Showing papers on "Methane published in 2021"

A review on ammonia, ammonia-hydrogen and ammonia-methane fuels

Abstract: Combustion of fuels to generate energy is integral to various human activities, both domestic and industrial. However, the predominance of hydrocarbon fuel usage produces emissions containing pollutants that cause multiple environmental complications and risks to human health. Therefore, replacement of conventional fuels to achieve zero carbon emission is of utmost importance. In terms of carbon-free fuel, ammonia offers several advantages over hydrogen. However, its low burning velocity and high fuel NOx emissions inhibit large-scale usage. Hence, hydrogen and methane have been studied in this review as possible secondary fuels to aid ammonia combustion and address the aforementioned issues. This review starts from the suitability of ammonia fuel as energy vector in terms of physicochemical and combustion characteristics, moving through the kinetics and mechanisms of ammonia-based and ammonia-fuel combustion. The impacts and limitations of each system are also addressed, thus providing a comparison on each system. Particularly, this review assesses and discusses the advantages and mechanisms involved with secondary fuel addition to the ammonia combustion, presenting the role of key reaction differences and the change in key reaction mechanism under different conditions at the level of reaction mechanisms. Finally, this review covers future perspectives and challenges on the usage and development of ammonia-based fuels, emphasizing the maturity of ammonia-based and ammonia-fuel combustion kinetics. Herein, this work summarizes the principles of the combustion reactions of ammonia-based and ammonia-fuel systematically and serves as a theoretical reference of ammonia-fuel combustion kinetics for transitioning into future practical applications where ammonia is an important energy vector.

Half of global methane emissions come from highly variable aquatic ecosystem sources

Abstract: Atmospheric methane is a potent greenhouse gas that plays a major role in controlling the Earth’s climate The causes of the renewed increase of methane concentration since 2007 are uncertain given the multiple sources and complex biogeochemistry Here, we present a metadata analysis of methane fluxes from all major natural, impacted and human-made aquatic ecosystems Our revised bottom-up global aquatic methane emissions combine diffusive, ebullitive and/or plant-mediated fluxes from 15 aquatic ecosystems We emphasize the high variability of methane fluxes within and between aquatic ecosystems and a positively skewed distribution of empirical data, making global estimates sensitive to statistical assumptions and sampling design We find aquatic ecosystems contribute (median) 41% or (mean) 53% of total global methane emissions from anthropogenic and natural sources We show that methane emissions increase from natural to impacted aquatic ecosystems and from coastal to freshwater ecosystems We argue that aquatic emissions will probably increase due to urbanization, eutrophication and positive climate feedbacks and suggest changes in land-use management as potential mitigation strategies to reduce aquatic methane emissions Methane emissions from aquatic systems contribute approximately half of global methane emissions, according to meta-analysis of natural, impacted and human-made aquatic ecosystems and indicating potential mitigation strategies to reduce emissions

A review of recent efforts to promote dry reforming of methane (DRM) to syngas production via bimetallic catalyst formulations

Abstract: Dry (CO2) reforming of methane (DRM) for syngas production, a critical feedstock for the production of hydrogen, ammonia, and Fischer-Tropsch derived liquid energy carriers, unequivocally ranks among the top issues of applied catalysis in the light of environmental protection, renewable energy production and circular economy. This mainly because DRM involves the simultaneous reduction of two key greenhouse gases (CO2 and CH4) and provides an efficient way for CO2 utilization/recycling and the direct implementation of biogas. The same advantages make DRM a more favorable process compared to steam- or oxi- reforming ones. The design of cost-effective, efficient and robust (coking- and sintering-resistant) DRM catalysts is a grand challenge in the topic. Bimetallic catalysts, providing synergistic effects via metal-to-metal interactions seem to be an effective strategy for achieving these goals. A review of the recent literature achievements on DRM using bimetallic catalyst formulations is provided herein in a comprehensive and comparative manner.

Selective capture of carbon dioxide from hydrocarbons using a metal-organic framework.

Abstract: Efficient and sustainable methods for carbon dioxide capture are highly sought after. Mature technologies involve chemical reactions that absorb CO2, but they have many drawbacks. Energy-efficient alternatives may be realised by porous physisorbents with void spaces that are complementary in size and electrostatic potential to molecular CO2. Here, we present a robust, recyclable and inexpensive adsorbent termed MUF-16. This metal-organic framework captures CO2 with a high affinity in its one-dimensional channels, as determined by adsorption isotherms, X-ray crystallography and density-functional theory calculations. Its low affinity for other competing gases delivers high selectivity for the adsorption of CO2 over methane, acetylene, ethylene, ethane, propylene and propane. For equimolar mixtures of CO2/CH4 and CO2/C2H2, the selectivity is 6690 and 510, respectively. Breakthrough gas separations under dynamic conditions benefit from short time lags in the elution of the weakly-adsorbed component to deliver high-purity hydrocarbon products, including pure methane and acetylene.

Self-assembled iron-containing mordenite monolith for carbon dioxide sieving

Abstract: The development of low-cost, efficient physisorbents is essential for gas adsorption and separation; however, the intrinsic tradeoff between capacity and selectivity, as well as the unavoidable shaping procedures of conventional powder sorbents, greatly limits their practical separation efficiency. Herein, an exceedingly stable iron-containing mordenite zeolite monolith with a pore system of precisely narrowed microchannels was self-assembled using a one-pot template- and binder-free process. Iron-containing mordenite monoliths that could be used directly for industrial application afforded record-high volumetric carbon dioxide uptakes (293 and 219 cubic centimeters of carbon dioxide per cubic centimeter of material at 273 and 298 K, respectively, at 1 bar pressure); excellent size-exclusive molecular sieving of carbon dioxide over argon, nitrogen, and methane; stable recyclability; and good moisture resistance capability. Column breakthrough experiments and process simulation further visualized the high separation efficiency.

Water enables mild oxidation of methane to methanol on gold single-atom catalysts.

Abstract: As a 100% atom-economy process, direct oxidation of methane into methanol remains as a grand challenge due to the dilemma between activation of methane and over-oxidation of methanol. Here, we report that water enabled mild oxidation of methane into methanol with >99% selectivity over Au single atoms on black phosphorus (Au1/BP) nanosheets under light irradiation. The mass activity of Au1/BP nanosheets reached 113.5 μmol gcatal−1 in water pressured with 33 bar of mixed gas (CH4:O2 = 10:1) at 90 °C under light irradiation (1.2 W), while the activation energy was 43.4 kJ mol−1. Mechanistic studies revealed that water assisted the activation of O2 to generate reactive hydroxyl groups and •OH radicals under light irradiation. Hydroxyl groups reacted with methane at Au single atoms to form water and CH3* species, followed by oxidation of CH3* via •OH radicals into methanol. Considering the recycling of water during the whole process, we can also regard water as a catalyst. It is important but challenging to oxidize methane by O2 into methanol under ambient conditions. Here, the authors achieved mild oxidation of methane into methanol over Au single atoms on black phosphorus nanosheets with the help of water under light irradiation.

Selective photocatalytic oxidation of methane by quantum-sized bismuth vanadate

Abstract: The direct oxidation of methane to more desirable, one-carbon oxygenated molecules such as methanol and formaldehyde offers a pathway towards a more sustainable chemical industry as the current commercial reforming process involving two steps features a high carbon footprint and energy consumption. Here, we report the selective photocatalytic oxidation of methane at room temperature using quantum-sized bismuth vanadate nanoparticles as the catalyst and oxygen as a mild oxidant. The reaction offers a high selectivity, of 96.6% for methanol or 86.7% for formaldehyde, under optimum wavelength and intensity of light, reaction time and amount of water solvent. Comprehensive characterizations disclose a multistep reaction mechanism in which the activation of methane by the hydroxyl radical determines the reaction rate. This work broadens the avenue towards the selective conversion of the greenhouse gas methane into desirable chemical products in a sustainable way. The conversion of methane to target one-carbon oxygenates relies on a two-step process that is carbon and energy intensive. Direct oxidation offers a sustainable alternative pathway. Here, the authors report on the selective photocatalytic oxidation of methane at room temperature using bismuth vanadate catalyst, realizing high methanol and formaldehyde selectivity.

Recent trends in developments of active metals and heterogenous materials for catalytic CO2 hydrogenation to renewable methane: A review

Abstract: Carbon dioxide is a greenhouse gas that is abundantly found in the atmosphere. Therefore, by utilizing carbon dioxide to produce methane would not only reduce the concentration of greenhouse gas in the atmosphere but would also be able to partially fulfill the energy demand. This review highlights current trends in various active metals and heterogeneous catalyst supports used for thermal hydrogenation of CO2 to methane. Initially, the fundamentals, challenges and thermodynamic analysis are discussed to understand the limitations as well as the nature and thermodynamics of the possible reactions. In the mainstream, various classification of active metals, heterogeneous supports and structured materials with their role in selective methane production are discussed. In addition, various operating parameters, engineering aspects, morphologies and physiochemical properties have been thoroughly discussed on the catalytic performance and stability for the methanation reaction. The active metals as well as structure of catalyst have been reported to reduce the activation energy for the CO2 methanation, which is highly beneficial for the progression of the hydrogenation reaction. Finally, the mechanism of the hydrogenation reaction was also reviewed to determine its relationship with the catalyst active site structures.

NixAl1O2-δ mesoporous catalysts for dry reforming of methane: The special role of NiAl2O4 spinel phase and its reaction mechanism

Abstract: The structure evolution of surface NiAl2O4 spinel phase in NixAl1O2-δ mesoporous catalysts, synthesized by the citric acid sol-gel method, was systematically investigated. Small-size Ni nanoparticles, obtained by partial reduction from NiAl2O4 spinel in NixAl1O2-δ catalysts with low Ni contents at high temperature, can effectively inhibit the carbon formation from kinetics, while the irreducible NiAl2O4 counterpart can participate in elimination of carbon deposition. The constructed structure of Ni0-NiAl2O4 interfaces, produced by exsolution of Ni from NiAl2O4 spinel, is responsible for its high long-term stability and excellent resistance to coking and sintering for dry reforming of methane (DRM) reaction. The structure sensitivity and kinetic compensation effect of CH4 dissociation on Ni0 active sites are observed. DRM reaction proceeds via a Langmuir-Hinshelwood mechanism accompanied by an additional redox mechanism. It is noteworthy that the active oxygen species generated by filling the oxygen vacancies of NiAl2O4 spinel by CO2 provide another rapid redox route to eliminate carbon species.

Five carbon- and nitrogen-bearing species in a hot giant planet's atmosphere.

Abstract: The atmospheres of gaseous giant exoplanets orbiting close to their parent stars (hot Jupiters) have been probed for nearly two decades1,2. They allow us to investigate the chemical and physical properties of planetary atmospheres under extreme irradiation conditions3. Previous observations of hot Jupiters as they transit in front of their host stars have revealed the frequent presence of water vapour4 and carbon monoxide5 in their atmospheres; this has been studied in terms of scaled solar composition6 under the usual assumption of chemical equilibrium. Both molecules as well as hydrogen cyanide were found in the atmosphere of HD 209458b5,7,8, a well studied hot Jupiter (with equilibrium temperature around 1,500 kelvin), whereas ammonia was tentatively detected there9 and subsequently refuted10. Here we report observations of HD 209458b that indicate the presence of water (H2O), carbon monoxide (CO), hydrogen cyanide (HCN), methane (CH4), ammonia (NH3) and acetylene (C2H2), with statistical significance of 5.3 to 9.9 standard deviations per molecule. Atmospheric models in radiative and chemical equilibrium that account for the detected species indicate a carbon-rich chemistry with a carbon-to-oxygen ratio close to or greater than 1, higher than the solar value (0.55). According to existing models relating the atmospheric chemistry to planet formation and migration scenarios3,11,12, this would suggest that HD 209458b formed far from its present location and subsequently migrated inwards11,13. Other hot Jupiters may also show a richer chemistry than has been previously found, which would bring into question the frequently made assumption that they have solar-like and oxygen-rich compositions. The signatures of water, carbon monoxide, hydrogen cyanide, methane, ammonia and acetylene are observed in the transmission spectrum of the hot Jupiter HD 209458b, with abundance ratios suggesting a super-solar carbon-to-oxygen ratio.

Low coordination number copper catalysts for electrochemical CO2 methanation in a membrane electrode assembly.

Abstract: The electrochemical conversion of CO2 to methane provides a means to store intermittent renewable electricity in the form of a carbon-neutral hydrocarbon fuel that benefits from an established global distribution network. The stability and selectivity of reported approaches reside below technoeconomic-related requirements. Membrane electrode assembly-based reactors offer a known path to stability; however, highly alkaline conditions on the cathode favour C-C coupling and multi-carbon products. In computational studies herein, we find that copper in a low coordination number favours methane even under highly alkaline conditions. Experimentally, we develop a carbon nanoparticle moderator strategy that confines a copper-complex catalyst when employed in a membrane electrode assembly. In-situ XAS measurements confirm that increased carbon nanoparticle loadings can reduce the metallic copper coordination number. At a copper coordination number of 4.2 we demonstrate a CO2-to-methane selectivity of 62%, a methane partial current density of 136 mA cm−2, and > 110 hours of stable operation. Electrochemical conversion of carbon dioxide to methane can store intermittent renewable electricity in a staple of global energy. Here, the authors develop a moderator strategy to maintain the catalyst in a low coordination state, thereby enabling stable and selective electrochemical methanation.

Effective radiative forcing from emissions of reactive gases and aerosols – a multi-model comparison

Abstract: . This paper quantifies the effective radiative forcing from CMIP6 models of the present-day anthropogenic emissions of NOx, CO, VOCs, SO2, NH3, black carbon and primary organic carbon. Effective radiative forcing from pre-industrial to present-day changes in the concentrations of methane, N2O and halocarbons are quantified and attributed to their anthropogenic emissions. Emissions of reactive species can cause multiple changes in the composition of radiatively active species: tropospheric ozone, stratospheric ozone, secondary inorganic and organic aerosol and methane. We therefore break down the ERFs from each emitted species into the contributions from the composition changes. The 1850 to 2014 mean ERFs are 1.1 ± 0.07 W m−2 for sulfate, −0.24 ± 0.01 W m−2 for organic carbon (OC), and 0.15 ± 0.04 W m−2 for black carbon (BC), and for the aerosols combined it is −0.95 ± 0.03 W m−2. The means for the reactive gases are 0.69 ± 0.04 W m−2 for methane (CH4), 0.06 ± 0.04 W m−2 for NOx, −0.09 ± 0.03 W m−2 for volatile organic carbons (VOC), 0.16 ± 0.03 W m−2 for ozone (O3), 0.27 W m−2 for nitrous oxide (N2O) and −0.02 ± 0.06 W m−2 for hydrocarbon (HC). Differences in ERFs calculated for the different models reflect differences in the complexity of their aerosol and chemistry schemes, especially in the case of methane where tropospheric chemistry captures increased forcing from ozone production.

Methane Cracking for Hydrogen Production: A Review of Catalytic and Molten Media Pyrolysis

Abstract: Currently, hydrogen is mainly generated by steam methane reforming, with significant CO2 emissions, thus exacerbating the greenhouse effect. This environmental concern promotes methane cracking, which represents one of the most promising alternatives for hydrogen production with theoretical zero CO/CO2 emissions. Methane cracking has been intensively investigated using metallic and carbonaceous catalysts. Recently, research has focused on methane pyrolysis in molten metals/salts to prevent both reactor coking and rapid catalyst deactivation frequently encountered in conventional pyrolysis. Another expected advantage is the heat transfer improvement due to the high heat capacity of molten media. Apart from the reaction itself that produces hydrogen and solid carbon, the energy source used in this endothermic process can also contribute to reducing environmental impacts. While most researchers used nonrenewable sources based on fossil fuel combustion or electrical heating, concentrated solar energy has not been thoroughly investigated, to date, for pyrolysis in molten media. However, it could be a promising innovative pathway to further improve hydrogen production sustainability from methane cracking. After recalling the basics of conventional catalytic methane cracking and the developed solar cracking reactors, this review delves into the most significant results of the state-of-the-art methane pyrolysis in melts (molten metals and salts) to show the advantages and the perspectives of this new path, as well as the carbon products’ characteristics and the main factors governing methane conversion.

Insights into the Nonthermal Effects of Light in Dry Reforming of Methane to Enhance the H2/CO Ratio Near Unity over Ni/Ga2O3

Abstract: Photothermal catalysis, which couples both solar and thermal energies, has burgeoned as a promising approach to drive catalytic reactions. However, the utilization of light irradiation to tune the ...

Undrained triaxial tests on water-saturated methane hydrate–bearing clayey-silty sediments of the South China Sea

Abstract: Approximately 90% of gas hydrates are buried in fine-grained sediments, especially in the South China Sea. The potential instability of fine-grained sediments induced by hydrate dissociation requir...

Ni/SiO2 Catalyst Prepared by Strong Electrostatic Adsorption for a Low-Temperature Methane Dry Reforming Reaction

Abstract: Low-temperature methane dry reforming (MDR) over supported Ni catalysts is a more economical way to convert greenhouse gases than high-temperature MDR. However, sintering from Ni aggregation and ca...

Experimental investigation on ammonia combustion behavior in a spark-ignition engine by means of laminar and turbulent expanding flames

Abstract: Ammonia combustion appears as a meaningful way to retrieve stored amounts of excess variable renewable energy, and the spark-ignition (SI) engine has been proposed as a practical conversion system. The present work aims at elucidating the combustion characteristics of ammonia blends in engine-relevant turbulent conditions. To that end, laminar and turbulent flame experiments were conducted in a constant-volume vessel at engine-relevant conditions of 445 K and 0.54 MPa to assess the combustion behavior of ammonia/hydrogen/air, ammonia/methane/air and methane/hydrogen/air mixtures observed in an all-metal single-cylinder SI engine. Results show that the respective accelerating or decelerating effects of hydrogen or methane enrichment observed in the SI engine could not be sufficiently explained by the measured laminar burning velocities of the mixtures. Since the latter are very low, the studied combustion regimes are at the boundary between the thin and broken reaction zones regimes, and thus strongly influenced by flame-turbulence interactions. The quantification of the flame response to turbulence shows much higher effects for ammonia blends, than for methane-based fuels. The aforementioned opposite effects of ammonia enrichment with hydrogen or methane are observed on the turbulent burning velocity during the turbulent flame experiments and correlated to the thermochemical properties of the reactants and the flame sensitivity to stretch. The latter may explain an unexpected bending effect on the turbulent-to-laminar velocity ratio when increasing the hydrogen fraction in the ammonia/hydrogen blend. Nevertheless, a very good correlation of the turbulent velocity was found with the Karlovitz and Damkohler numbers, that suggests that ammonia combustion in SI engines may be described following the usual turbulent combustion models. This encourages further investigations on ammonia combustion for the optimization of practical systems, by means of dedicated experiments and numerical simulations.

A promising plasma-catalytic approach towards single-step methane conversion to oxygenates at room temperature

Abstract: Direct conversion of methane into chemicals and fuels under mild conditions has been considered as a ‘holy grail’ of chemistry and catalysis in the 21st century. Plasma-catalytic partial oxidation of methane (POM) to higher-value liquid fuels and chemicals over supported transition metal catalysts (Ni/γ-Al2O3, Cu/γ-Al2O3 and Fe/γ-Al2O3) has been investigated in a co-axial dielectric barrier discharge (DBD) reactor at room temperature and atmospheric pressure. The selectivity of oxygenates was 58.3% in the plasma POM reaction without a catalyst, while the combination of DBD with the catalysts enhanced the selectivity of oxygenates up to 71.5%. Of the three catalysts, Fe/γ-Al2O3 showed the highest methanol selectivity of 36.0% and a significant methanol yield of 4.7%, while the use of Cu/γ-Al2O3 improved the selectivity of C2 oxygenates to 9.4%, which can be attributed to the presence of more acid sites on the surfaces of the Cu catalyst. The possible reaction pathways in the plasma-catalytic POM reaction have been explored by combined means of plasma electrical and optical diagnostics, analysis of gas and liquid products, as well as comprehensive catalyst characterization. The plausible reaction routes for the production of major oxygenate (methanol) on the Fe/γ-Al2O3 surfaces have been proposed. The surface CHx species are found to be critical for methanol synthesis; they can be formed through the direct adsorption of CHx radicals generated in the plasma gas-phase reactions or through the dissociation of adsorbed CH4 on the catalyst surface.