from a synthetic point of view yet constitutes a challenge in modern chemistry. Only the production of the so-called syngas, a mixture of CO and H2 derived from the complete cleavage of the methane molecule, operates at the industrial level. The relevance of methane in the current industry, mainly toward methanol production, is described in this Tutorial. The methanol economy has been already proposed as an alternative to current fuel sources. Methanol synthesis directly from methane would imply the activation of the latter. Toward this end, the different methodologies reported to activate methane with transition metal complexes as well as the few examples of the catalytic functionalization of methane are presented.

Sediment trapping by dams creates methane emission hot spots.

Abstract: Inland waters transport and transform substantial amounts of carbon and account for ∼18% of global methane emissions. Large reservoirs with higher areal methane release rates than natural waters contribute significantly to freshwater emissions. However, there are millions of small dams worldwide that receive and trap high loads of organic carbon and can therefore potentially emit significant amounts of methane to the atmosphere. We evaluated the effect of damming on methane emissions in a central European impounded river. Direct comparison of riverine and reservoir reaches, where sedimentation in the latter is increased due to trapping by dams, revealed that the reservoir reaches are the major source of methane emissions (∼0.23 mmol CH4 m(-2) d(-1) vs ∼19.7 mmol CH4 m(-2) d(-1), respectively) and that areal emission rates far exceed previous estimates for temperate reservoirs or rivers. We show that sediment accumulation correlates with methane production and subsequent ebullitive release rates and may therefore be an excellent proxy for estimating methane emissions from small reservoirs. Our results suggest that sedimentation-driven methane emissions from dammed river hot spot sites can potentially increase global freshwater emissions by up to 7%.

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

Abstract: 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% 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 H2 over a broad range of pressures and temperatures are also reported and agree with our computational findings.

High carbon-resistance Ni/CeAlO3-Al2O3 catalyst for CH4/CO2 reforming

Abstract: High carbon-resistance Ni/Ce-AlO catalysts have been developed for dry reforming of methane (DRM) that is attracting growing attention for chemical recycling of CO2 to fuels/chemicals. Cerium is definitely identified to exist in the form of CeAlO3 phase after reduction at 900 °C, and so is it under running conditions. The formation of CeAlO3 phase significantly enhances the catalyst carbon-resistance without decreasing the activity. Whereas the catalysts with or without CeAlO3 all show good activity maintenance within 250 h testing at 800 °C using 20,000 mL h−1 gcat−1, their carbon deposition amounts exhibit significant decrease from 0.92 to 0.29 g gcat−1 along with the increase of the CeAlO3 phase. The presence of CeAlO3 can inhibit growth of graphitic carbon on nickel surface while the formation of amorphous carbon is independent of the CeAlO3. The CeAlO3 species shows ability for decomposing CO2 to form active surface oxygen and therefore the carbon-resistance promotion by nature is suggested to be contributed to an oxidative environment around Ni particles.

Soil structure and greenhouse gas emissions: a synthesis of 20 years of experimentation

Abstract: Soil structure affects microbial activity and thus influences greenhouse gas production and exchange in soil. Structure is variable and increasingly vulnerable to compaction and erosion damage as agriculture intensifies and climate changes. Few studies have specifically related the impact of structure and its variability to greenhouse gas (GHG) emissions over a wide range of soils and management treatments. The objective of this study was to draw from research in Scotland, Japan and New Zealand, which examined how soil structures affected by wheel compaction, animal trampling, tillage and land-use change influence GHG emissions in order to help identify key controlling properties. Nitrous oxide (N2O) is the main focus, though carbon dioxide (CO2), methane (CH4) and nitric oxide (NO) are included. Gas emissions were measured by using static chambers in the field or incubated intact cores. Poor structure, measured as small relative gas diffusivities and air permeabilities, restricted aeration, resulting in N2O emission or consumption dependent on mineral nitrogen contents. Structural damage (identifiable using the Visual Evaluation of Soil Structure) was especially important near the soil surface where microsites of microbial activity were exposed and aeration was impaired. Moist, well-aerated soils favoured CH4 oxidation and CO2 exchange. N2O emissions were not necessarily increased in anaerobic soils because of possible N2O consumption and microbial adaptation. Soil matric potential, volumetric water content, relative diffusivity, air permeability and water-filled pore space are relevant indicators for N2O and CH4 flux and aeration status. As pore continuity and size are so relevant, pore-scale models are likely to have an increasing role in understanding mechanisms of GHG production, transport and release.