Showing papers on "Methane published in 2014"

Methane storage in metal–organic frameworks

Abstract: Natural gas (NG), whose main component is methane, is an attractive fuel for vehicular applications. Realization of safe, cheap and convenient means and materials for high-capacity methane storage can significantly facilitate the implementation of natural gas fuelled vehicles. The physisorption based process involving porous materials offers an efficient storage methodology and the emerging porous metal-organic frameworks have been explored as potential candidates because of their extraordinarily high porosities, tunable pore/cage sizes and easily immobilized functional sites. In this view, we provide an overview of the current status of metal-organic frameworks for methane storage.

Electrocatalytic Conversion of Carbon Dioxide to Methane and Methanol on Transition Metal Surfaces

Abstract: Fuels and industrial chemicals that are conventionally derived from fossil resources could potentially be produced in a renewable, sustainable manner by an electrochemical process that operates at room temperature and atmospheric pressure, using only water, CO2, and electricity as inputs. To enable this technology, improved catalysts must be developed. Herein, we report trends in the electrocatalytic conversion of CO2 on a broad group of seven transition metal surfaces: Au, Ag, Zn, Cu, Ni, Pt, and Fe. Contrary to conventional knowledge in the field, all metals studied are capable of producing methane or methanol. We quantify reaction rates for these two products and describe catalyst activity and selectivity in the framework of CO binding energies for the different metals. While selectivity toward methane or methanol is low for most of these metals, the fact that they are all capable of producing these products, even at a low rate, is important new knowledge. This study reveals a richer surface chemistry ...

Direct, Nonoxidative Conversion of Methane to Ethylene, Aromatics, and Hydrogen

Abstract: The efficient use of natural gas will require catalysts that can activate the first C-H bond of methane while suppressing complete dehydrogenation and avoiding overoxidation. We report that single iron sites embedded in a silica matrix enable direct, nonoxidative conversion of methane, exclusively to ethylene and aromatics. The reaction is initiated by catalytic generation of methyl radicals, followed by a series of gas-phase reactions. The absence of adjacent iron sites prevents catalytic C-C coupling, further oligomerization, and hence, coke deposition. At 1363 kelvin, methane conversion reached a maximum at 48.1% and ethylene selectivity peaked at 48.4%, whereas the total hydrocarbon selectivity exceeded 99%, representing an atom-economical transformation process of methane. The lattice-confined single iron sites delivered stable performance, with no deactivation observed during a 60-hour test.

Evaluating metal–organic frameworks for natural gas storage

Abstract: Metal–organic frameworks have received significant attention as a new class of adsorbents for natural gas storage; however, inconsistencies in reporting high-pressure adsorption data and a lack of comparative studies have made it challenging to evaluate both new and existing materials. Here, we briefly discuss high-pressure adsorption measurements and review efforts to develop metal–organic frameworks with high methane storage capacities. To illustrate the most important properties for evaluating adsorbents for natural gas storage and for designing a next generation of improved materials, six metal–organic frameworks and an activated carbon, with a range of surface areas, pore structures, and surface chemistries representative of the most promising adsorbents for methane storage, are evaluated in detail. High-pressure methane adsorption isotherms are used to compare gravimetric and volumetric capacities, isosteric heats of adsorption, and usable storage capacities. Additionally, the relative importance of increasing volumetric capacity, rather than gravimetric capacity, for extending the driving range of natural gas vehicles is highlighted. Other important systems-level factors, such as thermal management, mechanical properties, and the effects of impurities, are also considered, and potential materials synthesis contributions to improving performance in a complete adsorbed natural gas system are discussed.

Methane leaks from North American natural gas systems

Abstract: Natural gas (NG) is a potential “bridge fuel” during transition to a decarbonized energy system: It emits less carbon dioxide during combustion than other fossil fuels and can be used in many industries. However, because of the high global warming potential of methane (CH4, the major component of NG), climate benefits from NG use depend on system leakage rates. Some recent estimates of leakage have challenged the benefits of switching from coal to NG, a large near-term greenhouse gas (GHG) reduction opportunity ( 1 – 3 ). Also, global atmospheric CH4 concentrations are on the rise, with the causes still poorly understood ( 4 ).

Methane fluxes show consistent temperature dependence across microbial to ecosystem scales

Abstract: Methane (CH4) is an important greenhouse gas because it has 25 times the global warming potential of carbon dioxide (CO2) by mass over a century. Recent calculations suggest that atmospheric CH4 emissions have been responsible for approximately 20% of Earth's warming since pre-industrial times. Understanding how CH4 emissions from ecosystems will respond to expected increases in global temperature is therefore fundamental to predicting whether the carbon cycle will mitigate or accelerate climate change. Methanogenesis is the terminal step in the remineralization of organic matter and is carried out by strictly anaerobic Archaea. Like most other forms of metabolism, methanogenesis is temperature-dependent. However, it is not yet known how this physiological response combines with other biotic processes (for example, methanotrophy, substrate supply, microbial community composition) and abiotic processes (for example, water-table depth) to determine the temperature dependence of ecosystem-level CH4 emissions. It is also not known whether CH4 emissions at the ecosystem level have a fundamentally different temperature dependence than other key fluxes in the carbon cycle, such as photosynthesis and respiration. Here we use meta-analyses to show that seasonal variations in CH4 emissions from a wide range of ecosystems exhibit an average temperature dependence similar to that of CH4 production derived from pure cultures of methanogens and anaerobic microbial communities. This average temperature dependence (0.96 electron volts (eV)), which corresponds to a 57-fold increase between 0 and 30°C, is considerably higher than previously observed for respiration (approximately 0.65 eV) and photosynthesis (approximately 0.3 eV). As a result, we show that both the emission of CH4 and the ratio of CH4 to CO2 emissions increase markedly with seasonal increases in temperature. Our findings suggest that global warming may have a large impact on the relative contributions of CO2 and CH4 to total greenhouse gas emissions from aquatic ecosystems, terrestrial wetlands and rice paddies.

Tracing anthropogenic carbon dioxide and methane emissions to fossil fuel and cement producers, 1854–2010

Abstract: This paper presents a quantitative analysis of the historic fossil fuel and cement production records of the 50 leading investor-owned, 31 state-owned, and 9 nation-state producers of oil, natural gas, coal, and cement from as early as 1854 to 2010. This analysis traces emissions totaling 914 GtCO2e—63 % of cumulative worldwide emissions of industrial CO2 and methane between 1751 and 2010—to the 90 “carbon major” entities based on the carbon content of marketed hydrocarbon fuels (subtracting for non-energy uses), process CO2 from cement manufacture, CO2 from flaring, venting, and own fuel use, and fugitive or vented methane. Cumulatively, emissions of 315 GtCO2e have been traced to investor-owned entities, 288 GtCO2e to state-owned enterprises, and 312 GtCO2e to nation-states. Of these emissions, half has been emitted since 1986. The carbon major entities possess fossil fuel reserves that will, if produced and emitted, intensify anthropogenic climate change. The purpose of the analysis is to understand the historic emissions as a factual matter, and to invite consideration of their possible relevance to public policy.

Methane activation: the past and future

Abstract: The conversion of methane to more valuable chemicals is one of the most intensively studied topics in catalysis. The direct conversion of methane is attractive because the process is simple, but unfortunately its products are chemicals that are more reactive than methane. The current status of this research field is discussed with an emphasis on C–H bond activation and future challenges.

Methane on the Rise—Again

Abstract: Roughly one-fifth of the increase in radiative forcing by human-linked greenhouse gases since 1750 is due to methane. The past three decades have seen prolonged periods of increasing atmospheric methane, but the growth rate slowed in the 1990s ( 1 ), and from 1999 to 2006, the methane burden (that is, the total amount of methane in the air) was nearly constant. Yet strong growth resumed in 2007. The reasons for these observed changes remain poorly understood because of limited knowledge of what controls the global methane budget ( 2 ).

High Methane Storage Capacity in Aluminum Metal–Organic Frameworks

Abstract: The use of porous materials to store natural gas in vehicles requires large amounts of methane per unit of volume. Here we report the synthesis, crystal structure and methane adsorption properties of two new aluminum metal–organic frameworks, MOF-519 and MOF-520. Both materials exhibit permanent porosity and high methane volumetric storage capacity: MOF-519 has a volumetric capacity of 200 and 279 cm3 cm–3 at 298 K and 35 and 80 bar, respectively, and MOF-520 has a volumetric capacity of 162 and 231 cm3 cm–3 under the same conditions. Furthermore, MOF-519 exhibits an exceptional working capacity, being able to deliver a large amount of methane at pressures between 5 and 35 bar, 151 cm3 cm–3, and between 5 and 80 bar, 230 cm3 cm–3.

Yolk–Satellite–Shell Structured Ni–Yolk@Ni@SiO2 Nanocomposite: Superb Catalyst toward Methane CO2 Reforming Reaction

Abstract: The CO2 (dry) reforming of methane (DRM) reaction is an environmentally benign process to convert two major greenhouse gases into synthesis gas for chemical and fuel production. A great challenge for this process involves developing catalysts with high carbon resistance abilities. Herein we synthesize, for the first time, a yolk–satellite–shell structured Ni–yolk@Ni@SiO2 nanocomposite for the DRM reaction by varying the shell thickness of Ni@SiO2 core shell nanoparticles. The formation of Ni–yolk@Ni@SiO2 is proved to be shell thickness dependent. Compared with Ni@SiO2, Ni–yolk@Ni@SiO2 with 11.2 nm silica shell thickness shows stable and near equilibrium conversion for CH4 and CO2 for 90 h at 800 °C with negligible carbon deposition. The dual effects of formation of small satellite Ni particles due to strong Ni–SiO2 interactions and yolk shell structures contribute to its high activity and stability. These findings shed light on the design of other metal yolk silica shell nanocomposites to be utilized in r...

Review on dry reforming of methane, a potentially more environmentally-friendly approach to the increasing natural gas exploitation

Abstract: With the actual growth of the natural gas industry in the US as well as the potential and availability of this non-renewable carbon source worldwide, reforming of methane gas is getting increasing attention. Methane can be used for the production of heat or electricity, as well, it can be converted to syngas, a building block that could lead to the production of liquid fuels and chemical, a very promising pathway in light of the increasing price of oil. Amongst the different reforming techniques, dry reforming could represent a very interesting approach both to valorize a cheap source or carbon (CO2) as well as to reduce the overall carbon footprint of the increasing worldwide fossil-based methane consumption. In this short review, attention will be given on the thermodynamics of dry reforming followed by an investigation on dry reforming using heterogeneous catalyst by focusing on the mots popular elements used in literature for dry reforming. Attention will as well be given to different other emerging techniques that may allow countering at one point the high thermodynamic penalties that accompanies conversion of methane using carbon dioxide.

Methane dynamics regulated by microbial community response to permafrost thaw

Abstract: Permafrost contains about 50% of the global soil carbon. It is thought that the thawing of permafrost can lead to a loss of soil carbon in the form of methane and carbon dioxide emissions. The magnitude of the resulting positive climate feedback of such greenhouse gas emissions is still unknown and may to a large extent depend on the poorly understood role of microbial community composition in regulating the metabolic processes that drive such ecosystem-scale greenhouse gas fluxes. Here we show that changes in vegetation and increasing methane emissions with permafrost thaw are associated with a switch from hydrogenotrophic to partly acetoclastic methanogenesis, resulting in a large shift in the δ(13)C signature (10-15‰) of emitted methane. We used a natural landscape gradient of permafrost thaw in northern Sweden as a model to investigate the role of microbial communities in regulating methane cycling, and to test whether a knowledge of community dynamics could improve predictions of carbon emissions under loss of permafrost. Abundance of the methanogen Candidatus 'Methanoflorens stordalenmirensis' is a key predictor of the shifts in methane isotopes, which in turn predicts the proportions of carbon emitted as methane and as carbon dioxide, an important factor for simulating the climate feedback associated with permafrost thaw in global models. By showing that the abundance of key microbial lineages can be used to predict atmospherically relevant patterns in methane isotopes and the proportion of carbon metabolized to methane during permafrost thaw, we establish a basis for scaling changing microbial communities to ecosystem isotope dynamics. Our findings indicate that microbial ecology may be important in ecosystem-scale responses to global change.

Progress and perspectives in converting biogas to transportation fuels

Abstract: The discovery of abundant natural gas resources has greatly increased the study of using methane as a feedstock to produce transportation fuels. Biogas (primarily containing methane and CO2), which is generated from waste biomass via anaerobic digestion or landfills, is regarded as a renewable source of methane, and has the potential to achieve sustainable production of transportation fuels. Since biogas also contains a significant amount of impurities (e.g., H2S, NH3, and siloxane), a cleaning procedure is generally required prior to conversion to transportation fuels. Physical approaches, mainly compression and liquefaction, have been commercially applied to upgrade biogas to bio-compressed natural gas (CNG) and liquefied biogas (LBG). For chemical approaches, catalytic reforming is the dominant method for converting methane to syngas, followed by Fischer–Tropsch synthesis (FTS) or fermentation of syngas to a variety of alcohols (e.g., methanol, ethanol, and butanol) and liquid hydrocarbon fuels (e.g., gasoline, diesel, and jet fuels). High purity hydrogen, a clean fuel, can also be produced via reforming. Methanol can be produced by direct oxidation of methane, while interest in the biological conversion of methane to methanol has grown recently due to its mild operating conditions, high conversion efficiency, and potential for using raw biogas. The derived methanol can be further converted to gasoline via a methanol to gasoline (MTG) process. This paper provides a comprehensive review of major research progress on technologies for converting biogas/methane into transportation fuels, and discusses the principles, kinetics, operating conditions, and performance of each technology. Efficient direct conversion of biogas into ethanol and higher alcohol fuels (e.g. butanol), which is envisaged to be the focus of research pursuits in the near future, is also discussed, with emphasis on the development of methane-utilizing microbes through genetic engineering.

Catalytic aromatization of methane

Abstract: Recent developments in natural gas production technology have led to lower prices for methane and renewed interest in converting methane to higher value products Processes such as those based on syngas from methane reforming are being investigated Another option is methane aromatization, which produces benzene and hydrogen: 6CH4(g) → C6H6(g) + 9H2(g) ΔGor = +433 kJ mol−1 ΔHor = +531 kJ mol−1 Thermodynamic calculations for this reaction show that benzene formation is insignificant below ∼600 °C, and that the formation of solid carbon [C(s)] is thermodynamically favored at temperatures above ∼300 °C Benzene formation is insignificant at all temperatures up to 1000 °C when C(s) is included in the calculation of equilibrium composition Interestingly, the thermodynamic limitation on benzene formation can be minimized by the addition of alkanes/alkenes to the methane feed By far the most widely studied catalysts for this reaction are Mo/HZSM-5 and Mo/MCM-22 Benzene selectivities are generally between 60 and 80% at methane conversions of ∼10%, corresponding to net benzene yields of less than 10% Major byproducts include lower molecular weight hydrocarbons and higher molecular weight substituted aromatics However, carbon formation is inevitable, but the experimental findings show this can be kinetically limited by the use of H2 or oxidants in the feed, including CO2 or steam A number of reactor configurations involving regeneration of the carbon-containing catalyst have been developed with the goal of minimizing the cost of regeneration of the catalyst once deactivated by carbon deposition In this tutorial review we discuss the thermodynamics of this process, the catalysts used and the potential reactor configurations that can be applied

Toward a better understanding and quantification of methane emissions from shale gas development

Abstract: The identification and quantification of methane emissions from natural gas production has become increasingly important owing to the increase in the natural gas component of the energy sector. An instrumented aircraft platform was used to identify large sources of methane and quantify emission rates in southwestern PA in June 2012. A large regional flux, 2.0–14 g CH4 s−1 km−2, was quantified for a ∼2,800-km2 area, which did not differ statistically from a bottom-up inventory, 2.3–4.6 g CH4 s−1 km−2. Large emissions averaging 34 g CH4/s per well were observed from seven well pads determined to be in the drilling phase, 2 to 3 orders of magnitude greater than US Environmental Protection Agency estimates for this operational phase. The emissions from these well pads, representing ∼1% of the total number of wells, account for 4–30% of the observed regional flux. More work is needed to determine all of the sources of methane emissions from natural gas production, to ascertain why these emissions occur and to evaluate their climate and atmospheric chemistry impacts.

Ebullition and storm-induced methane release from the East Siberian Arctic Shelf

Abstract: Vast quantities of carbon are stored in shallow Arctic reservoirs, such as submarine and terrestrial permafrost. Submarine permafrost on the East Siberian Arctic Shelf started warming in the early Holocene, several thousand years ago. However, the present state of the permafrost in this region is uncertain. Here, we present data on the temperature of submarine permafrost on the East Siberian Arctic Shelf using measurements collected from a sediment core, together with sonar-derived observations of bubble flux and measurements of seawater methane levels taken from the same region. The temperature of the sediment core ranged from -1.8 to 0 degrees C. Although the surface layer exhibited the lowest temperatures, it was entirely unfrozen, owing to significant concentrations of salt. On the basis of the sonar data, we estimate that bubbles escaping the partially thawed permafrost inject 100-630 mg methane m(-2) d(-1) into the overlying water column. We further show that water-column methane levels had dropped significantly following the passage of two storms. We suggest that significant quantities of methane are escaping the East Siberian Shelf as a result of the degradation of submarine permafrost over thousands of years. We suggest that bubbles and storms facilitate the flux of this methane to the overlying ocean and atmosphere, respectively.

Fuel from Water: The Photochemical Generation of Hydrogen from Water

Abstract: ConspectusHydrogen has been labeled the fuel of the future since it contains no carbon, has the highest specific enthalpy of combustion of any chemical fuel, yields only water upon complete oxidation, and is not limited by Carnot considerations in the amount of work obtained when used in a fuel cell. To be used on the scale needed for sustainable growth on a global scale, hydrogen must be produced by the light-driven splitting of water into its elements, as opposed to reforming of methane, as is currently done. The photochemical generation of H2, which is the reductive side of the water splitting reaction, is the focus of this Account, particularly with regard to work done in the senior author’s laboratory over the last 5 years. Despite seminal work done more than 30 years ago and the extensive research conducted since then on all aspects of the process, no viable system has been developed for the efficient and robust photogeneration of H2 from water using only earth abundant elements. For the photogenera...

Pyrolysis of Cellulose under Ammonia Leads to Nitrogen-Doped Nanoporous Carbon Generated through Methane Formation

Abstract: Here, we present a simple one-step fabrication methodology for nitrogen-doped (N-doped) nanoporous carbon membranes via annealing cellulose filter paper under NH3. We found that nitrogen doping (up to 10.3 at %) occurs during cellulose pyrolysis under NH3 at as low as 550 °C. At 700 °C or above, N-doped carbon further reacts with NH3, resulting in a large surface area (up to 1973.3 m2/g). We discovered that the doped nitrogen, in fact, plays an important role in the reaction, leading to carbon gasification. CH4 was experimentally detected by mass spectrometry as a product in the reaction between N-doped carbon and NH3. When compared to conventional activated carbon (1533.6 m2/g), the N-doped nanoporous carbon (1326.5 m2/g) exhibits more than double the unit area capacitance (90 vs 41 mF/m2).

Methane yield phenotypes linked to differential gene expression in the sheep rumen microbiome

Abstract: Ruminant livestock represent the single largest anthropogenic source of the potent greenhouse gas methane, which is generated by methanogenic archaea residing in ruminant digestive tracts. While differences between individual animals of the same breed in the amount of methane produced have been observed, the basis for this variation remains to be elucidated. To explore the mechanistic basis of this methane production, we measured methane yields from 22 sheep, which revealed that methane yields are a reproducible, quantitative trait. Deep metagenomic and metatranscriptomic sequencing demonstrated a similar abundance of methanogens and methanogenesis pathway genes in high and low methane emitters. However, transcription of methanogenesis pathway genes was substantially increased in sheep with high methane yields. These results identify a discrete set of rumen methanogens whose methanogenesis pathway transcription profiles correlate with methane yields and provide new targets for CH4 mitigation at the levels of microbiota composition and transcriptional regulation.

Copper(I)-Catalyzed Synthesis of Nanoporous Azo-Linked Polymers: Impact of Textural Properties on Gas Storage and Selective Carbon Dioxide Capture

Abstract: A new facile method for synthesis of porous azo-linked polymers (ALPs) is reported. The synthesis of ALPs was accomplished by homocoupling of aniline-like building units in the presence of copper(I) bromide and pyridine. The resulting ALPs exhibit high surface areas (SABET = 862–1235 m2 g–1), high physiochemical stability, and considerable gas storage capacity especially at high-pressure settings. Under low pressure conditions, ALPs have remarkable CO2 uptake (up to 5.37 mmol g–1 at 273 K and 1 bar), as well as moderate CO2/N2 (29–43) and CO2/CH4 (6–8) selectivity. Low pressure gas uptake experiments were used to calculate the binding affinities of small gas molecules and revealed that ALPs have high heats of adsorption for hydrogen (7.5–8 kJ mol–1), methane (18–21 kJ mol–1), and carbon dioxide (28–30 kJ mol–1). Under high pressure conditions, the best performing polymer, ALP-1, stores significant amounts of H2 (24 g L–1, 77 K/70 bar), CH4 (67 g L–1, 298 K/70 bar), and CO2 (304 g L–1, 298 K/40 bar).

Methanation of CO2 - storage of renewable energy in a gas distribution system

Abstract: This article presents some crucial findings of the joint research project entitled «Storage of electric energy from renewable sources in the natural gas grid-water electrolysis and synthesis of gas components». The project was funded by BMBF and aimed at developing viable concepts for the storage of excess electrical energy from wind and solar power plants. The concept presented in this article suggests the conversion of CO2-containing gases into methane in a pressurized reactor using hydrogen produced via electrolysis. The produced gas can be upgraded to synthetic natural gas (SNG) and fed into the well-developed German natural gas grid. This concept benefits from the high storage capacity of the German gas grid and does not require any extensions of the current gas or power grid. The reaction heat released by the exothermic methanation reaction leads to a temperature rise of the gas in the fixed bed catalyst of the reactor. The conversion of carbon dioxide is limited in accordance to the chemical equilibrium which depends strongly on temperature and pressure. For maximum carbon dioxide conversion, it is convenient to split the methanation into several stages adding cooling sections in between. This article focuses on the methanation process and its transfer onto an industrial scale evaluating the different plant capacities and feedstock mixtures used. The methanation takes place in a staged fixed bed reactor. This staged reactor concept is an in-house development based on know-how from the sulfuric acid production technology.

Rethinking biological activation of methane and conversion to liquid fuels

Abstract: Methane is an energy resource that is currently being wasted through emissions, venting and flaring during petroleum extraction. Recent discoveries regarding the basis of enzyme function and microbial metabolism provide the foundation for new thinking about how to reclaim this resource through bioconversion. If methane, the main component of natural gas, can be efficiently converted to liquid fuels, world reserves of methane could satisfy the demand for transportation fuels in addition to use in other sectors. However, the direct activation of strong C-H bonds in methane and conversion to desired products remains a difficult technological challenge. This perspective reveals an opportunity to rethink the logic of biological methane activation and conversion to liquid fuels. We formulate a vision for a new foundation for methane bioconversion and suggest paths to develop technologies for the production of liquid transportation fuels from methane at high carbon yield and high energy efficiency and with low CO2 emissions. These technologies could support natural gas bioconversion facilities with a low capital cost and at small scales, which in turn could monetize the use of natural gas resources that are frequently flared, vented or emitted.